RESIN COMPOSITION, METHOD TO IMPROVE THE ADHESION OF SUCH RESIN COMPOSITION AND USE OF AT LEAST ONE

专利摘要:
adhesion promoters and gel modifiers for olefin metathesis compositions this invention relates to compositions and methods for improving adhesion of resin compositions to substrate materials, pretreatment of substrate materials to improve adhesion of resin compositions for substrate materials, and/or which control gel formation of resin compositions. more particularly, the invention relates to compositions and methods for improving the adhesion of ring-opening (romp) metathesis polymerization compositions to substrate materials with the use of adhesion promoters containing isocyanate groups in a resin composition. the invention also relates to methods for improving adhesion of resin compositions to substrate materials by pre-treating substrate materials with adhesion promoters containing isocyanate groups. The invention further relates to a method of providing a gel-modified rupture composition, wherein a hydroperoxide is added to a rupture polymerizable resin composition to control gel formation of the polymerization resin. an improved disruption composition is further described, comprising a cyclic olefin, a disruption metathesis catalyst, an adhesion promoter and an added hydroperoxide gel modifier. the polymer products produced by the disruption reactions of the invention can be used for a wide variety of materials and composite applications. the invention has utility in the field of catalysis, organic synthesis, and polymer and chemistry and materials fabrication.
公开号:BR112013032369B1
申请号:R112013032369-8
申请日:2012-06-17
公开日:2021-08-24
发明作者:Li-Sheng Wang；Anthony R. Stephen；Paul W. Boothe；Tessa Schulze；Michael A. Giardello；Mark S. Trimmer；Christopher J. Cruce；Farshad J. Motamedi；Brian Edgecombe
申请人:Materia, Inc；
IPC主号:

专利说明:

RELATED ORDERS
[001] This application claims the benefit of U.S. Provisional Patent Application No. 61/498,528, filed June 17, 2011, and U.S. Provisional Patent Application No. 61/654,744, filed June 1, 2012, and the contents of each being incorporated herein by reference. TECHNICAL FIELD
[002] The present invention relates to methods and compositions to improve the adhesion of olefin metathesis compositions to substrate materials, and to catalyze olefin metathesis and control reactions. More particularly, the invention relates to methods and compositions for improving adhesion of ring opening metathesis polymerization (ROMP) compositions to substrate materials, and for catalyzing and controlling ROMP reactions and the fabrication of polymer articles by means of ROMP. Polymer products produced through the metathesis reactions of the invention can be used for a wide variety of materials and composite applications. The invention has utility in the field of catalysis, organic synthesis, and polymers and materials chemistry and fabrication. BACKGROUND
[003] Polymer matrix composites offer unique combinations of properties and are useful in a wide range of applications. Such composites can be manufactured using thermosetting polymer matrix materials or thermoplastics with a variety of particulates and fillers or fibrous reinforcements. It is generally advantageous to have strong adhesion between the polymer matrix material and the surfaces of the various particulates or fibrous substrates, and there is considerable technique relating to substrate finishes and other treatments to optimize adhesion to polymer matrices. For example, in the production of long fiber reinforced composites, an improved adhesion between the polymer matrix and the fiber reinforcement leads to an increase in material performance. Good adhesion is particularly important when failures are likely to occur in delamination or other adhesive failure modes.
[004] As described, for example, in U.S. Patents Nos. 5,840,238, 6,310,121, and 6,525,125, the disclosures of each of which being incorporated herein by reference, polymers generated by olefin metathesis processes are attractive as composite matrix materials. Of particularly beneficial use are ROMP generated polymers of cyclic olefins. The low viscosity of cyclic olefin resin formulations and the ability to control ROMP kinetics (eg, US Patent Nos. 4,708,969 and 5,939,504, the disclosures of both of which are incorporated herein by reference) facilitate the composite processing and fabrication, and the corrosion resistance and high toughness of ROMP polymers lead to good composite durability. In addition, certain properties of ROMP polymers, eg mechanical strength and stiffness, heat distortion temperature and solvent resistance can be further improved by crosslinking induced by means of heat treatment (eg, US Patent No. 4,902 560, the disclosure of which being incorporated herein by reference) or chemically by the addition of peroxides (e.g., US Patent No. 5,728,785, the disclosure of which is being incorporated herein by reference).
[005] Commercially important ROMP resin formulations are generally based on readily available and inexpensive cyclic olefins such as dicyclopentadiene (DCPD), norbornenes, cyclooctadiene (COD), and various cycloalkenes. However, in contrast to traditional resin systems (eg epoxy, acrylate, urethane, resins and polyester) based on polar functional group chemistry, these non-polar ROMP resins have poor intrinsic adhesion to surfaces. relatively polar of common carbon, glass, or mineral fillers and reinforcements. The addition of various silanes to such resin formulations to improve the electrical and mechanical properties of ROMP polymers is described in U.S. 5,840,238, 6,001,909, and 7,339,006, the disclosures of each of which are incorporated herein by reference. Many widely used commercial silanes do not generate optimal properties with ROMP polymers, however, and the greatest improvements are only obtained when the silanes comprise groups with high metathesis activity (the relative reactivity of various metathesis active groups is described in J. Am. Chem. Soc., 2003, 125, 11360-11370).
[006] ROMP-generated polymers are particularly well suited for casting molded parts and infusing glass-resin and wood-resin composites, as non-limiting examples. According to a process of the method, the cyclic olefin monomer is mixed with suitable additives and fillers and then mixed with an olefin metathesis catalyst. The starting resin mixture is typically a low viscosity liquid, which allows for a wide variety of resin infusion and casting techniques. As polymerization proceeds, the resin first “gels” (increase in viscosity such that it no longer flows freely) and then “cures” as the resin reaches peak monomer conversion. The gel rate and cure kinetics of olefin metathesis polymerizations are dependent on the monomer, catalyst, and temperature.
[007] When manufacturing the articles using olefin metathesis polymerization, any casting or infusion of catalyzed resin must be completed before the resin viscosity increases to the point that the resin no longer flows to fill the mold in accordance with the manufacturing conditions. The infusion or leakage of highly viscous (pre-gelled) or gelled resin can lead to the inclusion of trapped air, or produce other defects or conditions that diminish the mechanical properties or visual appearance of the manufactured part. It would therefore be desirable to control the gel formation process, in particular to delay the onset of viscosity build and the onset of resin curing and gelling states, through the use of a gel modifying agent. Once casting or infusion is complete, it would be more advantageous for polymerization to commence within a reasonable time after the mold is filled, and proceed at a desirable cure rate.
[008] The time during which the catalyst/liquid monomer mixture can be worked after the catalyst and monomer are mixed is called "mix use time" (pot life) of the polymerization reaction mixture. The ability to control "mix wear time" becomes even more important for molding large parts and achieving defect-free infusion of porous materials. It would be particularly useful to be able to control the gel formation process, especially the onset of gel state, of catalyzed ROMP reactions when such large pieces must be produced, or when defects resulting from accumulated viscosity must be reduced or eliminated.
[009] Certain limited types of gel modifying agents for olefin metathesis polymerizations have been disclosed. For example, U.S. Patent No. 5,939,504 discloses the use of phosphines, pyridines, and other Lewis bases as gel modifiers. While useful, the effect of such gel modifiers on ROMP reactions can be difficult to control, particularly where relatively small variations at the start of polymerization are desired. For example, despite the addition of small amounts of tributylphosphine, a commercially attractive additive due to its low cost, it cannot produce any noticeable change in the use time of the mixture, the addition of a slightly larger amount can overcome the desired effect through creating a significantly longer delay in starting polymerization than desired. From a practical perspective, the inability to finely control the gel formation process makes these gel modifiers less useful in manufacturing large and variable sized articles. Certain gel modifiers, such as phosphines, also rapidly oxidize in the resin, thus decreasing the modifier's ability to extend storage life. Resin compositions which are based on phosphine compounds for gel modification, therefore, cannot be stored for an appreciable long time without reformulation with fresh gel modification additive.
[010] Despite acting as activators in some systems (eg, US Patent Nos. 4,380,617 and 4,049,616), compounds containing active oxygen, including hydroperoxides, are generally considered to have a negative impact on the metathesis catalyst performance. Olefins intended for use in metathesis reactions are often chemically treated (eg, US Patent No. 5,378,783.) or pretreated with an adsorbent such as alumina or zeolites (eg, US Patent No. 7,700 .698; 4,943,397; and 4,584,425) to reduce the concentration of oxygen-containing impurities such as hydroperoxides. For example, U.S. Patent No. 4,584,425 shows that hydroperoxide compounds have a significant negative impact on DCPD ROMP with two pieces of tungsten metathesis catalyst and U.S. Patent No. 4,584,425. 7,576,227 teaches that it is advantageous to remove hydroperoxides and other catalyst poisons to improve the cross-metathesis turnover number when using ruthenium alkylidene catalysts.
[011] Hydroperoxide additives have been suggested as post-polymerization radical crosslinking initiators for ROMP polymers (eg, U.S. Patent Nos. 7,025,851 and 7,476,716). However, U.S. Patent No. 5,728,785 specifically shows that dicyclopentadiene ROMP fails in the presence of 1% by weight (relative to dicyclopentadiene) of tert-butyl hydroperoxide, a level typically useful for effecting post-polymerization crosslinking. Others teach that additives used in ROMP formulations should not contain hydroperoxide functionalities in order to avoid adverse interactions with metathesis catalysts (eg, US Patent Nos. 6,323,296 and 6,890,650, the disclosures of which are hereby incorporated by reference).
[012] Despite advances made in the art, particularly in the properties of olefin metathesis polymers and their associated applications, there is a continuing need for further improvements in a number of areas, including the adhesion of olefin metathesis compositions, in particular, ROMP compositions, for substrate materials, especially the wide variety of existing substrate materials that have been used with traditional resin systems, and the use of certain gel modifiers to control the gel formation process of polymerization ROMP compositions . SUMMARY OF THE INVENTION
[013] The invention is directed to addressing one or more of the above-mentioned problems and relates to the use of an adhesion promoter in a resin composition, such as a ROMP composition, or as a pre-treatment of a resin material. substrate to provide useful improvements in the adhesion of a metathesis catalyzed composition to the substrate material, and the use of a hydroperoxide gel modifier in a ROMP composition to provide useful improvements in the ability to control a ROMP reaction. More particularly, the inventors have found that the addition of an adhesion promoter according to the invention to a resin composition, in particular a ROMP composition, allows to improve the adhesion of the polymerized composition (resin) to the substrate material, without adversely affect the mechanical properties of the polymerized resin. Alternatively, a substrate material can be pretreated with an adhesion promoter in accordance with the invention in order to improve the adhesion of the polymerized composition (resin) to the substrate material, without adversely affecting the mechanical properties of the polymerized resin. Furthermore, the inventors have found that the addition of a hydroperoxide to the reaction mixture of a ROMP composition allows superior control over the resin gel and cure formation process, without adversely affecting the mechanical properties of the ROMP material. polymerized. Furthermore, the gel modifying effect of hydroperoxides is remarkably stable on the resin compared to other gel modifying agents known in the art.
[014] In one embodiment, the invention provides a method for improving the adhesion of an olefin metathesis reaction, for example, a ROMP reaction, of a cyclic olefin catalyzed by an olefin metathesis catalyst (for example, a catalyst of cyclic olefin metathesis) for a substrate material, wherein an adhesion promoter is combined with a cyclic olefin, an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), and a substrate material, thus forming a resin composition with improved mechanical properties. In another embodiment, the invention provides a method for improving the adhesion of an olefin metathesis reaction, e.g., a ROMP reaction, of a cyclic olefin, catalyzed by an olefin metathesis catalyst (e.g., an olefin metathesis catalyst cyclic olefin metathesis) to a substrate material, such as, for example, a glass substrate material, wherein an adhesion promoter is combined with a cyclic olefin, an olefin metathesis catalyst (e.g. cyclic olefin metathesis), and a substrate material, such as, for example, a glass substrate material, thereby forming a composite resin substrate material with improved properties. The invention is further directed to a ROMP composition of a cyclic olefin, which can be functionalized or non-functionalized and can be substituted or unsubstituted, a cyclic olefin metathesis catalyst, a hydroperoxide gel modifier, and a promoter membership. The inventive ROMP compositions are easy to handle and use and, when combined with a substrate material and cured, form the composite resin substrate materials with improved properties. The adhesion promoter according to the invention, discussed below, generally comprises a compound containing at least two isocyanate groups. An optionally active metathesis compound containing at least one heteroatom may be present in the ROMP composition. The resin composition is then subjected to conditions effective to promote a cyclic olefin olefin metathesis reaction in the presence of the olefin metathesis catalyst, the adhesion promoter, and the substrate material. The resin composition may also be contacted with a substrate material instead of or in addition to the substrate material added to the resin composition and then subjected to conditions effective to promote an olefin metathesis reaction of the cyclic olefin in the presence of the olefin metathesis catalyst, the adhesion promoter, and the optional substrate material added and/or in contact with the substrate material.
[015] The invention is further directed to a resin composition, for example, a ROMP composition, of a cyclic olefin, which can be functionalized or non-functionalized and can be substituted or unsubstituted, an olefin metathesis catalyst , an adhesion promoter, and a substrate material, such as, for example, a glass substrate material. In general, the adhesion promoter comprises a compound with at least two isocyanate groups. The adhesion promoter should be present in an amount effective to increase adhesion of the resin composition to a substrate material when the resin composition is subjected to conditions of metathesis catalysis in the presence of the substrate material. The adhesion promoter can also be a mixture of compounds, where each compound contains at least two isocyanates. In another embodiment, the adhesion promoter contains at least two isocyanates and contains an olefin metathesis active group. In another embodiment, the adhesion promoter contains at least two isocyanates and does not contain an olefin metathesis active group. In another embodiment, the adhesion promoter may also contain an optional compound comprising a functional group containing a heteroatom and a metathesis active olefin.
[016] The addition of the adhesion promoter of the present invention provides beneficial improvements in the adhesion of an olefin metathesis composition (eg, ROMP) to the substrate material, such as, for example, a glass substrate material, in comparison with a resin composition that is the same, with the exception that the adhesion promoter of the present invention is not included.
[017] In another embodiment, the invention provides a method to modify the start of a ROMP reaction of a cyclic olefin, catalyzed by a cyclic olefin metathesis catalyst, in which a hydroperoxide gel modifier is combined with a cyclic olefin and a cyclic olefin metathesis catalyst, thus forming a ROMP composition. The ROMP composition is then subjected to conditions effective to promote a ROMP reaction of the cyclic olefin in the presence of the cyclic olefin metathesis catalyst and added hydroperoxide gel modifier.
[018] The invention is further directed to a ROMP composition of a cyclic olefin, which can be functionalized or non-functionalized and can be substituted or unsubstituted, a cyclic olefin metathesis catalyst, and a hydroperoxide gel modifier. The invention is also directed to a composition comprising a cyclic olefin, which may be functionalized or non-functionalized and may be substituted or unsubstituted, a cyclic olefin metathesis catalyst, a hydroperoxide gel modifier, and an adhesion promoter. invention.
[019] In general, the hydroperoxide gel modifier is added in an amount effective to increase the gelling time of a cyclic olefin ROMP reaction catalyzed by the cyclic olefin metathesis catalyst, in the presence of added hydroperoxide compared to a ROMP reaction of the same cyclic olefin catalyzed by the same cyclic olefin metathesis catalyst in the absence of the added hydroperoxide.
[020] Although the invention is particularly beneficial for ring opening metathesis polymerization (ROMP) reactions, it can also be used in combination with other metathesis reactions, such as a ring opening crossover metathesis reaction. ring, a crossover metathesis reaction, an autometathesis reaction, an ethenolysis reaction, an alkenolysis reaction, or an acyclic diene metathesis polymerization reaction, as well as combinations of such metathesis reactions.
[021] These and other aspects of the invention will be apparent to those skilled in the art in light of the following detailed description and examples. BRIEF DESCRIPTION OF THE DRAWINGS
[022] FIG. 1 represents the effect of cumyl hydroperoxide (CHP) on exotherm time as described in the Examples.
[023] FIG. 2 illustrates the viscosity profile for ROMP of CHP-modified DCPD resin as described in the Examples. DETAILED DESCRIPTION OF DISCLOSURES Terminology and Definitions
[024] Unless otherwise indicated, the invention is not limited to specific reagents, substituents, catalysts, reaction conditions, or the like, as these may vary. It should also be understood that the terminology used in this document is for the purpose of describing the particular modalities only and should not be construed as being limiting.
[025] As used in the specification and appended claims, the singular forms "a" "an" and "o, a" include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to "an α-olefin" includes a single α-olefin, as well as a combination or mixture of two or more α-olefins, reference to "a substituent" includes a single substituent as well as two or more substituents and the like.
[026] As used in the specification and in the appended claims, the terms "for example", "in the case of", "such as" or "including" are intended to present examples that further clarify the more general subject matter. Unless otherwise stated, these examples are provided only as an aid to understanding the invention and are not intended to be a limitation in any way.
[027] In this descriptive report and in the claims that follow, reference will be made to a number of terms that will be defined as having the following meanings:
[028] The term "alkyl" as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group, typically, though not necessarily, containing from 1 to about 24 carbon atoms, preferably , from 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, though again not necessarily, the alkyl groups herein contain from 1 to about 12 carbon atoms. The term "lower alkyl" refers to an alkyl group of 1 to 6 carbon atoms, and the specific term "cycloalkyl" refers to a cyclic alkyl group, typically having from 4 to 8, preferably from 5 to 7 carbon atoms. The term "substituted alkyl" refers to an alkyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to an alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms "alkyl" and "lower alkyl" include linear, branched, cyclic, unsubstituted, substituted alkyl, and/or an alkyl containing heteroatom and lower alkyl, respectively.
[029] The term "alkylene" as used herein refers to a bifunctional, branched, or a cyclic linear alkyl group, where "alkyl" is as defined above.
[030] The term "alkenyl" as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n -propenyl, iso-propenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups herein contain from 2 to about 12 carbon atoms. The term "lower alkenyl" refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term "cycloalkenyl" refers to a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term "substituted alkenyl" refers to alkenyl substituted with one or more substituent groups, and the terms "alkenyl containing heteroatoms" and "heteroalkenyl" refer to alkenyl, wherein at least one carbon atom is replaced with a heteroatom . If not otherwise indicated, the terms "alkenyl" and "lower alkenyl" include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
[031] The term "alkenylene" as used herein refers to a linear, bifunctional, branched, or cyclic alkenyl group, where "alkenyl" is as defined above.
[032] The term "alkynyl" as used herein refers to a straight or branched hydrocarbon group of 2 to about 24 carbon atoms, containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain from 2 to about 12 carbon atoms. The term "lower alkynyl" refers to an alkynyl group of 2 to 6 carbon atoms. The term "substituted alkynyl" refers to alkynyl substituted with one or more substituent groups, and the terms "alkynyl containing heteroatoms" and "heteroalkynyl" refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms "alkynyl" and "lower alkynyl" include linear, branched, unsubstituted, substituted alkynyl, heteroatom-containing alkynyl, and/or lower alkynyl, respectively.
[033] The term "alkoxy" as used herein refers to an alkyl group bonded through a single terminal ether bond; that is, an "alkoxy" group may be represented as -O-alkyl, where alkyl is as defined above. A "lower alkoxy" group refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenyloxy" and "lower alkenyloxy" refer, respectively, to a lower alkenyl and alkenyl group bonded through a single terminal ether bond, and "alkynyloxy" and "lower alkynyloxy", respectively, refer to a alkynyl group and lower alkynyl group bonded through a single terminal ether bond.
[034] The term "aryl" as used herein, and unless otherwise specified, refers to an aromatic substituent that contains a single aromatic ring or multiple aromatic rings, which are fused together, directly bonded, or indirectly bonded (so that the different aromatic rings are bonded to a common group such as an ethylene or methylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms. Examples of aryl groups contain an aromatic ring or two fused or linked aromatic rings, for example, phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone and the like. "Substituted aryl" refers to an aryl moiety substituted with one or more substituent groups, and the terms "aryl containing a heteroatom" and "heteroaryl" refer to aryl substituents, where at least one carbon atom is replaced by a heteroatom, as will be described in more detail below.
[035] The term "aryloxy" as used herein refers to an aryl group bonded through a single terminal ether bond, wherein "aryl" is as defined above. An "aryloxy" group can be represented as -O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy group d contain 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2, 4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
[036] The term "alkaryl" refers to an aryl group with an alkyl substituent, and the term "aralkyl" refers to an alkyl group with an aryl substituent, where "aryl" and "alkyl" are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnanaphthyl, 7-cyclooctylnanaphthyl, 3-ethyl-cyclopenta-1,4-diene, and similar. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms "alkaryloxy" and "aralkyloxy" refer to substituents of the formula -OR where R is alkaryl or aralkyl, respectively, as already defined.
[037] The term "acyl" refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, or -(CO)-aralkyl, and the term "acyloxy" refers to substituents having the formula -O(CO)-alkyl, -O(CO)-aryl, or -O(CO)-aralkyl, where "alkyl," "aryl," and "aralkyl" are as defined above. Additionally, the term "acyl" also refers to substituents having the formula -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl and the term "acyloxy" also refers to substituents having the formula -O(CO)-alkaryl, -O(CO)-alkenyl, or -O(CO)-alkynyl where "alkaryl", "alkenyl," and "alkynyl" are as defined above.
[038] The terms "cyclic" and "ring" refer to alicyclic or aromatic groups which may or may not be substituted and/or containing heteroatoms, and which may be monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used in the conventional sense to refer to an aliphatic cyclic fraction, as opposed to an aromatic cyclic fraction, and can be monocyclic, bicyclic, or polycyclic.
[039] The terms "halo" and "halogen" are used in the conventional sense to refer to a chlorine, bromine, fluoro, or iodine substituent.
[040] "Hydrocarbyl" refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, more preferably 1 to about 12 carbon atoms, including species linear, branched, cyclic, saturated and unsaturated, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term "lower hydrocarbyl" refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term "hydrocarbyl" refers to a divalent hydrocarbyl moiety containing 1 to about from 30 carbon atoms, preferably 1 to about 24 carbon atoms, more preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term "lower hydrocarbylene" refers to a hydrocarbylene group of 1 to 6 carbon atoms. "Substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituent groups, and The terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, "substituted hydrocarbylene" refers to hydrocarbylene substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to hydrocarbylene in which at least one carbon atom is replaced with one heteroatom. Unless otherwise indicated, the term "hydrocarbyl" and "hydrocarbylene" are to be interpreted to include heteroatom-containing and/or substituted hydrocarbyl and hydrocarbylene fractions, respectively.
[041] The term "heteroatom-containing" as in a "heteroatom-containing hydrocarbyl group" refers to a hydrocarbon molecule or molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, eg, nitrogen , oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl" refers to an alkyl substituent that contains heteroatom, the term "heterocyclic" refers to a cyclic substituent that contains heteroatom, The terms "heteroaryl" and "heteroaromatic" respectively refer to "aryl" and "aromatic" substituents that contain heteroatoms, and the like. It should be noted that a "heterocyclic" group or compound may or may not be aromatic, and further that "heterocycles" may be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl". Examples of heteroalkyl groups include alkoxyyl, substituted alkyl-alkyl sulfanyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of alicyclic groups containing heteroatoms are pyrrolidine, morpholino , piperazine, piperidino, etc.
[042] By "substituted" as in "substituted hydrocarbyl," "substituted alkyl" "substituted aryl" and the like, as alluded to in some of the above definitions, is meant in the hydrocarbyl, alkyl, aryl, or other moiety , at least one hydrogen atom bonded to a carbon (or other) atom is replaced with one or more substituents other than hydrogen. Examples of such substituents include, without limitation: functional groups referred to herein as "Fn," such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6- C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy (-- O-CO-alkyl) and C6-C24 arylcarbonyloxy (-O-CO-aryl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-O-aryl) , halocarbonyl (-CO)-X where X is halo), C2-C24 alkylcarbonate (-O-(CO)-O-alkyl), C6-C24 arylcarbonate (-O-(CO)-O-aryl), carboxy ( -COOH), carboxylate (-COO"), carbamolyl (-(CO)-NH2), mono-(C1 -C24 alkyl)-substituted carbamolyl (-(CO)-NH(C1-C24 alkyl)), di-( C1-C24 alkyl)-substituted carbamoyl (-(CO)-N(C1-C24 alkyl)2), mono-(C1-C24 haloalkyl)-substituted carbamolyl (-(CO)-NH(C1-C24 haloalkyl)), di-(C1-C24 haloalkyl)-substituted carbamoyl (-(CO)-N(C1- C24 haloalkyl)2), mono-(C5-C24 aryl)-substituted carbamolyl (-(CO)-NH-(C5-C24 aryl)), di-(C5-C24 aryl)-substituted carbamolyl (-(CO)- N(C5-C24 aryl)2), di-N-(C1-C24 alkyl)N-(C5-C24 aryl)-substituted carbamolyl (-(CO)-N(C1-C24 alkyl)(C5- C24 aryl)), thiocarbamoyl (-(CS)-NH2), mono-(C1-C24 alkyl)-substituted thiocarbamolyl (-(CS)-NH(C1-C24 alkyl)), di-(C1-C24 alkyl) )-substituted thiocarbamolyl (-(CS)-N(C1-C24 alkyl)2), mono-(C5-C24 aryl)-substituted thiocarbamolyl (-(CS)-NH-(C5-C24 aryl)), di-( C5-C24 aryl)-substituted thiocarbamoyl (-(CS)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl),N-(C5-C24 aryl)-substituted thiocarbamoyl (-(CS) )-N(C1-C24 alkyl)(C5-C24 aryl)), carbamido (-NH-(CO)-NH2), cyano (-C=N), cyanate (-OC=N), thiocyanate (-SC= N), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono-(C1-C24 alkyl)-substituted amino (-NH(C1-C24 alkyl) )), di-(C1-C24 alkyl)-substituted amino (-N(C1-C24 alkyl)2), mono-(C5-C24 aryl)-substituted amino (-NH(C5-C24 aryl)), di- (C5-C24 aryl )-substituted amino (-N(C5-C24 aryl)2), C2-C24 alkylamido (-NH-(CO)-alkyl), C6-C24 arylamido (-NH-(CO)-aryl), imino (-CR =NH where R = hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (-CR=N(alkyl), where R = hydrogen, C1 -C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), arylimino (-CR=N(aryl), where R = hydrogen, C1-C20 alkyl, C5-C24 aryl, C6- C24 alkaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonate (-SO2-O"), C1-C24 alkyl sulfanyl (-S- alkyl; also defined "alkylthio"), C5-C24 arylsulfanyl (-S-aryl; also defined "arylthio"), C1-C24 alkylsulfinyl (-(SO)-alkyl), C5-C24 arylsulfinyl (-(SO)- aryl), C1-C24 alkyl sulfonyl (-SO2-alkyl), C1-C24 monoalkyl aminosulfonyl -SO2-N(H) alkyl), C1-C24 dialkyl aminosulfonyl - SO2-N(alkyl)2, C5-C24 aryl sulfonyl ( -SO2-aryl), boryl (-BH2), boronate (-B(OH)2), boronate (-B(OR)2 where R is alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2 ), phosphonate (-P(O)(O')2), phosphinate (-P(O)(O")), phospho (-PO2), and phosphine (-PH2); and the hydrocarbyl C1 fractions -C24 alkyl (preferably C1-C12 alkyl, more preferably C1-C6 alkyl), C2-C24 alkenyl (preferably C2-C12 alkenyl, more preferably C2-C6 alkenyl), C2-C24 alkynyl (preferably C2-C12 alkynyl, more preferably C2-C6 alkynyl), C5-C24 aryl (preferably C5-C14 aryl), C6-C24 alkaryl (preferably C6-C16 alkaryl), and C6-C24 aralkyl (preferably C6-C16 aralkyl). Additional functional groups refer to referred to herein as "Fn" include without limitation, isocyanate (-N=C=O), and thioisocyanate (-N=C=S).
[043] By "functionalized" as in "functionalized hydrocarbon", "functionalized alkyl", "functionalized olefin", "functionalized cyclic olefin" and the like is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin fraction , or other moiety, at least one hydrogen atom bonded to a carbon (or other) atom is substituted with one or more functional groups, such as those described herein above. The term "functional group" is intended to include any functional species that are suitable for the uses described herein. In particular, as used herein, a functional group may necessarily have the ability to react with or bind to corresponding functional groups on a surface of the substrate.
[044] Furthermore, the aforementioned functional groups may, if a certain group permits, further be substituted with one or more additional functional groups, or with one or more hydrocarbyl moieties, such as those specifically mentioned above. Similarly, the above mentioned hydrocarbyl moieties may be further substituted with one or more additional functional groups or hydrocarbyl moieties as mentioned above.
[045] "Optional" or "optionally" means that the circumstance described subsequently may or may not occur, so the description includes cases where the circumstance occurs and cases where it does not. For example, the phrase "optionally substituted" means that a substituent other than hydrogen may or may not be present on a given atom, and thus the description includes structures in which a substituent other than hydrogen is present and structures in which a substituent other than hydrogen is present. of hydrogen is not present.
[046] The term "substrate material", as used herein, is generally intended to mean any material that the resin compositions of the present invention can be contacted with, applied to, or have the substrate material incorporated into the resin. Without limitation, these materials include reinforcing materials such as filaments, fibers, rovings, mats, weavings, fabrics, mesh materials, cloths or other known structures, glass fibers and fabrics, carbon fibers and fabrics, fibers and fabrics of aramid, and of polyolefins or other polymeric fibers or fabrics. Other suitable substrate materials include metallic density modulators, microparticulate density modulators such as microspheres, and macroparticulate density modulators such as glass or ceramic spheres.
[047] In reference to the ROMP reaction of a cyclic olefin catalyzed by the cyclic olefin metathesis catalyst, the term "start of a ROMP reaction" generally refers to a rapid initial increase in the viscosity of the resin composition, which occurs during polymerization just before gelling. The progress of an olefin metathesis polymerization can be monitored by measuring the increase in viscosity as the reaction proceeds from the monomer to the gelled state.
[048] The progress of an exothermic olefin metathesis polymerization can also be conveniently monitored by measuring the temperature rise as the metathesis reaction proceeds from the monomer to the cured state. In the context of the present invention, and as described in the examples presented herein, the term "exotherm time" (or "exotherm time") is defined as the last measured time point, after which the temperature of a catalyzed resin composition of metathesis increases for more than 1°C/second. As shown in FIG. 1, the initial rise in exotherm profile is distinct allowing for accurate measurement of exothermic onset, exothermic time, and peak exothermic temperature. The exothermic peak temperature is the maximum temperature that the resin reaches during polymerization and is related to the integrity of the polymerization reaction. Reduced peak temperatures may be an indication of incomplete polymerization. In general, measuring the exothermic profile is convenient and provides an understanding of the healing behavior and when the cured state is reached.
[049] The terms "mixing use time" and "gelling time" are generally used interchangeably. Various techniques and equipment useful for determining gel time are known in the art and can be used in the present invention. For example, the behavior of the gel, including the gelling time and the use time of the mixture, can be determined using a viscometer, as described in the examples, or by other suitable techniques. In many cases, it is convenient and sufficient to estimate the gelling time by qualitative observation of properties such as pourability or elasticity. Such techniques must necessarily allow an increase in gelling time to be determined such that, in the context of the present invention, the difference in gelling time can be determined between ROMP compositions containing added hydroperoxide and ROMP compositions that do not contain added hydroperoxide. The person skilled in the art will appreciate that the measurement of actual gelling time may depend on the equipment and techniques used, as well as the type of composition being evaluated. However, in the context of the present invention, the determination of the relative increase in gel time achieved by the addition of hydroperoxide to a ROMP composition should not be affected by the particular technique or equipment used to determine the gel time.
[050] The person skilled in the art will also realize that "working time" (or "feasible use time") may vary for different ROMP compositions and, for a particular ROMP composition, may also depend on the application or equipment used. Typically, the working time is longer than the time to start polymerization (eg when the viscosity starts to rise rapidly), but less than the exothermic time. Adhesion Promoter
[051] One aspect of the present invention is directed to adhesion promoters, in general, comprising a compound containing at least two isocyanate groups (such as, for example, methylene diphenyl diisocyanate and hexamethylene diisocyanate). In one embodiment, the adhesion promoter is a di-isocyanate, tri-isocyanate, or poly-isocyanate (ie, which contains four or more isocyanate groups). In another embodiment, the adhesion promoter is a mixture of at least one diisocyanate, triisocyanate or polyisocyanate. In a more particular aspect of the invention, the adhesion promoter comprises, or is limited to, a diisocyanate compound, or mixtures of diisocyanate compounds.
[052] In general, the adhesion promoter can be any compound having at least two isocyanate groups. Suitable adhesion promoters include, without limitation, isocyanate compounds which comprise at least two isocyanate groups, and wherein the compounds are selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and compounds of functionalized hydrocarbyls. As described above, suitable hydrocarbyl adhesion promoter compounds generally include alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkyaryl, and aralkyl compounds. Hydrocarbyl adhesion promoter compounds containing substituted heteroatoms, and functionalized include the hydrocarbyl compounds mentioned above, as well as the variations noted thereto.
[053] In one embodiment the adhesion promoter is an alkyl diisocyanate. An alkyl diisocyanate refers to a linear, branched, or cyclic, saturated or unsaturated hydrocarbon group typically though not necessarily containing 1 to about 24 carbon atoms, preferably a diisocyanate containing 2 to about 12 carbon atoms, and more preferably, a diisocyanate containing 6 to 12 carbon atoms such as hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. Cycloalkyl diisocyanates contain a cyclic alkyl group, typically having 4 to 16 carbon atoms. Preferred cycloalkyl diisocyanates containing 6 to about 12 carbon atoms are cyclohexyl, cycloctyl, cyclodecyl, and the like. A more preferred cycloalkyl diisocyanate originates from an acetone condensation product called 5-isocyanate-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, commonly known as isophorone diisocyanate (IPDI) and the isomers of isocyanate-[(isocyanatocyclohexyl)methyl] cyclohexane (H12MDI). H12MDI is derived from the hydrogenated form of aryl diisocyanate methylene diphenyl diisocyanate (MDI).
[054] In another embodiment, the adhesion promoter is an aryl diisocyanate. Aryl diisocyanates refer to an aromatic diisocyanate containing a single aromatic ring or multiple aromatic rings that are fused together, directly bonded, or indirectly bonded (such that the different aromatic rings are bonded to a common group such as a moiety of methylene or ethylene). Aryl diisocyanates contain 5 to 24 carbon atoms, and particularly preferred aryl diisocyanates contain 5 to 14 carbon atoms. Exemplary aryl diisocyanates contain an aromatic ring ring or two fused or linked aromatic rings, for example, phenyl, tolyl, xylene, nanaphthyl, biphenyl, diphenylether, benzophenone, and the like. Preferred aromatic diisocyanates include toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI), which can comprise any mixture of its three isomers, 2,2'- MDI, 2,4'-MDI, and 4.4'-MDI.
[055] In another embodiment, the adhesion promoter is a polymer-containing isocyanate, such as, for example, di-isocyanates. Polymer-containing isocyanates refer to a polymer containing two or more terminals and/or pendant alkyl or aryl isocyanate groups. Polymer-containing isocyanates generally must have minimal solubility in the resin to provide improved mechanical properties. Preferred polymer-containing isocyanates include, but are not limited to, PM200 (poly MDI), Lupranate® (poly MDI adjoining BASF), Krasol® isocyanate-terminated polybutadiene prepolymers such as, for example, Krasol® LBD2000 (at TDI based), Krasol® LBD3000 (TDI based), Krasol® NN-22 (MDI based), Krasol® NN-23 (MDI based), Krasol® NN-25 (MDI based) , and the like. pre-Krasol® isocyanate-terminated polybutadiene polymers are available from Cray Valley.
[056] In yet another embodiment, the adhesion promoter is a trimer of alkyl diisocyanates and aryl diisocyanates. In its simplest form, any combination of polyisocyanate compounds can be trimerized to form an isocyanurate ring containing isocyanate functional groups. Alkyl diisocyanate and aryl diisocyanate trimers may also be referred to as alkyl diisocyanate or aryl diisocyanate isocyanurates. Alkyl diisocyanate and preferred aryl diisocyanate trimers include, but are not limited to, hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl diisocyanate trimers, and the like. Preferred adhesion promoters are toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI) including any mixture of its three isomers 2,2'-MDI, 2,4 '-MDI and 4,4'-MDI; liquid MDI; solid MDI; hexamethylenediisocyanate trimer (HDIt); hexamethylenediisocyanate (HDI); isophorone diisocyanate (IPDI), 4,4'methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); 4,4'-MDI modified by liquid carbodiimide (Lupranate® MM103); liquid MDI (Lupranate® MI); Liquid MDI (Mondur® ML). Even more preferred adhesion promoters are methylene diphenyl diisocyanate (MDI) including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI; hexamethylenediisocyanate trimer (HDIt); hexamethylenediisocyanate (HDI); isophorone diisocyanate (IPDI), 4,4'methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); 4,4'-MDI modified by liquid carbodiimide (Lupranate® MM103); liquid MDI (Lupranate® MI); Liquid MDI (Mondur® ML).
[057] In other embodiments, the adhesion promoter may include an optional compound with a functional group containing a heteroatom and a metathesis active olefin. The compound containing a functional group containing a heteroatom and metathesis active olefin reacts with an isocyanate group and can provide the olefin metathesis composite with improved mechanical properties. The compound containing a functional group containing a heteroatom and a metathesis active olefin typically contains between 2 and 20 carbon atoms, with oxygen, nitrogen, sulfur, phosphorus, or silicon functional groups. Preferred compounds containing a functional group containing a heteroatom and metathesis active olefin typically contain between 5 and 10 carbon atoms with functional groups containing hydroxyl, amine, thiol, phosphorus, or silane functional groups. Phosphorus-containing functional groups include, for example, alkyl and aryl substituted phosphonate, phosphoryl, phosphanyl, and phosphine compounds. The most preferred compounds containing a functional group containing a heteroatom and metathesis active olefin are derived from norbornenes, oxanorbornenes, cyclooctenes and cyclooctadienes, which typically contain between 7 and 10 carbon atoms with functional groups containing hydroxyl, amine, thiol, phosphorus, or silane functional groups. Other preferred compounds containing a functional group containing a heteroatom and metathesis active olefin include, but are not limited to, 5-norbornene-2-methanol (NB-MeOH); 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB); and allyl alcohol.
[058] Any concentration of adhesion promoter, which improves the mechanical properties of the olefin composite is sufficient for the invention. In general, suitable amounts of adhesion promoter range from 0.001-50 phr, particularly 0.05-10 phr, more particularly 0.1-10 phr, or even more particularly 0.5-4.0 phr.
[059] In one embodiment, the adhesion promoter is contacted with a cyclic olefin, an olefin metathesis catalyst, and a substrate material such as, for example, a glass substrate material, thereby forming a resin composition, for example a ROMP composition. The resin composition is then subjected to conditions effective to promote an olefin metathesis reaction. In another embodiment, the adhesion promoter can be applied to, or contacted with, the substrate surface, such as, for example, a glass substrate, to functionalize the surface prior to application of the resin composition. In another embodiment, the adhesion promoter is combined with a resin composition comprising a cyclic olefin, the resin composition is combined with an olefin metathesis catalyst, and the resulting resin composition is applied to the substrate material, such as as, for example, a glass substrate.
[060] In a further embodiment, the adhesion promoter is contacted with a cyclic olefin, an olefin metathesis catalyst, a hydroperoxide gel modifier, and a substrate material, thus forming a resin composition, for example, a composition of ROMP. The resin composition is then subjected to conditions effective to promote an olefin metathesis reaction. In another embodiment, the adhesion promoter can be applied to, or contacted with, the substrate surface to functionalize the surface prior to application of the resin composition. In another embodiment, the adhesion promoter is combined with a resin composition comprising a cyclic olefin and a hydroperoxide gel modifier, the resin composition is combined with an olefin metathesis catalyst, and the resulting resin composition is applied to the substrate material. Substrate Surfaces
[061] The invention is generally suitable for use with any substrate material where the addition of the adhesion promoter provides beneficial improvements in adhesion of a resin composition (eg ROMP) to the substrate material as compared to a composition of resin which is the same with the exception that the adhesion promoter is not included. The invention is directed to the use of any substrate material, wherein the surfaces of such materials are capable of reacting with the adhesion promoters of the present invention having at least two isocyanate groups. The invention is particularly beneficial for use with glass and carbon material surfaces suitable for use with epoxy and methacrylate resins, including those containing finishes or glues, in which case the finishes or glues need not be removed (for example , by washing or heat cleaning) for the adhesion promoters of the invention to be effective. The invention is also suitable for use with wood and aluminum materials. Suitable substrate materials can also be selected from fibers, fabrics, microparticle, ceramic, metal, polymer, and semiconductor materials. Method for Modification of Gel Formation
[062] In another aspect, the invention provides a method for modifying the start of a ROMP reaction of a cyclic olefin, catalyzed by a cyclic olefin metathesis catalyst, wherein a hydroperoxide gel modifier is combined with a cyclic olefin and a cyclic olefin metathesis catalyst, thus forming a ROMP composition. The ROMP composition is then subjected to conditions effective to promote a cyclic olefin ROMP reaction in the presence of the cyclic olefin metathesis catalyst and the added hydroperoxide gel modifier.
[063] The addition of an olefin metathesis catalyst with an olefinic composition can, under appropriate conditions, initiate a polymerization reaction, thus forming a catalyst resin. The period of time during which the catalyzed resin has a sufficiently low viscosity that the resin flows into the manufacturing process is known as the shelf life. As the polymerization reaction progresses, the viscosity of the resin increases such that the resin is no longer able to flow freely. This is known as the gel state. After the resin has reached a gel state, the polymerization reaction continues until no monomer is consumed under the reaction conditions. This is known as the healed state. In some embodiments, polymerization can be exothermic, driving the polymerization to the cured state. The progress of an olefin metathesis polymerization is usually monitored by measuring the increase in the viscosity of the monomer in the gelled state, or by monitoring the temperature rise of an exotherm of polymerization of the monomer to the cured state.
[064] The onset of the gel state can be varied by several factors, including the chemical nature of the monomer, type of olefin metathesis catalyst, catalyst concentration, reaction temperature and the effect of various additives. It is often useful to be able to delay the onset of the gel state and increase the gelling time in a controlled manner to adapt the polymerization process to the desired reaction or application conditions. The use of gel modification additives allows the storage life of the catalyst resin to be extended such that the resin remains fluid during casting, casting, injecting or infusing into the mold. Gel modification additives must provide controlled changes in the viscosity profile and time to release heat such that the resin efficiently polymerizes once the mold is filled to minimize mold cycle time. Ideally, controlling the amount of gel modifying agent allows for controlling the gel time over several hours. Furthermore, it is important that the silica modifying agent does not adversely affect the mechanical properties of the cured resin.
[065] Applicants have found that the use of hydroperoxide-containing compounds allows the onset of resin gelling and curing states in olefin metathesis polymerizations to be delayed in a controlled manner. While, in general, the hydroperoxide can be any organic hydroperoxide that is effective to delay the onset of the gel state, the hydroperoxide is typically an alkyl group, e.g., C2-C24 alkyl, aryl, e.g., C5-C24 aryl , aralkyl, or alkaryl, for example C6-C24 alkaryl, hydroperoxide, especially secondary or tertiary aromatic or aliphatic hydroperoxides. More specific hydroperoxides suitable for use include tert-butyl hydroperoxide, tert-butyl amyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, (2,5-dihydroperoxy)-2,5-dimethyl-hexane, cyclohydroperoxide -hexyl, triphenylmethyl hydroperoxide, pinane hydroperoxide (eg Glidox® 500; LyondellBasell), and paramethane hydroperoxide (eg Glidox® 300; LyondellBasell). More preferably, hydroperoxides suitable for use include tert-butyl hydroperoxide and cumene hydroperoxide. Gel modifying additives can be added to the reaction mixture in the absence of solvent, or in the form of organic or aqueous solutions. A single hydroperoxide compound can be used as a gel modifying additive, or a combination of two or more different hydroperoxide compounds can be used.
[066] Hydroperoxide compounds can generally be added to the reaction mixture at any time before the onset of the gel state. Conveniently, an appropriate amount of a hydroperoxide gel modifier can be added to the resin during the formulation step, at which time any other additives can be included before contacting the catalyst. Unlike other gel-modifying additives known in the art, hydroperoxides can be added to a resin stock solution and have a shelf life of several weeks or months, while substantially maintaining gel-modifying activity. Alternatively, the hydroperoxide compound can be added directly to the catalyst and/or a catalyst carrier and delivered to the resin during the catalysis step. In another embodiment, hydroperoxide can be added to the catalyzed resin mixture after the addition of the catalyst.
[067] The present invention includes all hydroperoxide concentrations that delay the onset of the gel state of a particular metathesis polymerization. Advantageously, the use of hydroperoxide gel modifiers has been found to substantially maintain the properties of the cured polymer, including peak exotherm temperature and mechanical properties. Although not necessarily limited, the concentration of hydroperoxide is advantageously between 0.01 and 1,000 equivalents with respect to the catalyst. In other embodiments the concentration of hydroperoxide can be between 0.1 and 20 equivalents relative to the catalyst. Generally, higher concentrations of hydroperoxide will lead to a longer storage life. Furthermore, in other embodiments, the hydroperoxide concentration may be between 0.05 and 100 equivalents relative to the catalyst. Furthermore, in other embodiments, the hydroperoxide concentration may be between 0.1 and 50 equivalents relative to the catalyst.
[068] Modification of highly active polymerizations (due to higher resin temperatures, highly active metathesis catalyst, or other factors) typically requires addition of higher concentrations of hydroperoxide compounds. However, if the concentration of gel modifying agent is too high for a given catalyst, or reaction conditions, polymerization may be incomplete and the resin may fail to cure properly. This could result in lower exothermic temperatures or reduced mechanical properties.
[069] The use of hydroperoxide allows the time to gel state onset to be controlled based on the concentration of added hydroperoxide gel modifier. In general, the gelling time (eg, as controlled by exotherm time) can be delayed by about 2 minutes or up to about 12 hours. In more specific aspects, the gelling time (or exotherm time) can be delayed by about 10 minutes to about 6 hours, or, even more particularly, by about 20 minutes to about 2 hours. The time to gel state onset is influenced by the choice of olefin, catalyst, olefin/catalyst ratio and temperature among other factors. The desired time for the beginning of the gel state is often dependent on the conditions of the type of manufacture. Under some conditions, delaying the gel state onset of 10-60 minutes so that the resin can be poured without entrapped air or other defects is usually sufficient. In other applications, such as molding large parts with vacuum assisted resin transfer, delaying gel state onset by 6-12 hours may be desirable. Cyclic Olephin
[070] In addition to the adhesion promoter and/or hydroperoxide compound described above, resin compositions described herein include one or more cyclic olefins. In general, any suitable cyclic olefin can be used for the metathesis reactions disclosed herein. Such cyclic olefins can be optionally substituted C5 to C24 hydrocarbons, optionally containing heteroatoms, optionally functionalized, monounsaturated, di-unsaturated, or polyunsaturated which can be mono-, di-, or polycyclic. The cyclic olefin can, in general, be any strained or unstressed cyclic olefin, so long as the cyclic olefin is capable of participating in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition. Although some unstressed cyclic olefins like cyclohexene are generally understood to not undergo ROMP reactions by themselves, under appropriate circumstances such unstressed cyclic olefins may nevertheless be active in ROMP. For example, when present as a comonomer in a ROMP composition, unstressed cyclic olefins can be active in ROMP. Thus, as used herein and as would be appreciated by those skilled in the art, the term "unstrained cyclic olefin" is intended to refer to those unstressed cyclic olefins that can be subjected to a ROMP reaction under any conditions, or any ROMP composition, as long as the unstressed cyclic olefin is active in ROMP.
[071] In general, the cyclic olefin can be represented by the structure of formula (A)
where J and RA are as follows:
[072] RA is selected from the group consisting of hydrogen, hydrocarbyl (eg, C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (by example, substituted C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (for example, C1-C20 heteroalkyl, C5-C20 heteroaryl, C5-C30 aralkyl) heteroatom containing, or C5-C30 alkaryl containing heteroatom), and hydrocarbyl containing substituted heteroatom (eg, C1-C20 substituted heteroalkyl, C5-C20 heteroaryl, C5-C30 aralkyl containing heteroatom, or C5-C30 alkaryl containing heteroatom) and , if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups ("Fn") such as phosphonate, phosphoryl, phosphanyl, phosphine, sulfonate, C1C20 alkyl sulfanyl, C5-C20 aryl sulfanyl, C1-C20 alkyl sulfonyl , C5-C20 aryl sulfonyl, C1-C20 alkyl sulfinyl, C5-C20 aryl sulfinyl, sulfonamido, amino, ami do, imino, nitro, nitroso, hydroxyl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, carboxylate, carboxylate, mercapto, formyl, C1-C20 thioester, cyano, cyanate , carbamolyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronate, boryl, or halogen, or a metal-containing or metalloid-containing group (where the metal may be, for example, Sn or Ge). RA can by itself be one of the groups mentioned above, such that the Fn moiety is directly attached to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will generally not be directly attached to the olefinic carbon through a heteroatom containing one or more lone pairs of electrons, for example, an oxygen, sulfur, nitrogen, or phosphorus atom, or via a metalloid or electron-rich metal such as Ge, Sn, As, Sb, Se, Te, etc. With these functional groups, there will normally be an intervening bond Z*, such that RA then has a structure -(Z*)n-Fn where n is 1, Fn is the functional group, and Z* is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene bond , heteroarylene, or substituted heteroarylene. Furthermore, the functional groups ("Fn") can be thiocyanate, isocyanate or thioisocyanate.
[073] J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, hydrocarbylene containing a heteroatom, or substituted hydrocarbylene bond containing a heteroatom, wherein when J is substituted hydrocarbylene or hydrocarbylene containing a substituted heteroatom, the substituents may include one or more groups - (Z*)n-Fn, where n is zero or 1, and Fn and Z* are as defined above. In addition, two or more substituents attached to ring (or other) carbon atoms within J can be joined to form a bicyclic or polycyclic olefin. J will generally contain in the range of approximately 5 to 14 ring atoms, generally 5 to 8 ring atoms, for a monocyclic olefin, and for bicyclic and polycyclic olefins each ring will generally contain 4 to 8, usually 5 to 7, ring atoms.
[074] The monounsaturated cyclic olefin reactants encompassed by structure (A) can be represented by structure (B) (B)
Where b is an integer generally though not necessarily in the range of 1 to 10, typically 1 to 5,
[075] RA is as defined above, and RB1, RB2, RB3, RB4, RB5, and RB6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z*)n-Fn where n, Z* and Fn are as previously defined, and wherein if any one of the moieties from RB1 to RB6 is substituted hydrocarbyl or substituted heteroatom containing hydrocarbyl, the substituents may include one or more -(Z*)n-Fn groups. Therefore, RB1, RB2, RB3, RB4, RB5, and RB6 can be, for example, hydrogen, hydroxyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, amino, starch, nitro, etc. In addition, any of the RB1, RB2, RB3, RB4, RB5, and RB6 fractions can be linked to any other of the RB1, RB2, RB3, RB4, RB5 fractions , and RB6 to provide a bicyclic or polycyclic olefin, and the bond may include heteroatoms or functional groups, for example, the bond may include an ether, ester, thioether, amino, alkyl amino, imino, or anhydride moiety.
[076] Examples of monocyclic, monounsaturated olefins encompassed by structure (B) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.
[077] The monocyclic diene reagents encompassed by structure (A) can generally be represented by structure (C) RC5 RC6
Where c and d are independently integers in the range of 1 to about 8, typically 2 to 4, preferably 2 (such that the reactant is a cyclooctadiene), RA is as defined above, and RC1, RC2, RC3 , RC4, RC5, and RC6 are defined as for RB1 to RB6. In this case, it is preferable that RC3 and RC4 are substituents other than hydrogen, in which case the second olefinic moiety is tetrasubstituted. Examples of monocyclic diene reagents include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1 ,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogs thereof. Triene reagents are analogous to the diene structure (C), and will generally contain at least one methylene bond between any two olefinic segments.
[078] The bicyclic and polycyclic olefinic reagents encompassed by structure (A) can generally be represented by structure (D)
Where e is an integer in the range 1 to 8, typically 2 to 4, f is generally 1 or 2, T is lower alkylene, lower alkenylene generally methyl or substituted or unsubstituted ethyl, or heteroatom generally oxygen, sulfur, or nitrogen optionally substituted by lower alkyl or lower alkylene, RA is as defined above, and RD1, RD2, RD3, and RD4 are as defined for RB1 to RB6. Preferred olefinic reagents within this group are in the norbornene and oxanorbornene families, having the structures (E) and (F), respectively (E)

where RA and T are as defined above, RE1, RE2, RE3, and RE6 have the same definitions as RB1 to RB6, and RE4 and RE5 are defined as for RE2 and RE3, respectively.
[079] Additionally, any of the fractions RE1, RE2, RE3, RE4, RE5, and RE6 can be linked to any other of the fractions RE1, RE2, RE3, RE4, RE5, RE6 to provide a bicyclic or polycyclic olefin, and the The linkage can include heteroatoms or functional groups, for example, the linkage can include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.
[080] Examples of bicyclic and polycyclic olefinic reagents thus include, without limitation, dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl- 2-norbornene, 5,6-dimethyl-2-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5- cyanonorbornene, 5,5,6-trimethyl-2-norbornene, cyclohexenylnorbornene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo,exo-5,6-dimethoxycarbonylnorbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2,3-dimethoxynorbornene, norbornadiene, tricycloundecene, tetracyclododecene, 8-methyltetracyclododecene, 8-ethyl-tetracyclododecene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8- cyanotetracyclododecene, pentacyclopentadecene, pentacyclohexadecene, and the like. Additional examples of bicyclic and polycyclic olefins include, without limitation, higher order cyclopentadiene oligomers, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like; and C2-C12 substituted hydrocarbyl norbornenes such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene , 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like.
[081] Preferred cyclic olefins include C5 to C24 unsaturated hydrocarbons. Also preferred are C5 to C24 cyclic hydrocarbons which contain one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins can include several heteroatoms along the way. cycle, and these are within the scope of the invention. Furthermore, preferred cyclic olefins are C5 to C24 hydrocarbons which contain one or more olefins (typically 2 or 3). For example, the cyclic olefin can be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.
[082] Cyclic olefins can also comprise multiple rings (typically 2 or 3). For example, the cyclic olefin can be mono-, di-, or tri-cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused. Preferred examples of cyclic olefins comprising multiple rings include norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene.
[083] The cyclic olefin may also be substituted, for example, a C5 to C24 cyclic hydrocarbon in which one or more (typically 2, 3, 4, or 5) hydrogen atoms are replaced with non-hydrogen substituents. Suitable non-hydrogen substituents can be chosen from the substituents described above. For example, functionalized cyclic olefins, i.e., C5 to C24 cyclic hydrocarbons in which one or more (typically 2, 3, 4, or 5) hydrogens are replaced by functional groups, are within the scope of the invention. Suitable functional groups can be chosen from the functional groups described above. For example, a cyclic olefin functionalized with an alcohol group can be used to prepare a telechelic polymer comprising pendant alcohol groups. The functional groups on the cyclic olefin can be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art can be employed. Acceptable protecting groups can be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins include 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cidecanol, 5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene .
[084] Cyclic olefins incorporating any combination of the aforementioned characteristics (i.e. heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the invention described herein.
[085] The cyclic olefins useful in the invention disclosed herein can be strained or unstressed. It will be appreciated that the amount of ring tension varies for each cyclic olefin compound, and depends on a number of factors, including ring size, the presence, identity of the substituents, and the presence of multiple rings. Ring voltage is a factor in determining the reactivity of a molecule toward olefin ring-opening metathesis reactions. Highly stressed cyclic olefins, like certain bicyclic compounds, easily undergo ring opening reactions with olefin metathesis catalysts. Less stressed cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive. In some cases, ring-opening reactions of relatively unstressed (and therefore relatively unreactive) cyclic olefins may become possible when performed in the presence of the olefin compounds disclosed herein.
[086] A plurality of cyclic olefins can be used to prepare the metathesis polymers of the olefinic compound. For example, two cyclic olefins selected from the cyclic olefins described herein above can be employed to form metathesis products that incorporate both cyclic olefins. When two or more cyclic olefins are used, an example of a second cyclic olefin is a cyclic alkenol, i.e. a C5-C24 cyclic hydrocarbon, in which at least one of the hydrogen substituents is replaced with an alcohol or an alcohol moiety protected, to obtain a functionalized cyclic olefin.
[087] The use of a plurality of cyclic olefins, and, in particular, when at least one of the cyclic olefins is functionalized, allows greater control over the positioning of functional groups in products. For example, the density of crosslink points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows control over the physical properties (eg melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single cyclic olefin, but it will be appreciated that the use of a plurality of cyclic olefins further increases the range of possible metathesis products and formed polymers.
em que RA e T são como definidos acima, RF1, RF2, RF3, RF4, RF5, RF6, RF7, e RF8 são como definidos para RB1 a RB6, e “a” representa uma ligação dupla simples ou uma ligação dupla, f é geralmente 1 ou 2, g é um inteiro de 0 a 5, e quando “a” é uma ligação dupla um de RF5, RF6 e um de RF7, RF8 não está presente. Além disso, qualquer uma das frações RF5, RF6, RF7, e RF8 pode ser ligada a qualquer uma das outras frações RF5, RF6, RF7, e RF8 para fornecer um grupo alicíclico substituído ou não substituído contendo 4 a 30 átomos de carbono do anel ou um grupo aril substi-tuído ou não substituído contendo 6 a 18 átomos de carbono do anel ou combina- ções dos mesmos, e a ligação pode incluir heteroátomos ou grupos funcionais, por exemplo, a ligação pode incluir, sem limitação, uma fração de éter, éster, tioéter, amino, alquil amino, imino, ou anidrido. O grupo cíclico pode ser monocíclico, bicíclico ou policíclico. Quando o grupo cíclico insaturado pode conter monoinsaturação ou multi-insaturação, os grupos cíclicos mono-insaturados são preferidos. Quando substituídos, os anéis contêm monossubstituição ou multissubstituição em que os substituintes são selecionados independentemente de hidrogênio, hidrocarbil, hidrocarbil substituído, grupos funcionais (Fn), hidrocarbil contendo um heteroátomo, hidrocarbil substituído contendo um heteroátomo, e - (Z*)n-Fn, onde Fn n é zero ou 1, Z*, e Fn são como definidos acima.[088] In addition, the preferred cyclic olefins encompassed by structure (D) that are found in the norbornene family can generally be represented by structure (G): where RA and T are as defined above, RF1, RF2, RF3, RF4, RF5, RF6, RF7, and RF8 are as defined for RB1 to RB6, and "a" represents a single double bond or a double bond, f is usually 1 or 2, g is an integer from 0 to 5, and when “a” is a double bond one of RF5, RF6 and one of RF7, RF8 is not present. In addition, any of the RF5, RF6, RF7, and RF8 moieties can be linked to any of the other moieties RF5, RF6, RF7, and RF8 to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof, and the bond may include heteroatoms or functional groups, for example, the bond may include, without limitation, a moiety of ether, ester, thioether, amino, alkyl amino, imino, or anhydride. The cyclic group can be monocyclic, bicyclic or polycyclic. When the unsaturated cyclic group can contain monounsaturation or multi-unsaturation, monounsaturated cyclic groups are preferred. When substituted, rings contain mono- or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, functional groups (Fn), hydrocarbyl containing a heteroatom, substituted hydrocarbyl containing a heteroatom, and - (Z*)n-Fn , where Fn n is zero or 1, Z*, and Fn are as defined above.
em que, RG1, RG2, RG3, e RG4 são como definidos para RB1 a RB6, e “a” representa uma ligação dupla simples ou uma ligação dupla, g é um inteiro de 0 a 5, e quando “a” é uma ligação dupla um de RG1, RG2 e um de RG3, RG4 não está presente. Além disso, qualquer uma das frações RG1, RG2, RG3, e RG4 pode ser ligada a qualquer uma das outras frações RG1, RG2, RG3, e RG4 para fornecer um grupo alicíclico substituído ou não substituído contendo 4 a 30 átomos de carbono do anel ou um grupo aril substituído ou não substituído contendo 6 a 18 átomos de carbono do anel ou combinações dos mesmos, e a ligação pode incluir heteroátomos ou grupos funcionais, por exemplo, a ligação pode incluir, sem limitação, uma fração de éter, éster, tioéter, amino, alquil amino, imino, ou anidrido. O grupo alicíclico pode ser monocíclico, bicíclico ou policíclico. Quando o grupo cíclico insaturado pode conter monoinsaturação ou multi-insaturação, os grupos cíclicos mono-insaturados são preferido. Quando substituídos, os anéis contêm monossubstituição ou multissubstituição em que os substituintes são selecionados independentemente de hidrogênio, hidrocarbil, hidrocarbil substituído, grupos funcionais (Fn), hidrocarbil contendo um heteroátomo, hidrocarbil substituído contendo um heteroátomo, e - (Z*)n-Fn, onde Fn n é zero ou 1, Z*, e Fn são como definidos acima.[089] The most preferred cyclic olefins have at least a fraction of norbornene having the structure (H): where, RG1, RG2, RG3, and RG4 are as defined for RB1 to RB6, and "a" represents a single double bond or a double bond, g is an integer from 0 to 5, and when "a" is a bond double one of RG1, RG2 and one of RG3, RG4 is not present. In addition, any of the RG1, RG2, RG3, and RG4 moieties can be linked to any of the other moieties RG1, RG2, RG3, and RG4 to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof, and the bond may include heteroatoms or functional groups, for example, the bond may include, without limitation, an ether, ester, moiety, thioether, amino, alkyl amino, imino, or anhydride. The alicyclic group can be monocyclic, bicyclic or polycyclic. When the unsaturated cyclic group can contain monounsaturation or multi-unsaturation, monounsaturated cyclic groups are preferred. When substituted, rings contain mono- or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, functional groups (Fn), hydrocarbyl containing a heteroatom, substituted hydrocarbyl containing a heteroatom, and - (Z*)n-Fn , where Fn n is zero or 1, Z*, and Fn are as defined above.
em que RG1 a RG4 são como definidos acima.[090] One route for the preparation of substituted hydrocarbon and functionally substituted norbornenes employs the Diels-Alder cycloaddition reaction, in which the cyclopentadiene or substituted cyclopentadiene is reacted with a suitable dienophile at elevated temperatures to form the substituted norbornene adduct, generally represented by the following Reaction Scheme 1: SCHEME 1 where RG1 to RG4 are as defined above.
Em que g é um inteiro de 0 a 5, e RG1 a RG4 são como definidos acima.[091] Other adducts of norbornene can be prepared by thermal pyrolysis of dicyclopentadiene in the presence of a suitable dienophile. The reaction proceeds by initial pyrolysis from dicyclopentadiene to cyclopentadiene followed by Diels-Alder cycloaddition between the cyclopentadiene and dienophile to produce the adduct shown below in Scheme 2: Where g is an integer from 0 to 5, and RG1 to RG4 are as defined above.
em que g é um inteiro de 0 a 5, RG1 e RG4 são como definidos acima.[092] Norbornadiene and higher Diels-Alder adducts thereof, similarly can be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of an acetylenic reagent as shown below in Scheme 3: where g is an integer from 0 to 5, RG1 and RG4 are as defined above.
[093] The most preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl -2-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxy-carbonylnorbornene, 5-cyanonorbornene, 5,5,6-trimethyl -2-norbornene, cyclohexenylnorbornene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo,exo-5,6-dimethoxycarbonylnorbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2 ,3-dimethoxynorbornene, norbornadiene, tricycloundecene, tetracyclododecene, 8-methyltetracyclododecene, 8-ethyl-tetracyclododecene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene, pentacentycyclopentadecene superior cyclopentadiene such as cyclopentadiene tetramer, cyclopentadiene pentamer, and semel brackets; and C2-C12 substituted hydrocarbyl norbornenes such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5 -vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like. Even more preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, tetracyclododecene, norbornene, and C2-C12 hydrocarbyl norborne. such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like. Olefin Metathesis Catalyst
X2 em que: M é um metal de transição do Grupo 8; L1, L2, e L3 são ligantes doadores de elétron neutro; n é 0 ou 1, tal que L3 pode ou não estar presente; m é 0, 1, ou 2; k é 0 ou 1; X1 e X2 são ligantes aniônicos; e[094] The olefin metathesis catalyst complex according to the invention is preferably a Group 8 transition metal complex having the structure of formula (I) X2 where: M is a Group 8 transition metal; L1, L2, and L3 are neutral electron donor ligands; n is 0 or 1 such that L3 may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are anionic binders; and
[095] R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, where any two or more of X1, X2, L1, L2, L3, R1 , and R2 can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2 can be attached to a support.
[096] Additionally, in formula (I), one or both of R1 and R2 may have the structure -(W)n-U+V', where W is selected from hydrocarbylene, substituted hydrocarbylene, hydrocarbylene containing heteroatom, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is zero or 1. Furthermore, R1 and R2 can be taken together to form an indenylidene moiety.
[097] Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru particularly preferred.
[098] Several modalities of catalysts useful in the reactions described in this document are described in greater detail below. For the sake of convenience, catalysts are described in groups, but it should be noted that these groups are not intended to be limiting in any way. That is, any of the catalysts useful in the present invention may fit the description of more than one of the groups described herein.
[099] A first group of catalysts, then, is commonly referred to as First Generation Grubbs-type catalysts, and has the structure of formula (I). For the first group of catalysts, M and m are as described above, and n, X1, X2, L1, L2, L3, R1, and R2 are described as follows.
[100] For the first group of catalysts, n is 0, and L1 and L2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide , carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, and thioether. Exemplary ligands are trisubstituted phosphines. Preferred trisubstituted phosphines are of the formula PRH1RH2RH3, where RH1, RH2, RH3 are each independently substituted or unsubstituted aryl or C1-C10 alkyl, particularly, primary alkyl, secondary alkyl, or cycloalkyl. Most preferred, L1 and L2 are independently selected from the group consisting of trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PnBu3), tri(ortho-tolyl)phosphine (Po-tolyl3) , tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCyclopentyl3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triisobutylphosphine (Pi-Bu3), trioctylphosphine (POct3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph). Alternatively, L1 and L2 are independently selected from phosphobicycloalkane (eg, monosubstituted 9-phosphabicyclo[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane, such as cyclohexylfoban, isopropylfoban, ethylfoban, methylfoban, butylfoban, pentylfoban, and the like.
[101] X1 and X2 are anionic linkers, and may be the same or different, or are linked together to form a cyclic group, typically, though not necessarily, a five- to eight-membered ring. In preferred embodiments, X1 and X2 are each independently hydrogen, halide, or one of the following groups: C1-C20 alkyl, C5-C24 aryl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C6- C24 aryloxycarbonyl, C2-C24 acyl, C2-C24 acyloxy, C1-C20 alkyl sulfonate, C5-C24 aryl sulfonate, C1-C20 alkyl sulfanyl, C5-C24 aryl sulfanyl, C1-C20 alkyl sulfinyl, or C5-C24 aryl sulfinyl. Optionally, X1 and X2 can be substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which can, in turn, with the exception of the halide, be further substituted with one or more selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl. In more preferred embodiments, X1 and X2 are halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkyl sulfanyl, aryl, or C1-C6 alkyl sulfonyl. In even more preferred embodiments, X1 and X2 are each halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate , mesylate, or trifluoromethanesulfonate. In the most preferred embodiments, X1 and X2 are each chloride. Alternatively, X1 and X2 are independently NO3, -N=C=O, or -N=C=S.
[102] R1 and R2 are independently selected from hydrogen, hydrocarbyl (eg, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc. .), substituted hydrocarbyl (for example, substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), heteroatom-containing hydrocarbyl (for example , C1-C20 alkyl containing heteroatom, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), and hydrocarbyl containing substituted heteroatom (eg, C1- C20 alkyl containing substituted heteroatom, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), and functional groups. R1 and R2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.
[103] In preferred catalysts, R1 is hydrogen and R2 is selected from C1-C20 alkyl, C2-C20 alkenyl, and C5-C24 aryl, more preferably, C1-C6 alkyl, C2-C6 alkenyl, and C5- C14 aryl. Even more preferably, R2 is phenyl, vinyl, methyl, iso-propyl, or t-butyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl, and a functional group Fn as defined earlier in this document. More preferably, R2 is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chlorine, bromine, iodine, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. Ideally, R2 is phenyl or -C=C(CH3)2.
[104] Any two or more (typically two, three, or four) of X1, X2, L1, L2, L3, R1, and R2 can be taken together to form a cyclic group, including bidentate or multidentate linkers, as disclosed , for example, in US Patent No. 5,312,940, the disclosure of which being incorporated herein by reference. When any one of X1, X2, L1, L2, L3, R1, and R2 are linked to form cyclic groups, the cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or may comprise two or three of these rings, which can be either fused or linked. Cyclic groups can be aliphatic or aromatic, and can be heteroatom-containing and/or substituted. The cyclic group can, in some cases, form a bidentate linker or a tridentate linker. Examples of bidentate binders include, but are not limited to, bisphosphines, dialkoxides, alkyldiketones, and aryldiketones.
tal que o complexo podem ter a estrutura de fórmula (I-II) em que M, m, n, X1, X2, L2, L3, R1, e R2 são como definidos para o primeiro grupo de catalisadores, e e os substituintes restantes são como segue;[105] A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, having the structure of formula (I), where L1 is a carbene ligand having the structure of formula (II): such that the complex may have the structure of formula (I-II) wherein M, m, n, X1, X2, L2, L3, R1, and R2 are as defined for the first group of catalysts, and and the remaining substituents are as follows;
[106] X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S, and k is zero or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N;
[107] Q1, Q2, Q3, and Q4 are linkers, for example, hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as heteroatom-containing and/or substituted alkylene) or -(CO)-, ew, x, y, and z are independently zero or 1, meaning that each linker is optional. Preferably, w, x, y, and z are all zero. Furthermore, two or more substituents on adjacent atoms within Q1, Q2, Q3, and Q4 can be linked to form an additional cyclic group; and
[108] R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. Furthermore, X and Y can be independently selected from carbon and one of the heteroatoms mentioned above. Additionally, L2 and L3 can be taken together to form a single, bidentate electron-donating heterocyclic ligand. Furthermore, R1 and R2 can be taken together to form an indenylidene fraction. In addition, X1, X2, L2, L3, X, and Y are further coordinated with boron or a carboxylate.
[109] Furthermore, any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3, and Q4 can be taken together to form a group cyclic, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A can be attached to a support. Any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, and R4A can also be taken to be -A-Fn, where "A" is a selected divalent hydrocarbon moiety from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene may be substituted or unsubstituted substituted, and wherein heteroatoms and/or functional groups may be present in any of the aryl or alkyl moieties of the alkylene and arylalkylene groups, and Fn is a functional group, or together form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A can be attached to a bracket.
em que R3 e R4 são definidos acima, com preferência, pelo menos um de R3 e R4, e com mais preferência, ambos R3 e R4, sendo alicíclicos ou aromáticso de um a cerca de cinco anéis, e opcionalmente contendo um ou mais heteroátomos e/ou substi- tuintes. Q é um ligante, tipicamente um ligante de hidrocarbileno, incluindo hidrocarbile- no substituído, hidrocarbileno contendo heteroátomo, e ligante de hidrocarbileno contendo heteroátomo substituídos, em que dois ou mais substituintes em átomos adjacentes dentro de Q podem também ser ligados para formar uma estrutura cíclica adicional, que pode ser de modo semelhante substituída para fornecer uma estrutura policíclica fundida de dois a cerca de cinco grupos cíclicos. Q e, muitas vezes, embora não neces-sariamente, uma ligação de dois átomos ou uma ligação de três átomos.[110] Preferably, R3A and R4A are linked to form a cyclic group such that the carbene linker has the structure of formula (IV) wherein R3 and R4 are defined above, preferably at least one of R3 and R4, and more preferably both R3 and R4, being alicyclic or aromatic from one to about five rings, and optionally containing one or more heteroatoms and /or substitutes. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linker, wherein two or more substituents on adjacent atoms within Q may also be linked to form a cyclic structure additional, which can be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, though not necessarily, a two-atom bond or a three-atom bond.
[111] Examples of suitable N-heterocyclic carbene (NHC) linkers and acyclic diaminocarbene linkers as L1 thus include, but are not limited to, the following where DIPP is diisopropylphenyl and Mes is 2,4,6- trimethylphenyl:
em que RW1, RW2, RW3, RW4 são independentemente hidrogênio, hidrocarbil não substituído, hidrocarbil substituído, ou heteroátomo contendo hidrocarbil, e onde um ou ambos de RW3 e RW4 podem ser independentemente selecionados a partir de grupos de halogênio, nitro, amido, carboxil, alcóxi, ariloxi, sulfonil, carbonil, tio, ou nitroso.[112] Additional examples of NHC linkers and acyclic diaminocarbene linkers suitable as L1 thus include, but are not limited to, the following: where RW1, RW2, RW3, RW4 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom containing hydrocarbyl, and where one or both of RW3 and RW4 can be independently selected from halogen, nitro, starch, carboxyl groups , alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso.
[113] Additional examples of suitable NHC linkers such as L1 are further described in U.S. Patents Pat. Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635.768; and 6,552,139, the disclosures of which being incorporated herein by reference.
[114] Additionally, thermally activated N-Heterocyclic Carben Precursors as disclosed in U.S. Patent No. 6,838,489, the contents of which being incorporated herein by reference, may also be used with the present invention.
[115] When M is ruthenium, then preferred complexes have the structure of formula (V):
[116] In a more preferred embodiment, Q is a two-atom bond having the structure -CR11R12-CR13R14- or -CR11=CR13-, preferably -CR11R12-CR13R14-, wherein R11, R12, R13, and R14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups herein include carboxyl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C5-C24 alkoxycarbonyl, C2-C24 acyloxy, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkyl sulfonyl , and C1-C20 alkyl sulfinyl, optionally substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, hydroxyl, sulfhydryl, formyl, and halide. R11, R12, R13, and R14 are preferably independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R11, R12, R13, and R14 may be bonded together to an unsubstituted, saturated or unsaturated ring structure, for example, a C4C12 alicyclic group or a C5 or C6 aryl group, which may alone be substituted, for example, with attached or fused alicyclic or aromatic groups, or with other substituents. In a further aspect, any one or more of R11, R12, R13, and R14 comprises one or more of the linkers. Additionally, L2 can be L2(k), where k is zero or 1. R3 and R4 can be unsubstituted phenyl or substituted phenyl with one or more substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted heteroalkyl, C5-C24 aryl, C5-C24 substituted aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide. Also, X1 and X2 can be halogens.
[117] When R3 and R4 are aromatic, they are typically, though not necessarily, composed of one or two aromatic rings, which may or may not be substituted, for example, R3 and R4 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl , or the like. In a preferred embodiment, R3 and R4 are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C1-C20 alkyl, C1-C20 substituted alkyl, C1-C20 heteroalkyl, C1-C20 heteroalkyl substituted, C5-C24 aryl, C5-C24 substituted aryl, C5-C24 heteroaryl, C6C24 aralkyl, C6-C24 alkaryl, or halide. Preferably, any substituents present are hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, C5-C14 substituted aryl, or halide. As an example, R3 and R4 are mesityl (ie Mes as defined in this document).
[118] In a third group of catalysts having the structure of formula (I), M, m, n, X1, X2, R1, and R2 are as defined for the first group of catalysts, L1 is a neutral electron donor ligand of strong coordination such as any of those described for the first and second group of catalysts, and L2 and L3 are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is zero or 1, such that L3 may or may not be present. Generally, in the third group of catalysts, L2 and L3 are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, more preferably 1 to 2 heteroatoms, or are bicyclic structures or optionally substituted polycyclics composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it must not be substituted on a coordinating heteroatom, and any cyclic moiety within a heterocyclic group will generally be substituted with more than 3 substituents.
[119] For the third group of catalysts, examples of L2 and L3 include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.
[120] Examples of suitable nitrogen-containing heterocyclics for L2 and L3 include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinoline, quinazoline, naphthridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolilimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole. Nitrogen-containing heterocyclics can be optionally substituted on an uncoordinated heteroatom with a non-hydrogen substituent.
[121] Examples of suitable sulfur-containing heterocyclics for L2 and L3 include thiophene, 1,2-dithiol, 1,3-dithiol, tiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H- thiopyran, 4H-thiopyran, and thioanthrene.
[122] Examples of suitable oxygen-containing heterocyclics for L2 and L3 include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxine, oxepin, furan, 2H-1- benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxane, and dibenzofuran.
[123] Examples of suitable mixed heterocycles for L2 and L3 include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3 ,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxthiol, 1,3-oxthiol, 4H-1,2-oxazine, 2H-1 ,3-oxazine, 1,4-oxazine, 1,2,5-oxazine, o-iso-oxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazol, anthrani, and morpho- lino.
[124] Preferred L2 and L3 linkers are nitrogen-containing and oxygen-containing aromatic heterocyclics and particularly preferred linkers L2 and L3 are monocyclic N-heteroaryl linkers which are optionally substituted with 1 to 3, preferably 1 or 2 , substitutes. Specific examples of particularly preferred L2 and L3 linkers are substituted pyridines and pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4 -chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro 4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine , 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, and the like.
[125] In general, any substituents present on L2 and/or L3 are selected from halo, C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted heteroalkyl, C5-C24 aryl, C5 -C24 substituted aryl, C5-C24 heteroaryl, C5-C24 substituted heteroaryl, C6-C24 alkaryl, C6-C24 substituted alkaryl, C6-C24 heteroalkaryl, C6-C24 substituted heteroalkaryl, C6-C24 aralkyl, C6-C24 substituted aralkyl , C6C24 heteroaralkyl, substituted C6-C24 heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkylcarbonyl, C6-C24 arylcarbonyl, C2-C20 alkylcarbonyloxy, C6- C24 arylcarbonyloxy, C2C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20 alkylcarbonate, C6-C24 arylcarbonate, carboxy, carboxylate, carbamolyl, mono-(C1-C20 alkyl)-substituted carbamolyl, di-(C1-C20 alkyl)- substituted carbamolyl, di-N-(C1-C20 alkyl), N-(C5-C24 aryl)-substituted carbamolyl, mono-(C5-C24 aryl) )-substituted carbamolyl, di-(C6-C24 aryl)-substituted carbamolyl, thiocarbamolyl, mono-(C1-C20 alkyl)-substituted thiocarbamoyl, di-(C1-C20 alkyl)-substituted thiocarbamoyl, di-N-(C1- C20 alkyl)-N-(C6-C24 aryl)-substituted thiocarbamolyl, mono-(C6-C24 aryl)-substituted thiocarbamoyl, di-(C6-C24 aryl)-substituted thiocarbamolyl, carbamido, formyl, thioformyl, amino, mono- (C1-C20 alkyl)-substituted amino, di-(C1-C20 alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(C5-C24 aryl)-substituted amino, di-N- (C1-C20 alkyl), N-(C5-C24 aryl)-substituted amino, C2-C20 alkylamido, C6-C24 arylamido, imino, C1-C20 alkylimino, C5C24 arylimino, nitro, and nitroso. Furthermore, two adjacent substituents can be taken together to form a ring, generally a five- or six-membered alicyclic or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as above.
[126] Preferred substituents on L2 and L3 include, without limitation, halo, C1-C12 alkyl, C1-C12 substituted alkyl, C1-C12 heteroalkyl, C1-C12 substituted heteroalkyl, C5-C14 aryl, C5-C14 substituted aryl, C5-C14 heteroaryl, C5-C14 substituted heteroaryl, C6-C16 alkaryl, C6-C16 substituted alkaryl, C6-C16 heteroalkaryl, C6-C16 substituted heteroalkaryl, C6-C16 aralkyl, C6-C16 substituted aralkyl, C6-C16 heteroaralkyl, C6 -C16 substituted heteroaralkyl, C1-C12 alkoxy, C5-C14 aryloxy, C2-C12 alkylcarbonyl, C6-C14 arylcarbonyl, C2-C12 alkylcarbonyloxy, C6-C14 arylcarbonyloxy, C2-C12 alkoxycarbonyl, C6C14 aryloxycarbonyl, halocarbonyl, formyl, amino, -(C1-C12 alkyl)-substituted amino, di-(C1-C12 alkyl)-substituted amino, mono-(C5-C14 aryl)-substituted amino, di-(C5-C14 aryl)-substituted amino, and nitro.
[127] Of the above, the most preferred substituents are halo, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C1-C6 alkyl)amino, nitro, and nitrogen heterocycles As described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).
em que R15, R16, R17, e R18 hidrocarbil (por exemplo, C1-C20 alquil, C2-C20 al- quenil, C2-C20 alquinil, C5-C24 aril, C6-C24 alcaril, ou C6-C24 aralquil), hidrocarbil substituído (por exemplo, C1-C20 alquil substituído, C2-C20 alquenil, C2-C20 alquinil, C5-C24 aril, C6-C24 alcaril, ou C6-C24 aralquil), hidrocarbil contendo heteroátomo (por exemplo, C1-C20 heteroalquil, C5-C24 heteroaril, C6-C24 aralquil contendo heteroátomo, ou C6-C24 alcaril contendo heteroátomo), ou hidrocarbil contendo heteroátomo substituído (por exemplo, C1-C20 heteroalquil substituído, C5-C24 heteroaril, C6-C24 aralquil contendo heteroátomo, ou C6-C24 alcaril contendo heteroátomo), ou (1) R15 e R16, (2) R17 e R18, (3) R16 e R17, ou (4) ambos R15 e R16, e R17 e R18, podem ser tomados em conjunto para formar um anel, ou seja, um N-heterociclo. Os grupos cíclicos preferidos em tal caso são anéis de cinco- e seis- membros, tipicamente anéis aromáticos.[128] In certain embodiments, L2 and L3 can be taken together to form a bidentate or multidentate ligand containing two or more, usually two, coordinating heteroatoms such as N, O, S, or P, with such ligands preferred without - giving the Brookhart-type diimine binders. A representative bidentate linker has the structure of formula (VI) where R15, R16, R17, and R18 are hydrocarbyl (for example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), hydrocarbyl substituted (eg, substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), hydrocarbyl containing heteroatom (eg, C1-C20 heteroalkyl, C5-C24 heteroaryl, C6-C24 heteroatom-containing aralkyl, or heteroatom-containing C6-C24 alkaryl), or substituted heteroatom-containing hydrocarbyl (eg, C1-C20 substituted heteroalkyl, C5-C24 heteroaryl, C6-C24 heteroatom-containing aralkyl, or C6 -C24 heteroatom-containing alkaryl), or (1) R15 and R16, (2) R17 and R18, (3) R16 and R17, or (4) both R15 and R16, and R17 and R18, can be taken together to form a ring, i.e. an N-heterocycle. Preferred cyclic groups in such a case are five- and six-membered rings, typically aromatic rings.
[129] In a fourth group of catalysts having the structure of formula (I), two of the substituents are taken together to form a bidentate linker or a tridentate linker. Examples of bidentate binders include, but are not limited to, bisphosphines, dialkoxides, alkyldiketones, and aryldiketones. Specific examples include -P(Ph)2CH2CH2P(Ph)2-, -As(Ph)2CH2CH2As(Ph2)-, -P(Ph)2CH2CH2C(CF3)2O-, binaphtholate dianions, pinacolate dianions, - P(CH3 )2(CH2)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Preferred bidentate linkers are -P(Ph)2 CH2CH2P(Ph)2- and -P(CH3)2(CH2)2P(CH3)2-. Tridentate ligands include, but are not limited to, (CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2. Other preferred tridentate binders are those in which any three of X1, X2, L1, L2, L3, R1, and R2 (for example, X1, L1, and L2) are taken together to be cyclopentadienyl, indenyl, or fluorenyl , each optionally substituted with C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkyl sulfonyl, or C1-C20 alkyl sulfinyl, each of which may be further substituted with C1-C6 alkyl, halide, C1-C6 alkoxy or with a phenyl group optionally substituted with halide, C1-C6 alkyl, or C1-C6 alkoxy. More preferably, in compounds of this type, X, L1, and L2 are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C1-C10 alkyl, C5-C20 aryl, C1-C10 carboxylate, C2 -C10 alkoxycarbonyl, C1-C10 alkoxy, or C5-C20 aryloxy, each optionally substituted with C1-C6 alkyl, halide, C1-C6 alkoxy or with a phenyl group optionally substituted with halide, C1-C6 alkyl or C1-C6 alkoxy . More preferably, X, L1 and L2 can be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to, O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.
em que, M é um metal de transição do Grupo 8, particularmente, Ru ou Os, ou, mais particularmente, Ru; X1, X2, e L1 são como previamente definidos no presente documento; [1] é um heteroátomo selecionado a partir de N, O, S, e P; de preferência, Y é O ou N; R5, R6, R7, e R8 são, cada, independentemente, selecionados a partir do grupo que consiste em hidrogênio, halogênio, alquil, alquenil, alquinil, aril, heteroal- quil, heteroátomo contendo alquenil, heteroalquenil, heteroaril, alcóxi, alqueniloxi, ariloxi, alcóxicarbonil, carbonil, alquil amino, alquiltio, aminossulfonil, monoalquil aminossulfonil, dialquil aminossulfonil, alquil sulfonil, nitrila, nitro, alquil sulfinil, triha- loalquil, perfluoroalquil, ácido carboxílico, cetona, aldeído, nitrato, ciano, isocianato, hidroxil, éster, éter, amina, imina, amida, amida substituída com halogênio, trifluoro- amida, sulfeto, dissulfeto, sulfonato, carbamato, silano, siloxano, fosfina, fosfato, borato, ou -A-Fn, em que “A” e Fn foi definido acima; e qualquer combinação de Y, Z, R5, R6, R7, e R8 pode ser ligada para formar um ou mais grupos cíclicos; n é 0, 1, ou 2, tal que n é 1 para os heteroátomos divalentes O ou S, e n é 2 para os heteroátomos trivalentes N ou P; e Z é um grupo selecionado a partir de hidrogênio, alquil, aril, alquil funcionali- zado, aril funcionalizado onde o(s) grupo(s) funcionalizado pode ser um ou mais dos seguintes: alcóxi, ariloxi, halogênio, ácido carboxílico, cetona, aldeído, nitrato, ciano, isocianato, hidroxil, éster, éter, amina, imina, amida, trifluoroamida, sulfeto, dissulfe- to, carbamato, silano, siloxano, fosfina, fosfato, ou borato; metil, isopropil, sec-butil, t- butil, neopentil, benzil, fenil e trimetilsilil; e em que qualquer combinação ou combinações de X1, X2, L1,Y, Z, R5, R6, R7, e R8 pode ser ligada a um suporte. Adicionalmente, R5, R6, R7, e R8 pode, independentemente, ser tioisocianato, cianato, ou tio- cianato. Adicionalmente, Z pode, independentemente, ser tioisocianato, cianato, ou tiocianato.[130] Complexes where Y is metal-coordinated are examples of a fifth group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs metathesis-active metal carbene complexes- wherein, M is a Group 8 transition metal, particularly Ru or Os, or more particularly Ru; X1, X2, and L1 are as previously defined in this document; [1] is a heteroatom selected from N, O, S, and P; preferably Y is O or N; R5, R6, R7, and R8 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl-containing heteroatom, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkyl amino, alkylthio, aminosulfonyl, monoalkyl aminosulfonyl, dialkyl aminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, aldehyde ester, ether, amine, imine, amide, halogen substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where "A" and Fn was defined above; and any combination of Y, Z, R5, R6, R7, and R8 can be linked to form one or more cyclic groups; n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functionalized group(s) can be one or more of the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X1, X2, L1,Y, Z, R5, R6, R7, and R8 can be attached to a support. Additionally, R5, R6, R7, and R8 can independently be thioisocyanate, cyanate, or thiocyanate. Additionally, Z can independently be thioisocyanate, cyanate, or thiocyanate.
em que Y, n, Z, R5, R6, R7, e R8 são como previamente definidos no presente documento; Y, Z, e R5 podem, opcionalmente, ser ligados para formar uma estrutura cí- clica; e R9 e R10 são cada, independentemente, selecionados a partir de hidrogênio ou um grupo substituinte selecionado a partir de alquil, aril, alcóxi, ariloxi, C2-C20 alcóxicarbonil, ou C1-C20 trialquilsilil, em que cada um dos grupos substituintes é substituído ou não substituído; e em que qualquer combinação ou combinações de Z, Y, R5, R6, R7, R8, R9, e R10 pode ser ligada a um suporte. A fração de alquilideno quelante pode ser derivada a partir de um precursor de ligante tendo a fórmula: [131] In general, the Grubbs-Hoveyda complexes useful in the invention contain a chelating alkylidene moiety of formula (VIII): wherein Y, n, Z, R5, R6, R7, and R8 are as previously defined herein; Y, Z, and R5 can optionally be linked to form a cyclic structure; and R9 and R10 are each independently selected from hydrogen or a substituent group selected from alkyl, aryl, alkoxy, aryloxy, C2-C20 alkoxycarbonyl, or C1-C20 trialkylsilyl, wherein each of the substituent groups is substituted or not replaced; and wherein any combination or combinations of Z, Y, R5, R6, R7, R8, R9, and R10 can be attached to a support. The alkylidene chelating moiety can be derived from a ligand precursor having the formula:
em que, L1, X1, X2, e M são como descritos para qualquer um dos outros grupos de catalisadores. Os precursores de carbeno e carbenos quelantes adequados são ainda descritos por Pederson et al. (Patentes U.S. N°s. 7.026.495 e 6.620.955, as divulgações de ambas das quais sendo incorporadas aqui por referência) e Hoveyda et al. (U.S. Pat. No. 6.921.735 e WO0214376, as divulgações de ambas das quais sendo incorporadas aqui por referência).[132] Examples of complexes comprising Grubbs-Hoveyda ligands suitable in the invention include: wherein, L1, X1, X2, and M are as described for any of the other catalyst groups. Suitable chelating carbene precursors and carbenes are further described by Pederson et al. (US Patent Nos. 7,026,495 and 6,620,955, the disclosures of both of which are incorporated herein by reference) and Hoveyda et al. (US Pat. No. 6,921,735 and WO0214376, the disclosures of both of which are incorporated herein by reference).
[133] Other useful complexes include structures in which L2 and R2 according to formulas (I), (I-II), or (V) are attached, such as etyrenic compounds which also include a functional group for attachment to a support . Examples where the functional group is a functionalized trialkoxysilyl moiety include, but are not limited to, the following:
[134] Additional examples of complexes having bonded ligands include those having bonds between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L2 ligand, an NHC ligand neutral and an L3 ligand, an anionic ligand and an alkydine ligand, and any combination thereof. Although the possible structures are too numerous to list here, some suitable structures based on the for-
em que: M, X1, X2, L1, L2, L3, R1, e R2 são como definidos para qualquer um dos gru- pos de catalisadores definidos anteriormente; r e s são independentemente zero ou 1; t é um inteiro na faixa de zero a 5; k é um inteiro na faixa de zero a 1; Y é ânion de não coordenação (por exemplo, um íon de haleto, BF4-, etc.); Z1 e Z2 são independentemente selecionados a partir de -O-, -S-, -NR2-, - PR2-, -P(=O)R2-, -P(OR2)-, -P(=O)(OR2)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -S(=O)-, e -S(=O)2-; Z3 é qualquer fração catiônica tais como -P(R2)3+ ou -N(R2)3+; e quaisquer dois ou mais de X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, e R2 podem ser tomados em conjunto para formar um grupo cíclico, por exemplo, um ligante multi- dentado, e em que qualquer um ou mais de X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, e R2 pode ser fixo a um suporte. Adicionalmente, Z1 e Z2 podem também ser uma ligação de C1-C20 hidrocarbileno opcionalmente contendo heteroátomo e/ou opcionalmente substituído.[135] In addition to catalysts having the structure of formula (I) as described above, other transition metal carbene complexes include, but are not limited to: neutral ruthenium or osmium metal carbene complexes containing metal centers that they are formally in the +2 oxidation state, having an electron count of 16, are penta-coordinates, and are of general formula (IX); neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, having an electron count of 18, are hexa-coordinated, and are of general formula (X); cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, having an electron count of 14, are tetra-coordinated, and are of general formula (XI); and cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, having an electron count of 14 or 16, are tetra-coordinated or penta-coordinated, respectively. , and are of general formula (XI-I) wherein: M, X1, X2, L1, L2, L3, R1, and R2 are as defined for any of the catalyst groups defined above; res are independently zero or 1; t is an integer in the range zero to 5; k is an integer in the range zero to 1; Y is a non-coordinating anion (eg a halide ion, BF4-, etc.); Z1 and Z2 are independently selected from -O-, -S-, -NR2-, -PR2-, -P(=O)R2-, -P(OR2)-, -P(=O)(OR2) -, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -S(=O)-, and -S(=O )two-; Z3 is any cationic moiety such as -P(R2)3+ or -N(R2)3+; and any two or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 can be taken together to form a cyclic group, e.g., a multi-tooth linker, and in which any one or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 can be attached to a bracket. Additionally, Z1 and Z2 can also be an optionally heteroatom-containing and/or optionally substituted C1-C20 hydrocarbylene bond.
em que M é um metal de transição do Grupo 8, particularmente, rutênio ou ósmio, ou mais particularmente, rutênio; X1, X2, L1, e L2 são como definidos para os primeiro e segundo grupos de catalisadores definidos acima; e RJ1, RJ2, RJ3, RJ4, RJ5, e RJ6 são, cada um, independentemente selecionados a partir do grupo que consiste em hidrogênio, halogênio, alquil, alquenil, alquinil, aril, heteroalquil, heteroátomo contendo alquenil, heteroalquenil, heteroaril, alcóxi, alque- niloxi, ariloxi, alcóxicarbonil, carbonil, alquil amino, alquiltio, aminossulfonil, monoal- quil aminossulfonil, dialquil aminossulfonil, alquil sulfonil, nitrila, nitro, alquil sulfinil, trihaloalquil, perfluoroalquil, ácido carboxílico, cetona, aldeído, nitrato, ciano, isocia- nato, tioisocianato, cianato, tiocianato, hidroxil, éster, éter, tioéter, amina, alquilami- na, imina, amida, amida substituída com halogênio, trifluoroamida, sulfeto, dissulfeto, sulfonato, carbamato, silano, siloxano, fosfina, fosfato, borato, ou -A-Fn, em que “A” é uma fração de hidrocarboneto divalente selecionada a partir de alquileno e arilal- quileno, em que a porção de alquil dos grupos alquileno e arilalquileno pode ser linear ou ramificada, saturada ou insaturada, cíclica ou acíclica, e substituída ou não substituída, em que a porção de aril do arilalquileno pode ser substituída ou não substituída, e em que heteroátomos e/ou grupos funcionais podem estar presentes em qualquer uma das frações aril ou alquil dos grupos alquileno e arilalquileno, e Fn é um grupo funcional, ou qualquer um ou mais de RJ1, RJ2, RJ3, RJ4, RJ5, e RJ6 pode ser ligado junto para formar um grupo cíclico, ou qualquer um ou mais de RJ1, RJ2, RJ3, RJ4, RJ5, e RJ6 pode ser fixo a um suporte.[136] Additionally, another group of olefin metathesis catalyst that can be used in the invention disclosed herein is a Group 8 transition metal complex having the structure of formula (XI-II): wherein M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1, X2, L1, and L2 are as defined for the first and second catalyst groups defined above; and RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy , alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkyl amino, alkylthio, aminosulfonyl, monoalkyl aminosulfonyl, dialkyl aminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, cyanoaldehyde, nitrate , isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where "A" is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, where the alkyl portion of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene may be substituted or unsubstituted, and wherein heteroatoms and/or functional groups may be present in any of the aryl or alkyl moieties of the groups alkylene and arylalkylene, and Fn is a functional group, or any one or more of RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6 can be linked together to form a cyclic group, or any one or more of RJ1, RJ2, RJ3 , RJ4, RJ5, and RJ6 can be attached to a bracket.
em que M, X1, X2, L1, L2, são como definidos acima para o complexo de metal de transição do Grupo 8 de fórmula XI-II; e RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15 e RJ16 são como definidos acima para RJ1, RJ2, RJ3, RJ4, RJ5, e RJ6 para o complexo de metal de transição do Grupo 8 de fórmula XI-II ou qualquer um ou mais de RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15 e RJ16 pode ser ligado junto para formar um grupo cíclico, ou qualquer um ou mais de RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15 e RJ16 pode ser fixo a um suporte.[137] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula (XI-II) is a Group 8 transition metal complex of formula (XIV): wherein M, X1, X2, L1, L2 are as defined above for the Group 8 transition metal complex of formula XI-II; and RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15 and RJ16 are as defined above for RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6 for the transition metal complex of Group 8 of formula XI -II or any one or more of RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15 and RJ16 can be linked together to form a cyclic group, or any one or more of RJ7, RJ8, RJ9, RJ10 , RJ11, RJ12, RJ13, RJ14, RJ15 and RJ16 can be attached to a bracket.
tal de transição do Grupo 8 de fórmula (XI-II).[138] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula (XI-II) is a Group 8 transition metal complex of formula (XV): Group 8 transition tal of formula (XI-II).
em que M é um metal de transição do Grupo 8, particularmente, rutênio ou ósmio, ou mais particularmente, rutênio; X1 e L1 são como definidos para os primeiro e segundo grupos de catalisa- dores definidos acima; Z é selecionado a partir do grupo que consite em oxigênio, enxofre, selênio, NRK11, PRK11, AsRK11, e SbRK11; e RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, e RK11 são, cada um, independentemente selecionados a partir do grupo que consiste em hidrogênio, halogê- nio, alquil, alquenil, alquinil, aril, heteroalquil, heteroátomo contendo alquenil, hetero- alquenil, heteroaril, alcóxi, alqueniloxi, ariloxi, alcóxicarbonil, carbonil, alquil amino, alquiltio, aminossulfonil, monoalquil aminossulfonil, dialquil aminossulfonil, alquil sul- fonil, nitrila, nitro, alquil sulfinil, trihaloalquil, perfluoroalquil, ácido carboxílico, cetona, aldeído, nitrato, ciano, isocianato, tioisocianato, cianato, tiocianato, hidroxil, éster, éter, tioéter, amina, alquilamina, imina, amida, amida substituída com halogênio, tri- fluoroamida, sulfeto, dissulfeto, sulfonato, carbamato, silano, siloxano, fosfina, fosfato, borato, ou -A-Fn, em que “A” é uma fração de hidrocarboneto divalente selecionada a partir de alquileno e arilalquileno, em que a porção de alquil dos grupos alqui- leno e arilalquileno pode ser linear ou ramificada, saturada ou insaturada, cíclica ou acíclica, e substituída ou não substituída, em que a porção de aril do arilalquileno pode ser substituída ou não substituída, e em que heteroátomos e/ou grupos funcionais podem estar presentes em qualquer uma das frações aril ou alquil dos grupos alquileno e arilalquileno, e Fn é um grupo funcional, ou qualquer um ou mais de RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, e RK11 pode ser ligado junto para formar um grupo cíclico, ou qualquer um ou mais de RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, e RK11 pode ser fixo a um suporte.[139] Additionally, another group of olefin metathesis catalyst that can be used in the invention disclosed herein is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula ( XVI): wherein M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1 and L1 are as defined for the first and second catalyst groups defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRK11, PRK11, AsRK11, and SbRK11; and RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, and RK11 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl , heteroalkyl, alkenyl-containing heteroatom, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkyl aminosulfonyl, dialkyl aminosulfonyl, alkylsulfonyl, nitrile, nitroalkylsulfonyl, trialkylhalo perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where "A" is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, where the alkyl portion of the alkylene groups and arylalkylene can be lin ear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene may be substituted or unsubstituted, and wherein heteroatoms and/or functional groups may be present in any of the fractions aryl or alkyl of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, and RK11 can be linked together to form a cyclic group, or any one or more of RK1, RK2, RK3, RK4, RK5, RK6, RK7, RK8, RK9, RK10, and RK11 can be attached to a bracket.
em que M, X1, L1, Z, RK7, RK8, RK9, RK10, e RK11 são como definidos acima para o complexo de metal de transição do Grupo 8 de fórmula XVI; e RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, e RK21 são como definidos acima para RK1, RK2, RK3, RK4, RK5, e RK6 para o complexo de metal de transição do Grupo 8 de fórmula XVI, ou qualquer um ou mais de RK7, RK8, RK9, RK10, RK11, RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, e RK21 pode ser ligado junto para formar um grupo cíclico, ou qualquer um ou mais de RK7, RK8, RK9, RK10, RK11, RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, e RK21 pode ser fixo a um suporte.[140] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVII): wherein M, X1, L1, Z, RK7, RK8, RK9, RK10, and RK11 are as defined above for the Group 8 transition metal complex of formula XVI; and RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, and RK21 are as defined above for RK1, RK2, RK3, RK4, RK5, and RK6 for the Group 8 transition metal complex of formula XVI, or any one or more of RK7, RK8, RK9, RK10, RK11, RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, and RK21 can be linked together to form a cyclic group, or any one or more of RK7, RK8, RK9, RK10, RK11, RK12, RK13, RK14, RK15, RK16, RK17, RK18, RK19, RK20, and RK21 can be attached to a bracket.
em que M, X1, L1, Z, RK7, RK8, RK9, RK10, e RK11, são como definidos acima para o complexo de metal de transição do Grupo 8 de fórmula XVI.[141] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVI-II) : wherein M, X1, L1, Z, RK7, RK8, RK9, RK10, and RK11, are as defined above for the Group 8 transition metal complex of formula XVI.
em que M é um metal de transição do Grupo 8, particularmente rutênio ou ósmio, ou mais particularmente, rutênio; X1, L1, R1, e R2 são como definidos para os primeiro e segundo grupos de catalisadores definidos acima; Z é selecionado a partir do grupo que consite em oxigênio, enxofre, selênio, NRV5, PRV5, AsRV5, e SbRV5; m é 0, 1, ou 2; e RV1, RV2, RV3, RV4, e RV5 são, cada um, independentemente selecionados a partir do grupo que consiste em hidrogênio, halogênio, alquil, alquenil, alquinil, aril, heteroalquil, heteroátomo contendo alquenil, heteroalquenil, heteroaril, alcóxi, alque- niloxi, ariloxi, alcóxicarbonil, carbonil, alquil amino, alquiltio, aminossulfonil, monoal- quil aminossulfonil, dialquil aminossulfonil, alquil sulfonil, nitrila, nitro, alquil sulfinil, trihaloalquil, perfluoroalquil, ácido carboxílico, cetona, aldeído, nitrato, ciano, isocia- nato, tioisocianato, cianato, tiocianato, hidroxil, éster, éter, tioéter, amina, alquilami- na, imina, amida, amida substituída com halogênio, trifluoroamida, sulfeto, dissulfeto, sulfonato, carbamato, silano, siloxano, fosfina, fosfato, borato, ou -A-Fn, em que “A” é uma fração de hidrocarboneto divalente selecionada a partir de alquileno e arilal- quileno, em que a porção de alquil dos grupos alquileno e arilalquileno pode ser linear ou ramificada, saturada ou insaturada, cíclica ou acíclica, e substituída ou não substituída, em que a porção de aril do arilalquileno pode ser substituída ou não substituída, e em que heteroátomos e/ou grupos funcionais podem estar presentes em qualquer uma das frações aril ou alquil dos grupos alquileno e arilalquileno, e Fn é um grupo funcional, ou qualquer um ou mais de RV1, RV2, RV3, RV4, e RV5 pode ser ligado junto para formar um grupo cíclico, ou qualquer um ou mais de RV1, RV2, RV3, RV4, e RV5 pode ser fixo a um suporte.[142] Additionally, another group of olefin metathesis catalyst that can be used in the invention disclosed herein is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula ( XIX): wherein M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1, L1, R1, and R2 are as defined for the first and second catalyst groups defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRV5, PRV5, AsRV5, and SbRV5; m is 0, 1, or 2; and RV1, RV2, RV3, RV4, and RV5 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyl - nyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkyl amino, alkylthio, aminosulfonyl, monoalkyl aminosulfonyl, dialkyl aminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, - nate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where "A" is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, where the alkyl portion of the alkylene and arylalkylene groups may be linear or branched, saturated or i. unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene may be substituted or unsubstituted, and wherein heteroatoms and/or functional groups may be present in any of the aryl or alkyl moieties of the alkylene groups and arylalkylene, and Fn is a functional group, or any one or more of RV1, RV2, RV3, RV4, and RV5 can be linked together to form a cyclic group, or any one or more of RV1, RV2, RV3, RV4, and RV5 can be fixed to a bracket.
[143] Furthermore, catalysts of formulas (XVI) to (XIX) can optionally be contacted with an activating compound, where at least a partial cleavage of a bond between the Group 8 transition metal and at least one base linker Schiff's occurs, wherein the activating compound is either a metal or silicon compound selected from the group consisting of copper(I) halides; zinc compounds of the formula Zn(RY1)2, where RY1 is halogen, C1-7 alkyl or aryl; tin compounds represented by the formula SnRY2RY3RY4RY5 wherein each of RY2, RY3, RY4 and RY5 is independently selected from the group consisting of halogen, C1-20 alkyl, C3-C10 cycloalkyl, aryl, benzyl and C2-7 alkenyl; and silicon compounds represented by the formula SiRY6RY7RY8RY9 wherein each of RY6, RY7, RY8, RY9 is independently selected from the group consisting of hydrogen, halogen, C1-20 alkyl, halo, C1-7 alkyl, aryl, heteroaryl, and vinyl.
[144] Furthermore, catalysts of formulas (XVI) to (XIX) can optionally be contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one base linker Schiff's occurs, wherein the activating compound is inorganic acid such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, iodic acid, periodic acid, perchloric acid, HOClO, HOClO2 and HOIO3. Furthermore, catalysts of formulas (XVI) to (XIX) can optionally be contacted with an activating compound where at least a partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base linker occurs. , wherein the activating compound is an organic acid such as sulfonic acids including, but not limited to, methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulphanilic acid, and trifluoromethanesulfonic acid; monocarboxylic acids, including, but not limited to, acetoacetic acid, barbituric acid, bromoacetic acid, bromobenzoic acid, chlorobenzoic acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic acid, cis cinnamic acid, cyanoacetic acid, cyanobutyric acid, cyanophenoxyacetic acid, dichloroacetic acid, dichloroacetylacetic acid, dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furancarboxylic acid, furoic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid , lactic acid, lutidinic acid, mandelic acid, α-naphthoic acid, nitrobenzoic acid, nitrophenylacetic acid, o-phenylbenzoic acid, thioacetic acid, thiophene carboxylic acid, trichloroacetic acid, and trihydroxybenzoic acid and other acidic substances such as, but not, limited to, picric acid and uric acid.
[145] In addition, other examples of catalysts that can be used with the present invention are located in the following disclosures, each of which is incorporated herein by reference; U.S. Patents Nos. 7,687,635; 7,671,224; 6,284,852; 6,486,279; and 5,977,393; International Publication Number WO2010/037550; and U.S. Patent Applications Nos. 12/303,615; 10/590,380; 11/465,651 (U.S. Publication No. 2007/0043188); and 11/465,651 (U.S. Publication No. 2008/0293905 Corrected Publication); and European Patents Nos. EP1757613B1 and EP1577282B1.
[146] Non-limiting examples of catalysts that can be used to prepare supported complexes in the reactions disclosed herein include the following, some of which, for convenience, are identified throughout this disclosure with reference to molecular weights:
[147] Additional non-limiting examples of catalysts that can be used to prepare supported complexes and in the reactions disclosed herein include the following,
[148] In the above molecular structures and formulas, Ph represents phenyl, Cy represents cyclohexyl, Me represents methyl, Bu represents n-butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), Mes represents mesityl (i.e. 2,4,6-trimethylphenyl), DiPP and DIPP represents 2,6-diisopropylphenyl, MiPP represents 2-isopropylphenyl. Additionally, t-Bu represents tert-butyl, and Cp represents cyclopentyl.
[149] Additional examples of catalysts useful for preparing supported complexes and in the reactions disclosed herein include the following: ruthenium (I-I) dichloro(3-methyl-2-butenylidene) bis(tricyclopentylphosphine) (C716); ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclohexylphosphine) (C801); ruthenium (I-I) dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium (II) (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine) (C830), and ruthenium (II) dichloro (phenylvinylidene) bis(tricycle -hexylphosphine) (C835); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601), and ruthenium (II) (1,3-bis-(2, 4, 6,-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) bis-(3-bromopyridine) (C884)).
[150] Still other catalysts useful in ROMP reactions, and/or in other metathesis reactions, such as ring closing metathesis, cross metathesis, ring opening cross metathesis, autometathesis, polymerization of ethenolysis metathesis , alkenolysis, acyclic diene, and combinations thereof, include the
[151] Additional non-limiting examples of catalysts that can be used to prepare supported complexes and in the reactions disclosed herein include the following:
[152] In general, the transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Patent No. 5,312,940, and U.S. Patent No. 5,342,909, the disclosures of each of which are incorporated herein by reference. See also U.S. Patent Publication No. 2003/0055262 by Grubbs et al., filed April 16, 2002, for “Group 8 Transition Metal Carbene Complexes as Enantioselective Olefin Metathesis Catalysts”, International Patent Publication No. WO 02/079208, and U.S. Patent No. 6,613,910 to Grubbs et al., filed April 2, 2002, for "One-Pot Synthesis of Group 8 Transition Metal Carbene Complexes Useful as Olefin Metathesis Catalysts", the disclosures of each of which are incorporated herein by reference. Preferred synthetic methods are described in International Patent Publication No. WO 03/11455A1 by Grubbs et al. to “Hexacoordinated Ruthenium or Osmium Metal Carbene Metathesis Catalysts,” published February 13, 2003, the disclosure of which is incorporated herein by reference.
[153] Preferred olefin metathesis catalysts are Group 8 Transition Metal Complexes having the structure of formula (I) commonly called "First Generation Grubbs" catalysts, formula (II) commonly called "Second Generation Grubbs" catalysts , or formula (VI-I) commonly called "Grubbs-Hoveyda" catalysts.
[154] The most preferred olefin metathesis catalyst has the structure of formula (I): wherein:
[155] is a Group 8 transition metal;
[156] L2, and L3 are neutral electron donor ligands;
[157] is 0 or 1;
[158] is 0, 1, or 2;
[159] is 0 or 1;
[160] and X2 are anionic ligands; and R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1 , and R2 can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2 can be attached to a support.
[161] When expressed as the molar ratio of monomer to catalyst, the catalyst (the "monomer to catalyst ratio"), the charge will generally be present in an amount ranging from a minimum of about 10,000,000:1, 1,000 .000:1, or 200.00:1, for a maximum of about 100,000:1 66,667:1, 40,000:1.20,000:1, 10,000:1.5,000:1, or 1,000:1. Compositions and Articles of Cyclic Olefin (Resin)
[162] Cyclic olefin resin, particularly ROMP, compositions according to the invention generally comprise one or more cyclic olefins, an olefin metathesis catalyst, an adhesion promoter, and a substrate material such as, for example , a glass substrate material; one or more cyclic olefins, an olefin metathesis catalyst, an adhesion promoter, and a hydroperoxide gel modifier, or one or more cyclic olefins, an olefin metathesis catalyst, and a hydroperoxide gel modifier. In another embodiment, the cyclic olefin resin, particularly ROMP, compositions according to the invention generally comprise one or more cyclic olefins, an olefin metathesis catalyst, an adhesion promoter, and a heteroatom-functionalized substrate . The cyclic olefins described above are suitable for use and can be functionalized or unfunctionalized, and can be substituted or unsubstituted. In general, particularly advantageous results can be obtained by ROMP resin compositions in which the adhesion promoter is present in an amount effective to increase adhesion of the ROMP composition to a substrate material when the ROMP composition is subjected to conditions of metathesis catalysis in the presence of a substrate material. Furthermore, the cyclic olefin resin compositions according to the invention may also comprise one or more cyclic olefins and an adhesion promoter, wherein the resin composition is combined with an olefin metathesis catalyst, and the resulting resin composition is applied to a substrate, such as, for example, a glass substrate. Furthermore, the cyclic olefin resin compositions according to the invention may also comprise one or more cyclic olefins and an adhesion promoter, wherein the resin composition is combined with an olefin metathesis catalyst, and the composition of resulting resin is applied to a substrate, which substrate may be a substrate-functionalized, such as, for example, a substrate functionalized with heteroatoms, such as, for example, an amino-functionalized substrate. Furthermore, cyclic olefin resin compositions according to the invention may also comprise one or more cyclic olefins, an adhesion promoter, and a hydroperoxide gel modifier, wherein the resin composition is combined with a catalyst of olefin metathesis, and the resulting resin composition is applied to a substrate. Furthermore, the cyclic olefin resin compositions according to the invention may also comprise one or more cyclic olefins and a hydroperoxide gel modifier, wherein the resin composition is combined with an olefin metathesis catalyst, and the resulting resin composition is applied to a substrate.
[163] The amounts of adhesion promoter in the resin composition can vary over a wide range and may vary depending on the manufacturing operation or the particular end-use application. Generally, any level of adhesion promoter that produces a desired increase in mechanical properties is of particular interest. When formulated or combined with a resin composition, the concentration of the adhesion promoter typically ranges from 0.05-10 phr, more particularly from 0.5-4.0 phr. In a preferred aspect of the invention, increased mechanical properties can be obtained for resin compositions comprising the adhesion promoter and substrate materials, or resin compositions comprising the adhesion promoter that are applied to the substrate materials, in comparison with resin compositions without the adhesion promoter. For example, the inclusion of the adhesion promoter in resin compositions according to the invention can provide an improvement in mechanical properties, such as interlaminar shear strength (ILSS), of at least about 10% compared to the same composition of the resin that does not contain the adhesion promoter. Preferably, use of the adhesion promoter provides at least a 2% improvement in an adhesion property (e.g. ILSS as described in the examples), more particularly, at least a 5%, or 10%, or 15% , or 20%, or 30%, or 40%, or 50%, or 80% improvement in the adhesion property compared to the adhesion property value (eg ILSS) obtained for the same resin composition, which does not include the adhesion promoter. In particular aspects of the invention, substrate materials may advantageously comprise an aminosilane treated substrate.
[164] The amounts of hydroperoxide gel modifier in the resin composition can vary over a wide range and may vary depending on the manufacturing operation or the particular end-use application. Generally, any level of hydroperoxide gel modifier that delays the onset of the gel form of a particular metathesis polymerization is of particular interest. When formulated or combined with a resin composition, the concentration of the hydroperoxide gel modifier typically ranges between 0.01 and 1000 equivalents with respect to the catalyst, such as, for example, between 0.05 and 100 equivalents with respect to the catalyst, such as, for example, between 0.1 and 50 equivalents with respect to the catalyst, such as, for example, between 0.1 and 20 equivalents with respect to the catalyst.
[165] The resin compositions of the present invention may optionally be formulated with additives. The amount of additives present in resin compositions can vary depending on the particular type of additive used. The concentration of additives in resin compositions typically ranges from, for example, 0.001-85 percent by weight, particularly 0.1-75 percent by weight, or even more particularly 2-60 percent by weight. Suitable additives include, but are not limited to, additional gel modifiers, hardness modulators, antioxidants, stabilizers, fillers, binders, plasticizers, pigments, flame retardants, dyes, fibers and reinforcement materials, including glued reinforcements and substrates, such as those treated with finishes, coatings, coupling agents, film-forming agents, and/or lubricants.
[166] The resin compositions of the present invention can optionally be formulated without a cross-linking agent, for example, a cross-linking agent selected from dialkyl peroxides, diacyl peroxide, and peracids.
[167] Additionally, suitable elastomers or impact modifiers include, without limitation, natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene-butadiene-styrene triblock rubber, styrene-random butadiene rubber, styrene-isoprene-styrene triblock rubber, styrene-ethylene/butylene-styrene copolymer, styrene-ethylene/propylene-styrene copolymer, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate , and nitrile rubbers. Preferred impact modifiers or elastomers are Polybutadiene Diene 55AC10 (Firestone), Polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), Styrene-ethylene/butylene-styrene copolymer Kraton G1651H, Polysar Butil 301 (Bayer ), polybutadiene Taktene 710 (Bayer), styrene-ethylene/butylene-styrene Kraton G1726M, Ethylene-Octene Engage 8150 (DuPont-Dow), styrenebutadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML- 140 (Exxon). Such materials are commonly used in the resin composition, at levels from about 0.10 phr to 10 phr, but more preferably at levels from about 0.1 phr to 5 phr. Various impact modifiers or polar elastomers can also be used.
[168] Additionally, antioxidants and antiozonants include any antioxidant or antiozonant used in the rubber or plastics industry. An “Index of Commercial Antioxidants and Antiozonants,” Fourth Edition,” is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company, Akron, Ohio 44316. The right stabilizers ( i.e., antioxidants or antizonants) include, without limitation: 2,6-di-tert-butyl-4-methylphenol (BHT); styrene phenol such as Wingstay S (Goodyear); 2- and 3- tert-butyl-4-methoxyphenol; alkylated hindered phenols such as Wingstay C (Goodyear); 4-hydroxymethyl-2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2.2 ‘ - methylenebis(4-methyl-6-tert-butylphenol); 2.2 ‘ -methylenebis(4-ethyl-6-tert-butylphenol); 4,4' - methylenebis(2,6-di-tert-butylphenol); various biphenols, such as Cianox 53 and Permanax WSO; 2.2 ‘ -ethylidenebis(4,6-di-tert-butylphenol); 2.2 ‘ -methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4'-butylidenebis(6-tert-butyl-3-methylphenol); Polybutylated bisphenol A; 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-methylenebis(2,6-dimethylphenol); 1.1 ‘ -thiobis(2-naphthol); methylene bridged with polyalkylphenol, such as Ethyl Antioxidant 738; 2.2‘-thiobis(4-methyl-6-tert-butylphenol); 2.2 ‘ -isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction product of p-cresol and dicyclopentadiene, such as Wingstay L; tetrakis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane, i.e. Irganox 1010; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, e.g. Ethanox 330; 4,4'-methylenebis(2,6-di-tertiary-butylphenol), e.g. Ethanox 4702 or Ethanox 4710; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, ie Good-rite 3114, 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenylphosphite), bis(2,4-di-tert-butyl)pentaerythritol)diphosphite, distearyl pentaerythritol diphosphite, phenols and phosphate biphenols such as Naugard 492, phosphite/phenolic antioxidant blends such as Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate such as Irganox 1093; 1,6-hexamethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate), such as Irganox 259, and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, i.e. Irganox 1076, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosphonite, diphenylamine, and 4,4'-dimethoxydiphenylamine These materials are commonly employed in the resin composition at levels from about 0.10 phr to 10 phr, but more preferably at levels of about 0.1 phr to 5 phr.
[169] Suitable reinforcing materials include those that contribute to the strength and stiffness of a polymer composite when incorporated with the polymer. Reinforcement materials can be in the form of filaments, fibers, spins, mats, weavings, fabrics, mesh materials, fabric or other known structures. Suitable reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, and aramid fibers and fabrics, polyolefin fibers or fabrics (including extremely high molecular weight polyethylene fabrics such as those produced by Honeywell under the trade name Spectra) and polyoxazole fibers or fabrics (such as those produced by Toyobo Corporation under the trade name Zylon®). Reinforcement materials containing surface finishes, glues, or coatings are particularly suitable for the described invention including Ahlstrom glass spinning (R338-2400), Johns Manville glass spinning (Star ROV®-086), Owens Corning spinning (OCV 366- AG-207, R25H-X14-2400, SE1200-207, SE1500-2400, SE2350-250), PPG glass spinning (Hybon® 2002, Hybon® 2026), Toho Tenax® carbon fiber trailer (HTR-40) , and carbon fiber trailer Zoltek carbon fiber (Panex® 35). Furthermore, any fabrics prepared using reinforcement materials containing surface finishes, glues or coatings are suitable for the invention. Advantageously, the invention does not require the expensive process of removing finishes, glues, or surface coatings from reinforcement materials. In addition, glass fibers or fabrics may include, without limitation, A-glass, E-glass or S-glass, S-2 glass, C-glass, R-glass, ECR-glass, M-glass, D- glass, and quartz, and silica/quartz. Preferred fiberglass reinforcements are those with finishes formulated for use with epoxy, vinyl ester, and/or polyurethane resins. When formulated for use with a combination of these types of resins, reinforcements are sometimes described as "multi-compatible". Such reinforcements are generally treated during their manufacture with organosilane coupling agents comprising vinyl, amino, glycidoxy or methacryloxy functional groups (or various combinations thereof), and are coated with a coating to protect the fiber surface and facilitate its handling and processing (eg winding and weaving). Finishes typically comprise a mixture of polymeric and chemical compounds such as film formers, surfactants and lubricants. Especially preferred glass reinforcements are those which contain some amount of amino-functionalized silane coupling agent. Especially preferred finishes are those comprising epoxy-based and/or polyurethane-based film formers. Examples of preferred fiberglass reinforcements are those based on Hybon® 2026, 2002, and 2001 (PPG) multi-compatible yarns; wires bonded with Ahlstrom R338 epoxysilanes; StarRov® 086 (Johns Manville) multi-compatible wires bonded with soft silane; OCV™ 366, SE 1200, and R25H (Owens Corning) multi-compatible wiring; OCV™ SE 1500 and 2350 (Owens Corning) epoxy compatible wires; and Jushi Group's multi-compatible glass wires (type 752, type 396, type 312, type 386). Additional polymer fibers and fabrics may include without limitation one or more of polyester, polyamide (eg, NYLON polyamide available from EI DuPont, aromatic polyamide (such as, aromatic polyamide KEVLAR available from EI DuPont, or aromatic polyamide P84 available from Lenzing Aktiengesellschaft), polyimide (eg KAPTON polyimide available from EI DuPont, polyethylene (eg DYNEEMA polyethylene from Toyobo Co., Ltd.) Additional suitable carbon fibers may include without limitation: AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42/850 with Hexcel Corporation; TORAYCA T300, T300J, T400H, T600S, T700S, T700G, T800H, T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J, M30S, M30G and M40 from Toray Industries, Inc.; HTS12K/24K, G30-500 3k/6K/12K, G30-500 12K, G30-700 12K, G30-7000 24K F402, G40-800 24K, STS 24K, HTR 40 F22 24K 1550tex with Toho Tenax, Inc.; 34-700, 34-700WD, 34-600, 34-600WD, and 34-600 unglued with Graphil Inc.; T-300, T-650/35, T-300C, and T-650/35C from Cytec Industries.
[170] Other suitable fillers include, for example, metallic density modulators, microparticle density modulators such as, for example, microspheres, and macroparticulate density modulators such as, for example, glass or ceramic spheres. Metallic density modulators include, but are not limited to, powdered, sintered, sintered, scraped, flaked, filled, particulate, or granulated metals, metal oxides, metal nitrides, and/or metal carbides, and similar. Preferred metal density modulators include, but are not limited to, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Microparticle density modulators include, but are not limited to, glass, metal, thermoplastic (or expandable or pre-expanded) or thermoset, and/or ceramic/silicate microspheres. Macroparticulate density modulators include, but are not limited to, glass, plastic, or ceramic spheres, metal bars, pieces, parts, or trim, hollow glass, ceramic, plastic, or metallic spheres, spheres, or tubes. , and the like.
[171] The invention is also directed to articles made from a resin composition comprising a cyclic olefin, an olefin metathesis catalyst, such as a ROMP catalyst, the adhesion promoter, and a substrate material , such as, for example, a glass substrate material; a cyclic olefin, an olefin metathesis catalyst, such as a ROMP catalyst, the adhesion promoter, and the hydroperoxide gel modifier, and a cyclic olefin, an olefin metathesis catalyst, such as a catalyst for ROMP, and the hydroperoxide gel modifier. Articles may include, but are not limited to, those formed by conventional manufacturing techniques, including casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), transfer molding resin (RTM), pouring, vacuum impregnating, surface coating, filament winding, and other methods known to be useful for producing polymer articles. Molded parts include, but are not limited to, reaction injection molding, resin transfer molding, and vacuum assisted resin transfer molding. Furthermore, the compositions and articles of manufacture of the invention are not limited to a single polymer surface interface, but also include multilayers and laminates containing multiple polymer-surface interfaces. The invention is also suitable for manufacturing articles by infusing the resin into a porous material. Such porous materials include, but are not limited to, wood, cement, concrete, reticulated and open-cell foams and sponges, papers, cardboard, felts, ropes or braids of natural or synthetic fibers, and various sintered materials. In addition, other fabrication techniques include, without limitation, cell casting, dip casting, continuous casting, dipping, potting, encapsulating, film casting or solvent casting, closed casting, mold casting, slurry casting, extrusion , mechanical foam, chemical foam, physical foam, compression molding or matched dip molding, spraying, Vacuum Resin Transfer Assisted Molding (VARTM), Seeman Process Composite Resin Infusion Molding (SCRIMP), blow molding , mold coating, painting or mold injection, vacuum forming, Reinforced Reaction Injection Molding (RRIM), Structural Reaction Injection Molding (SRIM), Thermal Expansion transfer molding (TERM), recirculating injection molding resin (RICM), controlled atmospheric pressure resin infusion (CAPRI), hand rolled. For fabrication techniques that require the use of a RIM or collision style mixing head, including, without limitation, RIM, SRIM, and RRIM, articles of fabrication may be molded using a single mixing head or a plurality of mixing heads, as well as a plurality of material injection streams (eg two resin streams and one catalyst stream).
[172] Furthermore, the invention is also directed to articles made from a resin composition comprising a cyclic olefin and an adhesion promoter, wherein the resin composition is combined with an olefin metathesis catalyst, and the resulting resin composition is applied to a substrate, which may be, for example, a substrate functionalized, such as, for example, a substrate functionalized with heteroatoms, such as, for example, an amino-functionalized substrate.
[173] In addition, the present invention also allows for the molding of articles of manufacture of any configuration, weight, size, thickness, or geometric shape. Examples of articles of manufacture include, without limitation, any article molded or shaped for use as an aerospace component, a marine component, an automobile component, a sporting goods component, an electrical component, an industrial component, a medical component, or military component. In one embodiment an article may be a turbine component used in aircraft or power generation in general. In one embodiment, turbine components may include, without limitation, one or more of an inlet, a pylon, a pylon fairing, an acoustic panel, a reliable reversing panel, a fan blade, a fan containment housing, a bypass duct, an aerodynamic hood, or an airfoil component. In one embodiment, an article can be a turbine blade component or it can be a turbine blade. In one embodiment, an article may be a wind rotor blade, tower, mast cap, tower or nacelle for wind turbines. In one embodiment, an article can be a component of air structures. Examples of aerospace components may include, without limitation, one or more fuselage skin, wing, fairing, doors, access panel, aerodynamic control surfaces, or stiffner. In one embodiment, an article can be an automobile component. Examples of automobile components may include, without limitation, one or more of the body panels, fender, spoiler, truck bed, guard plate, hood, longitudinal rail, pillar, or door. Examples of industrial components may include, without limitation, one or more of the riser platforms, oil and gas impact protection structures; bridges, pipes, pressure vessels, power poles, coils, containers, reinforcement structures for concrete architectures and roads or radiators. Examples of electrical components may include, without limitation, one or more articles of winding, such as coils of electric motors. In one embodiment, an article may be an eddy current shielding component of a magnetic resonance imaging system or shielding component for any electromagnetic radiation. In one embodiment, an article may be a military component, including, without limitation, ballistics resistant armor for people or vehicles, or ballistics resistant structures to protect personnel or equipment. In one embodiment, an article may be a sporting goods component, including, without limitation, an arrow, a tennis racket frame, a hockey stick, compound bow members, or a golf club shaft.
[174] Resin compositions according to the invention may further comprise a sizing composition, or be used to provide better substrate adhesion of materials that are bonded with certain commercial silanes commonly used in industry. As is known in the art, glass fibers are typically treated with a chemical solution (e.g., a sizing composition) shortly after their formation to reinforce the glass fibers and protect the mechanical integrity of the strands during processing and composite fabrication. Sizing treatments compatible with olefin metathesis catalysts and polydicyclopentadiene compounds have been described in U.S. Pat. 6,890,650 and 6,436,476, the disclosures of both of which are incorporated herein by reference. However, these disclosures are based on the use of specialty silane treatments that are not commonly used in industrial glass manufacturing. By comparison, the present invention can provide improved mechanical properties for polymer-glass composites, which are bonded with silanes commonly used in industry.
[175] Glass sizing formulations typically comprise at least one film-forming agent (typically a film-forming polymer), at least one silane, and at least one lubricant. All components of a sizing formulation that do not interfere with, or substantially reduce, the effectiveness of the metathesis catalyst or olefin polymerization reaction are considered to be compatible with the present invention and can generally be used herein.
[176] Film formers that are compatible with ROMP catalysts include epoxies, polyesters, polyurethanes, polyolefins, and/or polyvinyl acetates. Other common film formers that do not adversely affect the performance of the olefin metathesis catalyst can also be used. Film formers are typically used as non-ionic aqueous emulsions. More than one film-forming agent can be used in a given sizing formulation to achieve a desirable balance of glass processability and composite mechanical properties.
[177] More particularly, the film former may comprise a low molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer with an epoxy group average molecular weight (EEW) of less than 500, and/ or a high molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer with an epoxy group average molecular weight (EEW) of more than 500. Examples of suitable low molecular weight products include aqueous epoxy emulsions produced by Franklin International, including Franklin K8-0203 (PEE 190) and Franklin E-102 (EEW 225-275). Other examples of low molecular weight epoxy emulsions are available from Hexion, including EPI-REZ™ 3510-W-60 (EEW 185-215), and EPI-REZ™ 3515-W-60 (EEW 225-275). Other examples of low molecular weight epoxy emulsions are available from COIM, including Filco 309 (EEW 270) and Filco 306 (EEW 330). Other examples of low molecular weight epoxy emulsions are available from DSM, including Neoxil® 965 (EEW 220-280) and Neoxil® 4555 (EEW 220260). Examples of suitable high molecular weight epoxy emulsion products include epoxy emulsions produced by Hexion, including REZ™ 3522-W-60 (EEW 615-715).
[178] Aqueous emulsions of modified epoxys, polyesters and polyurethanes can also be used in the film former. Examples of suitable modified epoxy products include emulsions produced by DSM, including Neoxil® 2626 (a plasticized epoxy with an EEW of 500-620), Neoxil® 962/D (an epoxy ester, with an EEW of 470-550 ), Neoxil® 3613 (an epoxy-ester, with an EEW of 500-800), Neoxil® 5716 (an epoxy-novolac with an EEW of 210-290), Neoxil® 0035 (a plasticized epoxy-ester with an EEW of 2500), and Neoxil® 729 (an epoxy lubricated with an EEW of 200-800). Other examples of modified epoxy emulsions are available from COIM, including Filco 339 (an unsaturated epoxy polyester with an EEW of 2000) and Filco 362 (an epoxy-ester with an EEW of 530). Examples of suitable polyester products include emulsions produced by DSM, including Neoxil® 954/D, Neoxil® 2635, and Neoxil® 4759 (bisphenolic unsaturated polyesters). Additional suitable DSM products include Neoxil® 9166 and Neoxil® 968/60 (adipate polyesters). Other examples of suitable products include emulsions produced by COIM, including Filco 354/N (unsaturated bisphenolic polyester), Filco 350 (unsaturated polyester), and Filco 368 (saturated polyester). Examples of suitable polyurethane products include emulsions produced with Bayer Material Science, including Baybond® 330 and Baybond® 401.
[179] The film former can also include polyolefins or polyolefin-acrylic copolymers, polyvinylacetates, modified polyvinylacetates, or polyolefin-acetate copolymers. Suitable polyolefins include, but are not limited to, polyethylenes, polypropylenes, polybutylenes and copolymers thereof, and the polyolefins can be oxidized, malleable, or otherwise treated for effective use of the above film. Examples of suitable products include emulsions produced by Michelman, including Michem® Emulsion 91735, Michem® Emulsion 35160, Michem® 42540 Emulsion, Michem® 69230 Emulsion, Michem® 34040M1 Emulsion, Michem® Prime 4983R, and Michem® Prime 4982SC. Suitable products include emulsions produced by HB Fuller, including PD 708H, PD 707, and PD 0166. Additional suitable products include emulsions produced by Franklin International, including Duracet® 637. Additional suitable products include emulsions produced by Celanese, including Vinamul® 8823 (plasticized polyvinyl acetate), DurO-Set® E-200 (ethylene-vinyl acetate copolymer), Dur-O-Set® TX840 (ethylene-vinyl acetate copolymer), and Resyn® 1971 (ethylene-vinyl acetate copolymer). epoxy-modified polyvinyl).
[180] While not limited to these, preferred film formers include low and high molecular weight, saturated and unsaturated epoxies, polyesters and polyolefins such as Franklin K80-203, Franklin E-102, Hexion 3510-W-60, Hexion 3515-W-60, and Michelman 35160.
[181] Non-ionic lubricants can also be added to the sizing composition. Suitable nonionic lubricants that are compatible with the ROMP compositions include polyethylene glycol esters and ethylene oxide propylene oxide block copolymers. More than one non-ionic lubricant can be used in a given sizing formulation, if at all, for example, to achieve a desirable balance of glass processability and composite mechanical properties.
[182] Suitable lubricants can contain polyethylene glycol (PEG) units with an average molecular weight between 200 and 2000, preferably between 200600. These PEG units can be esterified with one or more fatty acids, including oleate , tallate, laurate, stearate, and others. Particularly preferred lubricants include PEG 400 dilaurate, PEG 600 dilaurate, PEG 400 distearate, PEG 600 distearate, PEG 400 dioleate, and PEG 600 dioleate. Examples of suitable products include compounds produced by BASF, including MAPEG® 400 DO, MAPEG® 400 DOT, MAPEG® 600 DO, MAPEG® 600 DOT, and MAPEG® 600 DS. Suitable products include compounds produced by Zschimmer & Schwarz, including Mulsifan 200 DO, Mulsifan 400 DO, Mulsifan 600 DO, Mulsifan 200 DL, Mulsifan 400 DL, Mulsifan 600 DL, Mulsifan 200 DS, Mulsifan 400 DS, and Mulsifan 600 DS. Suitable products include compounds produced by Cognis, including Agnique® PEG 300 DO, Agnique® PEG 400 DO, and Agnique® PEG 600 DO.
[183] Suitable nonionic lubricants also include block copolymers of ethylene oxide and propylene oxide. Examples of suitable products include compounds produced by BASF, including Pluronic® L62, Pluronic® L101, Pluronic® P103, and Pluronic® P105.
[184] Cationic lubricants can also be added to the sizing composition. Cationic lubricants that are compatible with ROMP include modified polyethyleneimines such as Emery 6760L produced by Pulcra Chemicals.
[185] The ylane coupling agent may optionally be added to the sizing composition, including non-limiting examples, methacrylate, acrylate, amino, or epoxy-functionalized silanes, along with alkyl, alkenyl, and norbornenyl silanes.
[186] Optionally, the sizing composition can contain one or more additives to modify the pH of the sizing resin. A preferred pH modifier is acetic acid.
[187] The sizing composition may optionally contain other additives useful in glass sizing compositions. Such additives can include emulsifiers, defoamers, co-solvents, biocides, antioxidants and other additives intended to improve the effectiveness of the sizing composition. The sizing composition can be prepared by any method applied to the substrate and materials for use in the present invention, such as fiber or glass fabric, by any technique or method.
[188] In a preferred embodiment, the metathesis reactions disclosed herein are carried out under an inert dry atmosphere. Such an atmosphere can be created using any inert gas, including gases such as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions carried out under an inert atmosphere are typically carried out with relatively low catalyst loading. The reactions disclosed herein may also be carried out in an atmosphere containing oxygen and/or containing a water, and in one embodiment, the reactions are carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, require the use of higher catalyst loads compared to reactions carried out under an inert atmosphere. Wherever the vapor pressure of the reactants allows, the reactions disclosed here can also be carried out under reduced pressure.
[189] The reactions disclosed here can be carried out in a solvent, and any solvent that is inert towards cross-metathesis can be employed. Generally, solvents that can be used in metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Examples of solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. In a preferred embodiment, the reactions described in this document are carried out neat, that is, without the use of a solvent.
[190] It will be appreciated that the temperature at which a metathesis reaction according to the methods described herein is carried out can be adjusted as needed, and can be at least about -78°C, 40°C, -10°C, 0°C, 10°C, 20°C, 25°C, 35°C, 50°C, 70°C, 100°C, or 150°C, or the temperature may be in a range which has any of these values as the upper or lower bounds. In a preferred embodiment, the reactions are carried out at a temperature of at least about 35°C, and in another preferred embodiment, the reactions are carried out at a temperature of at least about 50°C. EXPERIMENTAL
[191] In the following examples, efforts have been made to ensure accuracy with respect to the numbers used (eg, quantities, temperature, etc.), but some experimental errors and deviations must be accounted for. Unless otherwise noted, temperature is in degrees C and pressure is or is close to atmospheric.
[192] The following examples are to be considered as not being limiting of the invention as described herein, and instead are provided as representative examples of the adhesion promoters and gel modifying compositions of the invention and methods for their use. EXAMPLES Materials and Methods
[193] All glassware was oven dried and reactions were carried out under ambient conditions, unless otherwise indicated. All solvents and reagents were purchased from commercial suppliers and used as received, unless otherwise noted.
[194] Dicyclopentadiene (Ultrene® 99) (DCPD) was obtained from Cymetech Corporation. Modified DCPD base resin containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologues) was prepared by heat treating Ultrene® 99 as generally described in U.S. 4,899,005.
[195] Solid MDI (4,4'--methylene diphenyl diisocyanate) was used as received from Sigma Aldrich (98% purity). Liquid MDI (50/50 blend of 4.4'--MDI and 2,4'-MDI) was used as received from Bayer Material Science (Mondur® ML). Hexamethylenediisocyanurate (hexamethylenediisocyanatotrimer, HDIt, CAS# 3779-63-3) was used as received from Bayer MaterialScience Science (Desmodur® N3300A). HDI (hexamethylenediisocyanate or diisocyanatohexane, CAS#822-06-0) was used as received from Sigma Aldrich (98% purity), Acros Organics (99 +% purity), TCI America (98 % purity), or Bayer Material Science ((Desmodur® H, 99.5% purity). Isophorone diisocyanate (IPDI) was used as received from Sigma Aldrich (98% purity). tetramethylxylylene diisocyanate (TMXDI®) was used as received from Cytec H12MDI (4,4'-methylenebis (cyclohexyl isocyanate) was used as received from Sigma Aldrich (90% purity) Polymeric MDI (PM200 ) was used as received from Yantai Wanhua Polyurethane Company Lupranate® 5080 (MDI prepolymer), Lupranate® MI (liquid MDI), and Lupranate® MM103 (4,4'-MDI modified by liquid carbodiimide) were used as received from BASF. In addition, 4-benzylphenyl isocyanate (CAS# 1823-37-6, 97% purity) and 2 biphenylyl isocyanate (CAS# 17337-13-2, 98% purity) were used such as o received from Sigma Aldrich.
[196] NB-MeOH (5-norbornene-2-methanol, CAS#95-12-5) was used as received from Sigma Aldrich or prepared by literature methods. HENB (2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) was prepared by literature methods. Allyl alcohol, 2-ethyl hexanol, and 1-octanol were used as received from Sigma Aldrich. DCPD-OH (dicyclopentadiene alcohol) was used as received by Texmark.
[197] Metathesis catalysts were prepared by conventional methods and include [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium (II) (C827), ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclohexylphosphine) (C801), ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601) , [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(tri(n-butyl)phosphine) ruthenium (II) (C771), and [1,3-bis -(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(tri(n-butyl)phosphine) ruthenium (II) (C871). Antioxidant Ethanox® 4702 (4,4'methylenebis (2,6-ditertiary-butylphenol), Albemarle Corporation) was used where indicated.
[198] Cumene hydroperoxide (CHP) was used as received from Sigma Aldrich (88% purity unless otherwise noted) or Syrgis Performance Initiators (Norox® CHP, 85%). CHP was added to the resin formulations as a 1000 ppm concentration stock solution in DCPD. Tert-butyl hydroperoxide was used as received from Sigma Aldrich (5.5 M solution in decane). mCPBA (3-chloroperoxybenzoic acid), benzoyl peroxide (97% purity), di-tert-butyl peroxide (98% purity), and tri-n-butylphosphine (TNBP) were used as received from Sigma Aldrich . Triphenylphosphine (TPP) was used as received from Arkema. In addition, the mineral oil used to prepare the catalyst slurries was Crystal Plus 70FG.
[199] Glass yarns and fabrics were used as supplied by Ahlstrom (R338-2400), Johns Manville (Star ROV®-086), Owens Corning (OCV 366-AG-207, R25H-X14-2400, SE1200 -207, SE1500-2400, SE2350-250), and PPG (Hybon® 2002, Hybon® 2026). Toho Tenax® HTR40 carbon fiber spinning was used as received.
[200] Additives to resin are reported in ppm, which is defined as the weight in grams of additive per million grams of resin, or as phc, which is defined as the weight in grams of the additive per hundred grams of resin.
[201] The spinning wrap composites were prepared using a small-scale variation of a hand-rolling technique. The glass spin was saturated with catalyzed dicyclopentadiene resin and dipped into a 1/4" x 6" bar mold under moderate tension. The bar mold was compressed to achieve a fiber volume of approximately 50% at 1/8" thick, and made with C-clamps during the oven curing process. The composites in the spinning wrap were heated from that temperature ambient up to 120°C at 1°C/min, and kept at 120°C for two hours.
[202] The composite glass laminates were prepared using the VARTM process. The laminate was constructed by cutting and arranging the glass fabric screens over an aluminum tool to achieve approximately 50% fiber volume at 1/8” of thickness. A rigid plate was placed on top of the layer stack to ensure that pressure was applied evenly across the surface. Using braided tubes, an infusion inlet and outlet vent was properly positioned close to the glass tissue. A sheet of vacuum bagging film and sticky tape was used to create an airtight cap over the glass and tube and evacuated to a vacuum level of between 25 inches Hg to 28 inches Hg. A mixture of resin and catalyst was degassed under vacuum for 15 minutes and then refilled with argon. The mixture was then infused into the glass tissue, due to the pressure gradient between ambient pressure and the evacuated glass tissue assembly. After infusion was completed, the composite laminate was heated from room temperature to 75°C at a heating rate of 1°C/min, and then the composite laminate was heated to 120°C and held at that temperature for two hours.
[203] Gel modifier ppm is defined as the grams of gel modifier per million grams of resin. Fixes for gel modifier purity were made. With respect to other formulation additives, PHR is defined as the weight of the additive per hundred grams of base resin.
[204] Viscosity profiles were measured on a Brookfield LVDVII viscometer, and the data were analyzed by Wingather V3.0-1 software. Measurements were made with Axis#1 set to 50 RPM on 400 g of samples equilibrated to 20-25°C. Data points were recorded at intervals of two seconds to two minutes, depending on the experimental scale time. Temperatures were measured using J-type thermocouples, sampling at five second intervals and collected by Omega 2.0 OM-CP series data logging software.
[205] Mechanical properties were measured using standard techniques. All values shown are the average of 3 samples. The interlaminar shear strength (ILSS) at 10% strain was measured by the short beam shear method according to ASTM D2344 on 1" x 1/4" x 1/8" samples. ILSS values were reported in units of pounds per square inch (psi). Interlaminar shear strength (ILSS) is a measure of adhesion and/or compatibility between polymer matrix and fiber reinforcement in a composite. The following criteria, based on values of interlaminar shear strength, were used to characterize adhesion and/or compatibility between the polymer matrix and carbon fiber or glass reinforcement materials. Composites that have poor adhesion and/or compatibility between the polymer matrix and fiber reinforcement have been characterized as having ILSS values of less than about 3000 psi, suggesting a lack of covalent adhesion between the polymer matrix and the fiber reinforcement. between the polymer matrix and the fiber reinforcement were characterized as having ILSS values of about 3000 psi to about 6000 psi suggesting minimal or no covalent adhesion between the polymer matrix and the fiber reinforcement. Composites that have superior adhesion and/or compatibility between the polymer matrix and fiber reinforcement have been characterized as having ILSS values greater than about 6000 psi, suggesting a high degree of covalent adhesion between the polymer matrix and the fiber reinforcement. The heat deflection temperature was measured according to ASTM D648 on 5" x %" x %" samples. Peak bending strength and bending modulus were tested according to ASTM D790 using 5 samples. "x%" x%". The impact strength of the Izod pendulum was tested in accordance with ASTM D526 using samples of 2.5" x %" x %". All samples were stored and tested under ambient conditions. Synthesis of HENB (2-Hydroxyethyl Bicycle [2.2. 1] hept-2-ene-5-carboxylate)
[206] HEA (2-hydroxyethyl acrylate) (640 g, 1.0 mol eq.) was added to a 3L round bottom flask containing toluene (1 kg). DCPD (dicyclopentadiene) (1.5 kg) was added to a separate 3L round bottom flask, and the 3L flask containing DCPD was affixed with a Vigreaux column and distillation head connected to a condenser. The 3L flask containing HEA and toluene was connected to the condenser. DCPD was heated to >160°C under an inert atmosphere to "break down" the DCPD to form CPD (cyclopentadiene). CPD (740 g, 2.0 eq) was added dropwise to the HEA/toluene mixture at 10-40°C under an inert atmosphere. Conversion from HEA to HENB (2-hydroxyethyl bicyclo[2.2.1] hept-2-ene-5-carboxylate) was monitored by GC (gas chromatography). Toluene and reformed DCPD (364 g) were removed from the reaction mixture by vacuum distillation to yield the desired HENB product as a colorless liquid (1004 g, quantitative yield, approx. 98% purity). Examples 1(a-l)-4(a-l) Spinning Composites Prepared with Isocyanate Adhesive Agents
[207] The resin was prepared using the modified DCPD (containing 2025% tricyclopentadiene), 20 ppm CHP, 2 phr of Ethanox® 4702 antioxidant, and 2 phr of the appropriate isocyanate adhesion promoter. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. Wire-wrapped composites based on glass spinning (Examples 1 (a-1) PPG2002; Examples 2 (a-1) PPG2026; Examples 3 (a-1) Ahlstrom R338-2400; Examples 4 (a-1) from Star ROV®-086) were saturated with the catalyzed dicyclopentadiene resin and layered in a 1/4" x 6" bar mold under moderate tension. The bar mold was compressed to approximately 50% fiber volume at 1/8" thick, and clamped with C-clamps during the oven curing process. The spin-wrapped composites were heated from room temperature to 120°C °C at 1 °C/min, and kept at 120 °C for two hours. The ILSS of the resulting composites were measured (Table 1) Samples without adhesion promoter (Examples 1a, 2a, 3a, 4a) all had weak Mechanical properties Generally, all of the adhesion promoters tested improved the mechanical properties of the PPG2026 composites. Several adhesion promoters improved the mechanical properties of all four test composites: 4,4'-MDI(c), the blend of 4 ,4'-MDI/2,4'-MDI (b), and hexamethylenediisocyanurate (HDIt, d) (Table 1).
[208] The “untested” samples were damaged during manufacture so that ILSS cannot be evaluated. Examples 5(a-h)-8(a-h) Spinning Composites Prepared with Isocyanate and HENB Adhesive Agents
[209] The resin was prepared using the modified DCPD (containing 2025% tricyclopentadiene), 20ppm CHP, 2phr Ethanox® 4702 antioxidant, 2phr suitable diisocyanate adhesion promoter, and 2phr HENB. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. Glass-spun-wrapped composites (Examples 5 (ah) PPG2002; Examples 6 (ah) PPG2026; Examples 7 (ah) Ahlstrom R338-2400; Examples 8 (ah) Star ROV®-086) were prepared as described in Example 1. The ILSS of the resulting composites were measured (Table 2). In most cases, the addition of HENB further improved the mechanical properties of the resulting composites compared to those using the diisocyanate adhesion promoter alone (1b-1h, 2h-2b, 3b-3h, and 4h-4b from Table 1). HENB Alone does not improve adherence (5h-8h). Examples 10(a-f); 11(a-f) Spinning Composites Prepared with Isocyanate Adhesive Agents
Exemplos 12(a-g)-15(a-g) Compósitos de fiação Preparados com HDIt Promotor de adesão e Various Alcohols[210] The resin was prepared using the modified DCPD (Containing 2025% tricyclopentadiene), 20ppm CHP, 2phr Ethanox® 4702 antioxidant, and either 2phr 4.4'-MDI/2.4'-MDI (Examples 10(af)) or HDIt (Examples 11(af)) of diisocyanate adhesion promoter. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. The spinning wrapped composites based on glass spinning were prepared as described in Example 1. The ILSS of the resulting composites were measured (Tables 3 and 4). 4,4'-MDI/2,4'-MDI and HDIt are effective adhesion promoters for all yarns tested, which were indicated for use with epoxy resins. Examples 12(ag)-15(ag) Spinning composites Prepared with HDIt Adhesion Promoter and Various Alcohols
[211] The resin was prepared using the modified DCPD (Containing 2025% tricyclopentadiene), 20 ppm CHP, 2 phr of Ethanox® 4702 antioxidant, 2 phr of HDIt adhesion promoter, and 2 phr of various alcohols. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. The spinning wrapped composites based on glass spinning (Examples 12 (ag) PPG2002; Examples 13 (ag) PPG2026; Examples 14 (ag) Ahlstrom R338-2400, Examples 15 (ag) Star ROV®-086) were prepared as described in Example 1. The ILSS of the resulting composites were measured (Table 5). Examples 16(a-f)-19(a-f) Composite Spinnings with 1 phr Adhesion Promoter
Exemplos 20(a-k)-23(a-k) Fiações de Compósito com Várias cargas de Promotor de Adesão e HENB[212] Resin was prepared using DCPD (containing 20-25% tricyclopentadiene), 20 ppm CHP, 2phr Ethanox® 4702 antioxidant, 4,4'-MDI/2.4'-MDI or HDIt adhesion promoter, and 1 phr of optional alcohol compounds. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. The spinning wrapped composites based on glass spinning (Examples 16(af) PPG2002; Examples 17(af) PPG2026; Examples 18(af) Ahlstrom R338-2400, Examples 19(af) Star ROV®-086) were prepared as described in Example 1. The ILSS of the resulting composites were measured (Table 6). At 1 phr, 4,4'-MDI/2.4'-MDI was an effective adhesion promoter, and the addition of 1 phr of HENB or NBMeOH improved adhesion promoter performance. HDIt improved the composite properties significantly for PPG 2026 and Ahlstrom R338-2400 and slightly for both spins (PPG 2002 and Star-ROV-086). Addition of HENB and NBMeOH improved adhesion promoter effectiveness (Table 6). Examples 20(ak)-23(ak) Composite Spinnings with Various Loads of Adhesion Promoter and HENB
Exemplos 24(a-d)-26(a-d) VARTM com Promotor de Adesão e tecidos Comerciais[213] The resin was prepared using the modified DCPD (containing 2025% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox® 4702 antioxidant, 0.1,0.5, or 2 phr MDI adhesion promoter ( 4.4'-MDI/2.4'-MDI), and 0, 0.1, 0.5, 1, or 2 phr of HENB. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. Spun-wrapped composites based on glass spinning (Examples 20 (ak) PPG2002; Examples 21 (ak) PPG2026; Examples 22 (ak) Ahlstrom R338 -2400; Examples 23 (ak) Star ROV®-086) were prepared using a small scale variation of a hand laminating technique. The glass spin was saturated with catalyzed dicyclopentadiene resin and dipped into a 1/4" x 6" bar mold under moderate tension. The bar mold was compressed to approximately 58% fiber volume at 1/8" thick, and clamped with C-clamps during the oven curing process. The spin-wrapped composites were heated from room temperature to room temperature to 120°C at 1°C/min, and held at 120°C for two hours The ILSS of the resulting composites was measured (Table 7). Examples 24(ad)-26(ad) VARTM with Adhesion Promoter and Commercial Fabrics
Exemplo 27(a-c): Compósito Unidirecional Envolto com Fibra de Carbono [214] Modified DCPD (containing 20-25% tricyclopentadiene) was formulated with 20ppm CHP, 2phr Ethanox® 4702 antioxidant, 2phr 4.4'-MDI/2.4'-MDI, and with and without 2 phr of HENB (24 (a,b), 25 (a,b), 26 (a,b)). The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. VARTM samples were prepared using commercial unidirectional fabrics including Vectorply ELR 2410 fabric (made from PPG 2026 spin), fabric based on Ahlstrom R338, and fabric based on OC SE-1500. The laminated composites were cured at 120°C for 2 hours. The ILSS of the resulting composites were measured (Table 8). Modified DCPD (containing 2025% tricyclopentadiene) was formulated with 20ppm CHP, 2phr Ethanox® 4702 antioxidant, and 2phr 2-biphenylyl isocyanate (24(c)) or 2phr 4-isocyanate benzylphenyl (24(d)). The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. VARTM samples were prepared using commercial unidirectional Vectorply ELR 2410 fabric (made from PPG 2026 spinning). The ILSS of the resulting composites were measured (Table 8). Compositions containing diisocyanate (24(a,b), 25(a,b), 26(a,b)) showed superior adhesion, whereas compositions containing monoisocyanates (24c,24d) demonstrated poor adhesion. Example 27(ac): Carbon Fiber Wrapped Unidirectional Composite
Exemplo 28(a-e) VARTM com Promotor de Adesão e uma Faixa de Catalisadores[215] The resin was prepared using the modified DCPD (containing 2025% tricyclopentadiene), 20 ppm CHP, and 2 phr of Etanox® 4702 antioxidant. Samples without adhesion promoter (a), 2 phr of 4.4'-MDI/2.4'-MDI (b), and 2 phr of 4.4'-MDI/2.4'-MDI and 2 phr of HENB (c) were prepared. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. Carbon fiber trailer composites based on Toho Tenax® HTR40 were prepared as described in Example 1. The ILSS of the resulting composites were measured (Table 9). Isocyanate adhesion promoter is effective for carbon wires Example 28(ae) VARTM with Adhesion Promoter and a Range of Catalysts
[216] Modified DCPD (containing 20-25% tricyclopentadiene) was formulated with 2 phr of 4702 Etanox®, 2 phr of 4.4'-MDI/2.4'-MDI, and with the inhibitor described in Table 10 The resin was catalyzed by the addition of catalyst listed in Table 10 (ratio of monomer to catalyst between 5,000:1 and 45,000:1 as listed in Table 10), in mineral oil suspension. VARTM samples were prepared using commercial Vectorply ELR 2410 fabric (made from PPG 2026 spin). The ILSS of the resulting composites were measured (Table 10). For a variety of catalysts, the adhesion promoter improves the physical properties of the composites as compared to Example 2(a). Example 29 (a-h) VARTM with Adhesion Promoter and Carbon Fabric
Exemplos 30(a-f)-32(a-f): Compósitos de Fiação Preparados com Promotor de adesão 4,4'-MDI/2,4'- MDI e Vários Álcoois[217] The resin was prepared using the modified DCPD (containing 2025% tricyclopentadiene), 20 ppm CHP, and 2 phr of Etanox® 4702 antioxidant. The samples were prepared with different isocyanate adhesion promoter compositions. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. VARTM samples were prepared using Zoltek UD500 carbon cloth. The ILSS of the resulting composites were measured (Table 11). Examples 30(af)-32(af): Spinning Composites Prepared with 4.4'-MDI/2.4'-MDI Adhesion Promoter and Various Alcohols
Exemplo 33 Efeito de hidroperóxido de cumeno no início do estado de gel[218] The resin was prepared using the modified DCPD (containing 20-25% tricyclopentadiene), 20ppm CHP, 2phr Ethanox® 4702 antioxidant, 2phr 4.4'-MDI/2.4 adhesion promoter -MDI, and 2 phr of various alcohols. The resin was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. The spinning wrapped composites based on glass spinning (Examples 30(af) PPG2002; Examples 31(af) PPG2026; Examples 32(af) Star ROV®-086) were prepared as described in Example 1. The ILSS of the resulting composites were measured (Table 12). Example 33 Effect of cumene hydroperoxide on onset of gel state
Exemplo 34 Efeito de hidroperóxido de cumeno (CHP) no perfil de polimerização de DCPD[219] A 250 mL plastic beaker was loaded with 100 g of dicyclopentadiene base resin (containing 20-25% tricyclopentadiene) and 0-100 ppm cumene hydroperoxide (CHP) was added as a stock concentration solution 1000 ppm in resin. The beaker was placed in an oil bath, and a temperature probe was placed in the reaction vessel. Once the sample was equilibrated to the test temperature (30°C) the metathesis catalyst was added. Polymerizations 33a-33h were catalyzed by adding 9.6 mg of catalyst C827 dissolved in a mixture of 1 g of toluene and 2 g of mineral oil (ratio of monomer to catalyst 60000:1). The 33i-33m polymerizations were catalyzed by the addition of 19.2 mg of C827 catalyst suspended in 2 g of mineral oil (30,000:1 monomer to catalyst ratio). The temperatures of the reaction mixtures were monitored throughout the polymerizations. The exothermic time is related to the start of polymerization. The exothermic temperature of Pico is related to the completeness of the polymerization reaction. Lower peak temperatures are an indication of incomplete polymerization. The exothermic times and peak temperatures for the unmodified and modified polymerizations can be seen in Table 13. The increase in CHP concentrations in the resin resulted in an increase in the time to reach the polymerization exotherm, no significant loss in peak temperature exothermic. At both catalyst concentrations, in addition to CHP effectively modifying the start of polymerization, the delay time can be controlled over several hours by controlling the amount of CHP added. FIG. 1 shows the temperature profiles of examples 33a-33c, with 0, 2.5, and 5 ppm CHP. The gel modification of the invention is particularly useful because it increases the functional life of the catalyzed resin without otherwise necessarily changing the overall temperature profile of the polymerization. Example 34 Effect of Cumene Hydroperoxide (CHP) on DCPD Polymerization Profile
[220] Dicyclopentadiene base resin (containing 20-25% tricyclopentadiene) was filtered through alumina gel and activated silica to remove any contaminants. A 500 mL plastic beaker was loaded with 400 g of filtered resin as a control. The additional 500ml plastic beaker was loaded with 400 g of the filtered resin and 4, 25, or 100 ppm of cumene hydroperoxide (CHP) was added as a 1000 ppm concentration stock solution in resin. Each resin sample was equilibrated at a temperature of 23-25°C, and catalyzed by adding 9.6 mg of C827 suspended in 2 g of mineral oil. Viscosity profiles are shown in FIG. 2, where the cure profile of the filtered control sample is shown along with the cure profiles of CHP-modified resin compositions having CHP concentrations of 4, 25, and 100 ppm. The reaction modification of the present invention is especially useful as it extends the life of the workable mixture of the catalyzed resin and allows low viscosity characteristics to be retained for a long period of time. Example 35 Mechanical Properties of Unmodified and Modified PolyDCPD Plates
Exemplo 36 Esabilidade do armazenamento do modificador de gel de fosfina[221] To assess the mechanical properties of polydicyclopentadiene (polyDCPD) formulations, 200 g of dicyclopentadiene base resin (containing 20-25% tricyclopentadiene) was formulated with 2 PHR of Ethanox® 4702 antioxidant and 0-100 ppm of hydroperoxide of cumene, equilibrated at 30°C and catalyzed by the addition of 19.2 mg of C827 suspended in 2 g of mineral oil. After mixing, the catalyzed resin was poured into a 10x10x0.5" glass and aluminum mold and placed in a 40°C oven until exothermic reaction (Example 35a-d). After curing, the polyDCPD panels were cut to size. in samples for measuring Thermal Deflection Temperature (HDT, ASTM D648), Izod Pendulum Impact Strength (ASTM D526), and bending properties (ASTM D790) As shown in Table 14, there is no significant deviation in mechanical properties of the panel over a range of hydroperoxide-to-catalyst ratios Table 14: Effect of hydroperoxide gel modification on the mechanical properties of polyDCPD Example 36 Storage stability of phosphine gel modifier
[222] A resin formulation was prepared by mixing dicyclopentadiene base resin (containing 20-25% tricyclopentadiene) with 2 PHR of Ethanox® 4702 Antioxidant and 0.5 PHR of a 0.15% by weight solution of TNBP in dicyclopentadiene as the gel modifier. An exothermic test was carried out on a 100 g aliquot of this resin equilibrated at 40°C according to the procedure described in Example 33, using C771 as the olefin metathesis catalyst (15,000:1 monomer to catalyst ratio) dissolved in a mixture of 1 g of toluene and 2 g of mineral oil (Example 36a). The remainder of the stock formulation was sparged with nitrogen, and the solution was sealed and stored at room temperature. Additional exothermic tests were performed according to the procedure of Example 36a in 100 g aliquots at 4 hour, 8 hour, and 24 hour intervals (Examples 36b-36d). The effectiveness of phosphine in delaying the onset of polymerization dropped dramatically during these time intervals, with an almost complete loss of storage life span within 24 hours. (Table 15). Example 37 Storage stability of cumene hydroperoxide gel modifier
Tempo Exotérmico não modificado para esta resina foi de 10,9 minutos Exemplos 36a-36b: C771; razão de monômero para catalisador = 15.000:1; 40°C Exemplos 37a-37d: C827; razão de monômero para catalisador = 30.000:1; 30°C Exemplo 38 Modificação de Gel por outros hidroperóxidos (TBHP)[223] A stock resin formulation was prepared by mixing dicyclopentadiene base resin (containing 20-25% tricyclopentadiene) with 2 PHR of Ethanox® 4702 antioxidant and 23 ppm of cumene hydroperoxide in dicyclopentadiene as the modifier. reaction gel. An exothermic test was performed on a 100 g aliquot of this resin, equilibrated at 30°C according to the procedure described in Example 33, using 19.2 mg of C827 as the olefin metathesis catalyst (ratio of monomer to catalyst of 30,000:1) suspended in 2 g of mineral oil (example 37a). The remainder of the stock formulation was sparged with nitrogen, and the solution was sealed and stored at room temperature. Additional exothermic tests were carried out according to the procedure described in Example 37a at 100 g aliquots at intervals of 15 days (360 hours), 35 days (840 hours), and 90 days (2160 hours) (Table 15). Unlike standard phosphine gel modified resin (Example 36), the ability of cumene hydroperoxide to delay the onset of polymerization remains stable. The modified cumene hydroperoxide resin maintained 84% of the delayed exothermic time effect after 90 days, with no significant change in the peak exothermic temperature. Unmodified Exothermic Time for this resin was 10.9 minutes Examples 36a-36b: C771; ratio of monomer to catalyst = 15,000:1; 40°C Examples 37a-37d: C827; monomer to catalyst ratio = 30,000:1; 30°C Example 38 Gel Modification by Other Hydroperoxides (TBHP)
Exemplo 39 Modificação de gel de CHP de resinas com catalisadores de 1° geração[224] An exothermic test was performed according to the procedure described in Example 33, using 40°C as the resin and oil bath temperature. The resin was formulated with 0 - 21 ppm tert-Butyl hydroperoxide (TBHP), one and the polymerization reaction was catalyzed by the addition of 9.6 mg of C827 dissolved in a mixture of 1 g of toluene and 2 g of oil mineral (Examples 38a - 38e). The exothermic time and peak exothermic temperature can be seen in Table 16. The addition of increasing amounts of TBHP resulted in rise times reaching the polymerization exotherm and no significant loss in peak exothermic temperature. Table 16: Gel Modification by Tert-Butyl Hydroperoxide Example 39 CHP gel modification of resins with 1st generation catalysts
[225] An exothermic test was performed according to the procedure described in Example 33, using 0-100 ppm cumene hydroperoxide and resin equilibrated at 30°C. The polymerization reaction was catalyzed by the addition of first generation ruthenium metathesis catalyst C801 dissolved in a mixture of 1 g toluene and 2 g mineral oil (5,000:1 monomer to catalyst ratio) (Examples 39a-39d). The exothermic times and peak exothermic temperatures can be seen in Table 17. The addition of increasing amounts of CHP resulted in increasing times to reach the polymerization exotherm and no significant loss in peak exothermic temperature. Example 40 CHP gel modification of resin formulated with 2nd generation catalyst
Exemplo 41 Hidroperóxido gel modification at higher loadings[226] An exothermic test was performed according to the procedure described in Example 33, using 0-50 ppm cumene hydroperoxide and resin equilibrated at 60°C. The polymerization reaction was catalyzed by the addition of 2nd generation metathesis catalyst C771 dissolved in a mixture of 1 g of toluene and 2 g of mineral oil (ratio of monomer to catalyst 60,000:1) (Examples 40a-40d). The exothermic times and peak exothermic temperatures can be seen in Table 17. The addition of increasing amounts of CHP resulted in increasing times to reach the polymerization exotherm and no significant loss in peak exothermic temperature. Table 17: CHP gel modification using 1st and 2nd generation ruthenium catalysts Example 41 Hydroperoxide gel modification at higher loadings
Exemplo 42 Efeito de peróxido de benzoíla - peróxidos de diacila não são modificadores de Gel[227] Exothermic tests were carried out according to the procedure described in Example 33 using 0-5000 ppm CHP. The resin was equilibrated at 60°C to accelerate the polymerization rate. The polymerization reaction was catalyzed by the addition of 9.6 mg of metathesis catalyst C827 dissolved in a mixture of 1 g of toluene and 2 g of mineral oil (Examples 41a-d). Exothermic times and peak exothermic temperatures can be seen in Table 18. Comparison of exothermic times and peak exothermic temperatures shows the increase in time required to reach the polymerization exotherm, which demonstrates that the start of polymerization can be effectively retarded with high CHP:catalyst ratios if reaction conditions require. However, as hydroperoxide concentrations reach high levels, global exortemic peak temperatures begin to decline (Example 41c), demonstrating some negative impact of high cumene hydroperoxide levels on polymerization completion. Since the hydroperoxide loading becomes too high for a given setting of polymerization conditions, the polymerization will no longer be exothermic (Example 41d). The upper concentration limit for the effective use of hydroperoxide compounds as gel modifying agents will vary depending on the metathesis catalyst, olefin resin, and reaction conditions. However, as shown by Examples 33b-33g and Examples 41b-41d, there is a wide range of hydroperoxide:catalyst molar ratios that yield useful modification of the start of polymerization. The time required to reach gelling and cure states can be controlled over a wide range for a given polymerization. Table 18: Gel modification using higher concentrations of CHP Example 42 Effect of benzoyl peroxide - diacyl peroxides are not Gel modifiers
[228] Exothermic tests were carried out according to the procedure described in Example 33 using 0-2000 ppm benzoyl peroxide and resin equilibrated at 40°C. The polymerization reaction was catalyzed by the addition of metathesis catalyst C827 dissolved in a mixture of 1 g toluene and 2 g mineral oil (60,000:1 monomer to catalyst ratio) (Examples 42a-42f). Exothermic times and peak exothermic temperatures can be seen in Table 19. Increasing amounts of benzoyl peroxide did not result in any significant delay in polymerization initiation (exothermic time) to relatively large peroxide:catalyst ratios. At such extremely high concentrations of benzoyl peroxide, the exortemic peak temperature dramatically decreased. This indicates that the di-acyl peroxide functional group is not an effective gel modifier compared to the hydroperoxide functional group. Example 43 Effect of mCPBA - peroxycarboxylic acids are not gel modifiers
[229] Exothermic tests were carried out according to the procedure described in Example 42, with the addition of 20-2000 ppm of mCPBA (3-chloroperoxybenzoic acid) to the resin formulation, prior to the addition of catalyst (Examples 43a-43d). No significant exotherm delay was noted at any concentration of mCPBA (Table 19). The exothermic time accelerated a little, and the peak exothermic temperature dropped dramatically. This indicates that the peroxycarboxylic acid functional group does not act to moderate the onset of polymerization as the hydroperoxide functional group does. Example 44 Effect of di-tert-butyl peroxide - Dialkyl peroxides are not gel modifiers
Exemplos 45(a-c) e 46(a-c)[230] An exothermic test was performed according to the procedure described in Example 42, with the addition of 10,000 ppm of di-tert-butyl peroxide. Only a very small modification of the exotherm is observed, even with this high peroxide:catalyst ratio (Table 19). This indicates that the dialkyl peroxide functional group does not act in the same way in gel modification as the hydroperoxide functional group. Table 19: Gel Modification Using Other Peroxide Types Examples 45(ac) and 46(ac)
[231] The resin was prepared using modified DCPD (containing 2025% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox® 4702 antioxidant and either no adhesion promoter or no alcohol compound (examples 45a, 46a) , or 2 phr of diisocyanate adhesion promoter (4,4'-MDI/2,4'-MDI) (Examples 45b, 46b) or 2 phr of diisocyanate adhesion promoter (4,4'- MDI/2,4'-MDI) and 2 phr alcohol compound (HENB) (Examples 45c, 46c). The resin in Examples 45a and 46a was catalyzed by the addition of C827 (60,000:1 monomer to catalyst ratio) in a mineral oil suspension. The resin in Examples 45b, 46b, 45c, and 46c was catalyzed by the addition of C827 (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. VARTM samples were prepared using the following glass fabrics (Hexcel 7781-F12; no heat-cleaned silane coupling agents); (BGF 7781-497A; amino- and methacrylate-silane coupling agents only). The ILSS of the resulting composites were measured (Table 20). Heat-cleaned glass fabric without silane coupling agent (Hexcel 7781 -F12) demonstrated (i) poor adhesion without adhesion promoter and alcohol (Example 45a), (ii) moderate adhesion with adhesion promoter alone (Example 45b) ; and (iii) moderate adhesion with adhesion promoter and alcohol (Example 45c). Multicompatible glass with amino- and silane-methacrylate coupling agent only (BGF 7781-497A) demonstrated (i) moderate adhesion without adhesion promoter and alcohol (Example 46a), (ii) moderate adhesion with adhesion promoter only (Example 46b); and (iii) superior adhesion with adhesion promoter and alcohol (Example 46c). Commercially available glass fiber and/or fabric with a complete sizing composition (eg film formers, lubricants, silane coupling agents, etc.) showed poor adhesion without adhesion promoter and alcohol (Table 1. Examples 1a -4a), showed superior adhesion with adhesion promoter alone (Table 1. Examples 1b-4b &Table 8. Examples 24a -26a) and superior adhesion with adhesion promoter and alcohol (Table 2. Examples 5a-8a &Table 8. Examples 24b-26b).
[232] The resin was prepared with 150 grams of dicyclopentadiene (containing 20-25% tricyclopentadiene) and 2 phr of Ethanox® 4702 and either 20,000 ppm of di-tert-butyl peroxide (Examples 47a, 48a), or 20,000 ppm cumene hydroperoxide (Examples 47b, 48b), or 2000 ppm di-tert-butyl peroxide (Examples 47c, 48c), or 2000 ppm cumene hydroperoxide (Examples 47d, 48d), or without peroxide (Examples 47e, 48e ). The prepared resin was equilibrated at 30°C and combined with a C827 catalyst (30,000:1 monomer to catalyst ratio) in a mineral oil suspension. After mixing, the combined resin was poured into a 5" x 7" x 1/4" aluminum mold placed in a 30°C oven. Prior to exotherm, the uncured polymer was removed from the mold and then post-cured. for 2 hours at either 180°C or 200°C Examples 47b and 48b, containing 20,000 ppm cumene hydroperoxide did not polymerize after 18 hours at 30°C and therefore no Polymer sample was available for measuring the temperature of glass transition (Tg). The glass transition temperature. (Tg) was measured by thermal mechanical analysis (TMA) in accordance with ISO 11359-2 on 1/4" x 1/4" x 1/4 samples ”. Cumene hydroperoxide (CHP) (80% purity) was used as received from Sigma Aldrich. Di-tert-butyl peroxide (98% purity) was used as received from Sigma Aldrich.
NR= sem reação[233] The data in Table 21 shows that (i) alkyl hydroperoxides, such as CHP, are gel modifiers and dialkyl peroxides, such as di-tert-butyl peroxide, are not gel modifiers; and (ii) Dialkyl peroxides, such as di-tert-butyl peroxide, increase polymer crosslinking, resulting in higher Tg, and alkyl hydroperoxides, such as CHP, do not increase polymer crosslinking. butyl NR=no reaction
[234] It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, that the above description as well as the examples which follow are intended to illustrate and not to limit the scope of the invention. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention belongs.

权利要求:
Claims (24)
[0001]
1. Resin composition CHARACTERIZED in that it comprises: at least one cyclic olefin; at least one olefin metathesis catalyst; at least one adhesion promoter containing at least one compound containing at least two isocyanate groups and one compound containing a heteroatom-containing functional group and an active olefin with metathesis, and wherein the at least one compound containing at least two isocyanate groups is selected to from methylene-diphenyl MDI diisocyanate including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI; polymeric MDI; MDI prepolymer; and 4,4'-MDI modified by liquid carbodiimide, and wherein the compound containing a functional group containing heteroatom and a metathesis active olefin is selected from 5-norbornene-2-methanol (NB-MeOH); 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB); and allyl alcohol; and wherein the at least one cyclic olefin is not NB-MeOH or HENB.
[0002]
2. A method for improving adhesion of the resin composition as defined in claim 1 to a substrate material CHARACTERIZED in that it comprises: combining the adhesion promoter, the cyclic olefin and the olefin metathesis catalyst to form the composition of resin, contacting the resin composition with the substrate material, and subjecting the resin composition to conditions effective to promote a cyclic olefin olefin metathesis reaction.
[0003]
3. Use of at least one adhesion promoter as defined in claim 1, CHARACTERIZED by the fact that it is for adhering a polymerized metathesis resin composition to a substrate material.
[0004]
4. Resin composition according to claim 1, CHARACTERIZED by the fact that the cyclic olefin is selected from linear cyclic olefins (strained cyclic olefins) and non-linear cyclic olefins (unstrained cyclic olefins), or combinations thereof, wherein the cyclic olefin may contain a functional group, or be substituted with a group, selected from halogen, hydroxyl, hydrocarbyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy, alkoxycarbonyl, alkylcarbonate, arylcarbonate, carboxy, carboxylate, carbamoyl, alkyl substituted carbamoyl, haloalkyl substituted carbamoyl, aryl substituted carbamoyl, thiocarbamoyl alkyl substituted thiocarbamoyl, aryl substituted thiocarbamoyl, carbamido, cyano, cyanate, thiocyanate, amino, thioformyl alkyl substituted amino, aryl substituted amino, alkylamido, arylamido, imino, alkylimino, arylimino, nitro, nitroso, sulfo, sulfonate, alkyl 1sulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, alkylaminosulfonyl, arylsulfonyl, boryl, boron, boronate, phosphono, phosphonate, phosphinate, phospho, phosphine or a combination thereof.
[0005]
5. Resin composition according to claim 1, CHARACTERIZED by the fact that the cyclic olefin is selected from cyclobutene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclone-nadiene, cyclododecatriene, tetracyclododecadiene, substituted norbornenes , substituted dicyclopentadienes, dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5- phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 5,5,6-trimethyl-2-norbornene, cyclo- hexenylnorbornene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo,exo-5,6-dimethoxycarbonylnorbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2,3-dimethoxynorbornene, norbornadiene, tricycloundece - no, tetracyclododecene, 8-methyltetracyclododecene, 8-ethyl- tetracyclododecene, 8-cyanotetracyclododecene, pentacyclopentadecene or pentacyclohexadecene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene and 5-butenyl-2-norbornene.
[0006]
hidrocarbileno substituído, hidrocarbileno contendo heteroátomo ou hidrocarbileno contendo heteroátomo substituído; U é um elemento do Grupo 15 ou Grupo 16 carregado positivamente substituído com hidrogênio, hidrocarbil, hidrocarbil substituído, hidrocarbil contendo heteroátomo ou hidrocarbil contendo heteroátomo substituído; V é um contraíon carregado negativamente; e n é zero ou 1, em que quaisquer dois ou mais de X1, X2, L1, L2, L3, R1 e R2 podem ser tomados em conjunto para formar um ou mais grupos cíclicos, e ainda em que qualquer um ou mais de X1, X2, L1, L2, L3, R1 e R2 pode ser fixo a um suporte.6. Resin composition according to any one of claims 1, 4 and 5, CHARACTERIZED by the fact that the olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I) substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is zero or 1, where any two or more of X1, X2, L1, L2, L3, R1 and R2 can be taken together to form one or more cyclic groups, and further where any one or more of X1, X2, L1, L2, L3, R1 and R2 can be fixed to a bracket.
[0007]
7. Resin composition according to claim 6, CHARACTERIZED by the fact that at least one from L1, L2 and L3 is an N-heterocyclic carbene binder.
[0008]
em que, M é um metal de transição do Grupo 8; n é 0 ou 1; m é 0, 1 ou 2; k é 0 ou 1; X1 e X2 são independentemente selecionados a partir de ligantes aniônicos; L2 e L3 são independentemente selecionados a partir de ligantes neutros do- adores de elétrons ou podem ser tomados em conjunto para formar um único ligante heterocíclico doador de elétrons bidentado; R1 e R2 são independentemente selecionados a partir de hidrogênio, hidro- carbil, hidrocarbil substituído, hidrocarbil contendo heteroátomo, hidrocarbil contendo heteroátomo substituído e grupos funcionais; X e Y são independentemente selecionados a partir de C, N, O, S e P; p é zero quando X é O ou S, e p é 1 quando X é N ou P; q é zero quando Y é O ou S, e q é 1 quando Y é N ou P; Q1, Q2, Q3 e Q4 são independentemente selecionados a partir de hidrocarbi- leno, hidrocarbileno substituído, hidrocarbileno contendo heteroátomo, hidrocarbile- no contendo heteroátomo substituído, e -(CO)-, e ainda em que dois ou mais substi- tuintes em átomos adjacentes dentro de Q podem ser ligados para formar um grupo cíclico adicional; w, x, y e z são independentemente zero ou 1; e R3, R3A, R4 e R4A são independentemente selecionados a partir de hidrogênio, hidrocarbila, hidrocarbila substituída, hidrocarbila contendo heteroátomo e hidro- carbila substituída contendo heteroátomo, em que quaisquer dois ou mais de X1, X2, L2, L3, R1, R2, Q1, Q2, Q3, Q4, R3, R3A, R4 e R4A podem ser tomados em conjunto para formar um grupo cíclico e, ainda, em que qualquer um ou mais de X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4 e R4A podem ser fixados a um suporte.8. Resin composition according to any one of claims 1, 4 and 5, CHARACTERIZED by the fact that the olefin metathesis catalyst has the structure wherein, M is a Group 8 transition metal; n is 0 or 1; m is 0, 1 or 2; k is 0 or 1; X1 and X2 are independently selected from anionic binders; L2 and L3 are independently selected from neutral electron-donating ligands or can be taken together to form a single bidentate electron-donating heterocyclic ligand; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; X and Y are independently selected from C, N, O, S and P; p is zero when X is O or S, and p is 1 when X is N or P; q is zero when Y is O or S, and q is 1 when Y is N or P; Q1, Q2, Q3 and Q4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and -(CO)-, and further in which two or more atom substituents adjacents within Q can be linked to form an additional cyclic group; w, x, y and z are independently zero or 1; and R3, R3A, R4 and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and heteroatom-containing substituted hydrocarbyl, wherein any two or more of X1, X2, L2, L3, R1, R2 , Q1, Q2, Q3, Q4, R3, R3A, R4 and R4A can be taken together to form a cyclic group, and further wherein any one or more of X1, X2, L2, L3, Q1, Q2, Q3 , Q4, R1, R2, R3, R3A, R4 and R4A can be attached to a bracket.
[0009]
9. Resin composition according to claim 8, CHARACTERIZED by the fact that R1 and R2 are taken together to form an indenylidene portion.
[0010]
em que Q é um hidrocarbileno, hidrocarbileno substituído, hidrocarbileno contendo heteroátomo ou ligante de hidrocarbileno contendo heteroátomo substituído e ainda em que dois ou mais substituintes em átomos adjacentes dentro de Q podem ser ligados para formar um grupo cíclico adicional.10. Resin composition according to claim 8, CHARACTERIZED by the fact that M is ruthenium, w, x, y and z are zero, X and Y are N and R3A and R4A are bonded to the -Q- form, so that the complex has the structure wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.
[0011]
11. Resin composition according to any one of claims 1 and 4 to 10, CHARACTERIZED by the fact that it further comprises a substrate material.
[0012]
12. Resin composition according to claim 11, CHARACTERIZED by the fact that the substrate material is selected from reinforcement materials, glass fibers, glass fabrics, carbon fibers, carbon fabrics, aramid fibers , aramid fabrics, polyolefin fibers, polyolefin fabrics, polymer fibers or polymer fabrics.
[0013]
13. Method according to claim 2, CHARACTERIZED by the fact that the cyclic olefin is selected from cyclobutene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecatriene, tetracyclododecadiene, substituted norbornenes, substituted dicyclopentadienes, dicyclopentadienes tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2 norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene , 5-methoxycarbonylnorbornene, 5-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 5,5,6-trimethyl-2-norbornene, cyclohexenylnorbornene, endo, exo-5,6 -dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo,exo-5,6-dimethoxycarbonylnorbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2,3-dimethoxynorbornene, norbornadiene, tricycloundecene, tetracyclododecene, 8-methyltetracyclododecene, 8-ethyl-tetracyclododecene, 8- cyanotetarcyclododecene, pentacyclopentadecene or pentacyclohexadecene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5- vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene and 5-butenyl-2-norbornene.
[0014]
X ter a estrutura -(W)n-U+V’, em que W é selecionado a partir de hidrocarbileno, hidro- carbileno substituído, hidrocarbileno contendo heteroátomo ou hidrocarbileno contendo heteroátomo substituído; U é um elemento do Grupo 15 ou Grupo 16 carregado positivamente substituído com hidrogênio, hidrocarbil, hidrocarbil substituído, hi- drocarbil contendo heteroátomo ou hidrocarbil substituído contendo heteroátomo; V é um contraíon carregado negativamente; e n é zero ou 1, em que quaisquer dois ou mais de X1, X2, L1, L2, L3, R1 e R2 podem ser tomados em conjunto para formar um ou mais grupos cíclicos, e ainda em que qualquer um ou mais de X1, X2, L1, L2, L3, R1 e R2 podem ser fixados a um suporte.14. The method of claim 2, CHARACTERIZED by the fact that the olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I) X has the structure -(W)n-U+V', wherein W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or heteroatom-containing substituted hydrocarbyl; V is a negatively charged counterion; and n is zero or 1, where any two or more of X1, X2, L1, L2, L3, R1 and R2 can be taken together to form one or more cyclic groups, and further where any one or more of X1, X2, L1, L2, L3, R1 and R2 can be attached to a bracket.
[0015]
15. Method according to claim 14, CHARACTERIZED by the fact that at least one of L1, L2 and L3 is an N-heterocyclic carbene ligand.
[0016]
em que, M é um metal de transição do Grupo 8; n é 0 ou 1; m é 0, 1 ou 2; k é 0 ou 1; X1 e X2 são independentemente selecionados a partir de ligantes aniônicos; L2 e L3 são independentemente selecionados a partir de ligantes neutros doadores de elétrons ou podem ser tomados em conjunto para formar um único ligante heterocíclico doador de elétrons bidentado; R1 e R2 são independentemente selecionados a partir de hidrogênio, hidro- carbil, hidrocarbil substituído, hidrocarbil contendo heteroátomo, hidrocarbil substituído contendo heteroátomo e grupos funcionais; X e Y são independentemente selecionados a partir de C, N, O, S e P; p é zero quando X é O ou S, e p é 1 quando X é N ou P; q é zero quando Y é O ou S, e q é 1 quando Y é N ou P; Q1, Q2, Q3 e Q4 são independentemente selecionados a partir de hidrocarbi- leno, hidrocarbileno substituído, hidrocarbileno contendo heteroátomo, hidrocarbile- no contendo heteroátomo substituído, e -(CO)-, e ainda em que dois ou mais substi- tuintes em átomos adjacentes dentro de Q podem ser ligados para formar um grupo cíclico adicional; w, x, y e z são independentemente zero ou 1; e R3, R3A, R4 e R4A são independentemente selecionados a partir de hidrogênio, hidrocarbila, hidrocarbila substituída, hidrocarbila contendo heteroátomo e hidro- carbila substituída contendo heteroátomo, em que quaisquer dois ou mais de X1, X2, L2, L3, R1, R2, Q1, Q2, Q3, Q4, R3, R3A, R4 e R4A podem ser tomados em conjunto para formar um grupo cíclico e, ainda, em que qualquer um ou mais de X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4 e R4A podem ser fixados a um suporte.16. Method according to claim 2, CHARACTERIZED by the fact that the olefin metathesis catalyst has the structure wherein, M is a Group 8 transition metal; n is 0 or 1; m is 0, 1 or 2; k is 0 or 1; X1 and X2 are independently selected from anionic binders; L2 and L3 are independently selected from neutral electron-donating ligands or can be taken together to form a single, bidentate, electron-donating heterocyclic ligand; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, heteroatom-containing substituted hydrocarbyl, and functional groups; X and Y are independently selected from C, N, O, S and P; p is zero when X is O or S, and p is 1 when X is N or P; q is zero when Y is O or S, and q is 1 when Y is N or P; Q1, Q2, Q3 and Q4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and -(CO)-, and further in which two or more atom substituents adjacents within Q can be linked to form an additional cyclic group; w, x, y and z are independently zero or 1; and R3, R3A, R4 and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and heteroatom-containing substituted hydrocarbyl, wherein any two or more of X1, X2, L2, L3, R1, R2 , Q1, Q2, Q3, Q4, R3, R3A, R4 and R4A can be taken together to form a cyclic group, and further wherein any one or more of X1, X2, L2, L3, Q1, Q2, Q3 , Q4, R1, R2, R3, R3A, R4 and R4A can be attached to a bracket.
[0017]
17. Method according to claim 16, CHARACTERIZED by the fact that R1 and R2 are taken together to form an indenylidene moiety.
[0018]
em que Q é um hidrocarbileno, hidrocarbileno substituído, hidrocarbileno contendo heteroátomo ou ligante de hidrocarbileno substituído contendo heteroáto- mo e ainda em que dois ou mais substituintes em átomos adjacentes dentro de Q podem ser ligados para formar um grupo cíclico adicional.18. Method according to claim 17, CHARACTERIZED by the fact that M is ruthenium, w, x, y and z are zero, X and Y are N and R3A and R4A are linked to the form -Q-, so that the complex has the structure wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or heteroatom-containing substituted hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.
[0019]
19. Method according to any one of claims 2 and 13 to 18, CHARACTERIZED by the fact that the substrate material is selected from reinforcement materials, glass fibers, glass fabrics, carbon fibers, carbon fabrics , aramid fibers, aramid fabrics, polyolefin fibers, polyolefin fabrics, polymer fibers or polymer fabrics.
[0020]
20. Resin composition according to claim 1, CHARACTERIZED by the fact that the concentration of the adhesion promoter is from 0.5 to 4.0 phr, based on the weight of the adhesion promoter per hundred grams of base resin.
[0021]
21. Resin composition according to claim 10, CHARACTERIZED by the fact that Q is -CR11R12-CR13R14- or -CR11=CR13-, wherein R11, R12, R13 and R14 are independently selected from hydrogen, hi - drocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted hydrocarbyl containing heteroatom and functional groups or in which any two of R11, R12, R13 and R14 can be joined together to form a substituted or unsubstituted, saturated or unsaturated ring; R3 and R4 are aromatic; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, heteroatom-containing substituted hydrocarbyl, and functional groups; or R1 and R2 are taken together to form an indenylidene moiety; and X1 and X2 are halogen.
[0022]
22. Resin composition according to claim 21, CHARACTERIZED by the fact that Q is -CR11R12-CR13R14- wherein R11, R12, R13 and R14 are independently selected from hydrogen, C1-C12 alkyl, C1-alkyl substituted C12, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl and substituted phenyl; and R3 and R4 are unsubstituted phenyl or phenyl substituted with one or more substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, C5-aryl substituted C24, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl or halogen.
[0023]
em que, M é um metal de transição do grupo 8; X1 e X2 são independentemente ligantes aniônicos; L1 é selecionado dentre ligantes neutros doadores de elétrons; Y é um heteroátomo selecionado de N, O, S e P; R5, R6, R7 e R8 são cada um, independentemente, selecionados do grupo que consiste em hidrogênio, halogênio, alquil, alquenil, alquinil, aril, heteroalquil, he- teroátomo contendo alquenil, heteroalquenil, heteroaril, alcoxi, alqueniloxi, ariloxi, alcoxicarbonil, carbonil, alquilamino, alquiltio, aminosulfonil, monoalquilaminosulfonil, dialquilaminosulfonil, alquilsulfonil, nitrilo, nitro, alquilsulfinil, trihaloalquil, perfluoroal- quil, ácido carboxílico, cetona, aldeído, nitrato, isocianato, hidroxila, éster, éter, amina, imina, amida, trifluoramina, sulfeto, dissulfeto, sulfonato, carbamato, silano, siloxano, fosfina, fosfato, borato ou -A-Fn, em que A é uma fração de hidrocarbone- to divalente selecionada a partir de alquileno e arilalquileno, em que a porção alquila dos grupos alquileno e arilalquileno pode ser linear ou ramificada, saturada ou insa- turada, cíclica ou acíclica e substituída ou não substituída, em que a porção aril do arilalquileno pode ser substituída ou não substituída e em que grupos heteroatomos e/ou funcionais podem estar presentes nas porções aril ou alquil dos grupos alquile- no e arilalquileno, e Fn é um grupo funcional; e qualquer combinação de R5, R6, R7 e R8 pode ser ligada para formar um ou mais grupos cíclicos; n é 1 ou 2, de modo que n é 1 para os heteroátomos divalentes O ou S e n é 2 para os heteroátomos trivalentes N ou P; e Z é um grupo selecionado dentre hidrogênio, alquil, aril, alquil funcionalizado, aril funcionalizado, em que o grupo funcional pode ser independentemente um ou mais ou dos seguintes: alcoxi, ariloxi, halogênio, ácido carboxílico, cetona, aldeído, nitrato, isocianato, hidroxila, éster, éter, amina, imina, amida, trifluoroamida, sulfeto, dissulfeto, carbamato, silano, siloxano, fosfina, fosfato ou borato; metil, isopropil, sec-butil, t-butil, neopentil, benzil, fenil e trimetilsilil; e em que qualquer combinação ou combinações de X1, X2, L1, Y, Z, R5, R6, R7 e R8 podem ser fixadas a um suporte.23. Resin composition according to claim 1, CHARACTERIZED by the fact that the olefin metathesis catalyst has the structure wherein, M is a group 8 transition metal; X1 and X2 are independently anionic ligands; L1 is selected from electron-donating neutral ligands; Y is a heteroatom selected from N, O, S and P; R5, R6, R7 and R8 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl-containing heteroatom, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl , carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine trifluoroamine, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate or -A-Fn, where A is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, where the alkyl portion of alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or not sub- formed and in which heteroatoms and/or functional groups may be present on the aryl or alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group; and any combination of R5, R6, R7 and R8 can be linked to form one or more cyclic groups; n is 1 or 2, so that n is 1 for the divalent heteroatoms O or S and n is 2 for the trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl, where the functional group can independently be one or more of the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate , hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X1, X2, L1, Y, Z, R5, R6, R7 and R8 can be attached to a bracket.
[0024]
24. Resin composition according to claim 1, CHARACTERIZED by the fact that the compound containing a functional group containing heteroatom and an active olefin with metathesis is 2-hydroxyethylbicyclo[2.2.1]hept-2-ene-5 -carboxylate (HENB).

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同族专利:

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EP2721106B1|2020-06-03|

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JP2015500889A|2015-01-08|

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US20140329017A1|2014-11-06|

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BR112013032369A2|2017-01-03|

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WO2012174502A2|2012-12-20|

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ES2805289T3|2021-02-11|

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IN2014DN00290A|2015-06-05|

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US20200115277A1|2020-04-16|

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EP2721106A4|2015-09-23|

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DK2721106T3|2020-08-03|

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CN103748165A|2014-04-23|

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EP2721106A2|2014-04-23|

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US10457597B2|2019-10-29|

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KR20140047659A|2014-04-22|

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SG10201601566TA|2016-03-30|

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AU2012271297B2|2016-08-04|

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AU2012271297A1|2014-01-16|

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PL2721106T3|2021-03-08|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-02-02| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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