UNIMODAL ETHYLENE POLY HOMOPOLYMER RESIN, FILM AND METHOD

专利摘要:
NEW CATALYST SYSTEMS AND POLYMER RESINS HAVING IMPROVED BARRIER PROPERTIES Unimodal polymeric resin having a density of approximately 0.946 g / ml to approximately 0.97 g / ml and zero cut viscosity of approximately 8 x 102 Pa-s to approximately 6 x 104 Pa -s. a method comprising (a) providing a catalyst system comprising a sandwich transition metal complex; (b) contact of the catalyst system with an olefin under suitable conditions to form a polyolefin, where the polyophylline is unimodal; and (c) recovery of the polyolefin, where in the polyolefin it has a density of approximately 0.946 g / ml to approximately 0.97 g / ml and zero cut viscosity of approximately 8 x 102 Pa-s to approximately 6 x 104 Pa-s. a unimodal polymeric resin having a density of approximately 0.946 g / ml to approximately 0.97 g / ml and a CY-a parameter of approximately 0.5 to approximately 0.6.
公开号:BR112013006889B1
申请号:R112013006889-2
申请日:2011-09-20
公开日:2020-11-17
发明作者:Guylaine St Jean；Errun Ding；Chung C. Tso；Qing Yang；Albert P. Masino；Joel L. Martin
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[001] The subject of this application relates to US Patent Application No. 12 / 890,455 [Attorney Docket No. 211273US00 (4081-14700)], filed simultaneously with this and entitled “Novel Catalyst Systems and Polymer Resins Having Improved Barrier Properties , ”Which is hereby incorporated by reference in its entirety for all purposes. BACKGROUND OF THE INVENTION
[002] The present disclosure generally relates to catalyst systems and polymer resins prepared using them. More particularly, the present disclosure relates to the use of catalyst systems comprising chromium sandwich compounds to prepare polymer resins, exhibiting the enhanced barrier properties. FIELD OF THE INVENTION
[003] Polyolefins are plastic materials useful for making a wide variety of valued products due to their combination of rigidity, ductility, barrier properties, temperature resistance, optical properties, availability, and low cost. One of the most valuable products is plastic films. In particular, PE is one of the largest volume polymers consumed in the world. This is a versatile polymer that offers high performance over other polymers and alternative materials such as glass, metal, or paper. Plastic films, such as PE films, are mainly used in packaging applications, but they also find use in the agricultural, medical, and engineering fields.
[004] PE films are manufactured in a variety of grades that are generally differentiated by the density of the polymer, for example, low density polyethylene (LDPE), medium density polyethylene (PEMD), high density polyethylene and (HDPE) , where each density range has a unique combination of properties that makes it suitable for a given application.
[005] Despite the many positive attributes of PE, the film product remains permeable to gases and / or moisture (eg water) such as oxygen and carbon dioxide. Thus, it would be desirable to develop a PE film product exhibiting enhanced barrier properties. It is of additional interest to develop new catalyst systems capable of producing polymer resins that can be formed into films, exhibiting the desirable properties mentioned above. BRIEF SUMMARY OF THE INVENTION
[006] This document features a unimodal polymeric resin having a density of approximately 0.946 g / ml to approximately 0.97 g / ml and zero cut viscosity of approximately 8 x 102 Pa-s to approximately 6 x 104 Pa-s.
[007] A method is also presented in this document comprising (a) providing a catalyst system comprising a half-sandwich transition metal complex, (b) contacting the catalyst system with an olefin under conditions suitable to form a polyolefin, in that the polyolefin is unimodal; and (c) recovering the polyolefin in which the polyolefin has a density of approximately 0.946 g / ml to approximately 0.97 g / ml and a zero shear viscosity of approximately 8 x 102 Pa-s to approximately 6 x 104 Pa-s .
[008] Also shown is a unimodal polymeric resin having a density of approximately 0.946 g / ml to approximately 0.97 g / ml and a CY-a parameter of approximately 0.5 to 0.6. BRIEF DESCRIPTION OF THE DRAWINGS
[009] Figure 1 is a graph of the molecular weight distribution of polymer samples from Example 1.
[0010] Figure 2 is a graphical representation of the rotation radius as a function of the molecular weight for the samples of Example 1.
[0011] Figures 3 and 4 are graphs of the molecular weight distribution of the polymer samples of Example 2.
[0012] Figure 5 is a graphical representation of the moisture vapor transmission rate as a function of the zero shear viscosity for the samples in Example 2. DETAILED DESCRIPTION OF THE INVENTION
[0013] Catalyst compositions and methods for producing and using them are disclosed here. In one embodiment, the catalyst system comprises a transition metal complex, an activator support, an optional additional activator and an optional cocatalyst. Such catalyst systems can be used in the preparation of polymer resins such as polyolefins. In one embodiment, the polymer resin comprises polyethylene, alternatively high density polyethylene. Polymer resins of the type described in this document can be formed into films that exhibit improvements in barrier properties and as such may find specific utility in food packaging applications. Further such polymer resins are called enhanced barrier polymer (BIP) compositions. In one embodiment, a BIP composition is a polyethylene homopolymer (for example, a unimodial polyethylene homopolymer), having the physical properties and characteristics described in more detail in this document.
[0014] In one embodiment, a method of preparing a BIP composition comprises that an alpha-olefin monomer comes into contact with a catalyst system under conditions suitable for the formation of a polymer of the type described in this document. Any catalyst system compatible with and capable of producing polymers with the characteristics disclosed here can be employed. In one embodiment, the catalyst system comprises a transition metal complex, an activator support, and an optional cocatalyst.
[0015] The terms "catalyst composition", "catalyst mixture", "catalyst system," and the like, do not depend on the actual product resulting from the reaction or contact of the components of the mixtures, the nature of the active catalytic site, or the destination of the cocatalyst, the transition metal complexes, any olefin monomer used to prepare a pre-contacted mixture, or the support-activator, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", and the like, can include both homogeneous compositions and heterogeneous compositions. With respect to the chemical groups defined in this document, in one aspect, a chemical "group" can be defined or described according to branch that group is formally derived from a "original" reference or compound, for example, by the number of hydrogen atoms which are formally removed from the original compound to generate the group, even if that group is not literally synthesized that way. These groups can be used as substituents or coordinated or attached to metal atoms. For example, a "alkyl group" can formally be derived by removing a hydrogen atom from an alkane, a "alkenyl" group by removing a hydrogen atom from an alkene, or an alkene group, removing a an alkaline hydrogen atom, while an "alkylene group", "alkenylene group" or "alkynylene group" can be formally derived by removing two hydrogen atoms from an alkane, alkene, or alkane, respectively. In addition, a more general term can be used to encompass a variety of formally derived groups, removing any number hydrogen atoms ("one or more") from an original compound that, in this example, can be described as an "alkane group" ", and which encompasses an" alkyl group, "an" alkylene group, "and the material has three or more hydrogen atoms, as needed for the situation, taken from an alkane. In any disclosure that a substituent, linker, or other chemical moiety may constitute a particular "group" implies that well-known rules of chemical structure and bonding are followed when that group is employed as described. When describing a branch group being "derived from", "derived from", "formed by," or "formed from", these terms are used in a formal sense and are not intended to reflect any specific synthetic procedures or methods, unless otherwise specified or the context requires otherwise.
[0016] The term "organyl group" is used in this document, in accordance with the definition specified by IUPAC: an organic substituent group, regardless of the functional type, having a free valence on a carbon atom. Similarly, an "organylene group" refers to an organic group, regardless of the functional type, derived by the removal of two hydrogen atoms from an organic compound, or two hydrogen atoms from a carbon atom or a carbon atom. hydrogen from each of the two different carbon atoms. An "organic group" refers to a generalized group formed by removing one or more hydrogen atoms from carbon atoms in an organic compound. Thus, an "organyl group", an "organylene group", and an "organic group" can contain different functional organic group (s) and / or hydrogen and carbon atom (s), that is, an organic group that it can comprise functional groups and / or atoms in addition to hydrogen and carbon. For example, non-limiting examples of different carbon and hydrogen atoms include halogens, oxygen, nitrogen, phosphorus, and the like. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, and phosphines, and so on. In one aspect, the hydrogen atom (s) removed to form the "organyl group", "organylene group", or "organic group" can be attached to a carbon atom belonging to a functional group, for example, an acyl group (- C (O) R), a formyl group (-C (O) H), a carboxy group (-C (O) OH), a hydrocarboxycarbonyl group (-C (O) OR) , a cyano group (-CHN), a carbamoyl group (-C (O) NH2), an N-hydrocarbilcarbamoyl group (-C (O) NHR), or an N, N'-dihydrocarbilcarbamoyl group (-C (O ) NR2), among other modalities. In one aspect, the hydrogen atom (s) removed to form the "organyl group", "organylene group", or "organic group" can be attached to a carbon atom not belonging to, and removed of, a functional group, for example, -CH2C (O) CH3, - CH2NR2, and the like. An "organila group", "organylene group", or "organic group" can be aliphatic, including being cyclic or acyclic, or it can be aromatic. "Organyl groups", "organylene groups", and "organic groups" can encompass rings containing heteroatom, ring systems containing heteroatom, heteroaromatic rings, and heteroaromatic ring systems. "Organyl groups", "organylene groups", and "organic groups" may be straight or branched unless otherwise specified. Finally, it is observed that the definitions of "organyl group", "organylene group", or "organic group" include "hydrocarbyl group", "hydrocarbene group", "hydrocarbon group", respectively, and "alkyl group", "group alkylene ”, and“ alkane group ”, respectively, as elements.
[0017] The term “hydrocarbyl group” is used in this document according to the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (ie, a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl, and the like. Similarly, a "hydrocarbilene group" refers to a group formed by removing two hydrogen atoms from a hydrocarbon, both hydrogen atoms from a carbon atom or a hydrogen atom from each of the two different carbon atoms. Therefore, according to the terminology used in this document, a “hydrocarbon group” refers to a generalized group formed by removing one or more hydrogen atoms (as needed for the specific group) from a hydrocarbon. A "hydrocarbyl group", "hydrocarbene group", and "hydrocarbon group" can be acyclic or cyclic groups, and / or can be straight or branched. A "hydrocarbyl group", "hydrocarbene group", and "hydrocarbon group" can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen. "Hydrocarbyl groups", "hydrocarbene groups", and "hydrocarbon groups" include, by way of example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane groups, aralkyl, aralkylene and aralkane groups, respectively, among other groups as elements.
[0018] The term "alkyl group" is used in this document according to the definition specified by IUPAC: a univalent group formed by the removal of a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by the removal of two hydrogen atoms from an alkane (both hydrogen atoms from one carbon atom or a hydrogen atom from two different carbon atoms). An "alkane group" is a general term that refers to a group formed by the removal of one or more hydrogen atoms (as necessary for the specific group) from an alkane. An "alkyl group", "alkylene group", and "alkane group" can be acyclic or cyclic groups, and / or can be straight or branched unless otherwise specified. Primary, secondary and tertiary alkyl groups are derived by removing a hydrogen atom from a primary, secondary, tertiary carbon atom, respectively, from an alkane. The n-alkyl group derived by removing a hydrogen atom from a terminal carbon atom of a linear alkane. The groups RCH2 (R # H), R2CH (R # H), and R3C (R + H) are primary, secondary and tertiary alkyl groups, respectively.
[0019] In one embodiment, a catalyst system for preparing a BIP comprises the contact product of a transition metal complex, an activator support and an optional cocatalyst. The transition metal complex can be characterized by the general formula M (Z) (R1) (R2) Ln where M is a transition metal, alternatively chromium and Z, R1, and R2 are linkers coordinated to M, and l_n is a neutral donor group where n is 0, 1 or 2. In another embodiment l_n can be tetrahydrofuran (THF), acetonitrile, pyridine, diethylether or bipyridine. In one embodiment, Z comprises a portion η3 to η5-cycloalkadienyl. Non-limiting examples of η3 to η5-cycloalkadienyl moieties suitable for use in this disclosure include cyclopentadienyl binders, indenyl binders, fluorenyl binders, and the like, including substituted or partially saturated derivatives or analogues of any of these. Possible substituents on these binders include hydrogen, so the description "substituted derivatives thereof" in this disclosure comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In one embodiment, Z comprises a cyclopentadienyl moiety and the transition metal complex is called a "half-sandwich complex". The cyclopentadienyl portion can be characterized by the general structure;

[0020] In one embodiment, each R of the cyclopentadienyl portion may be different. In some embodiments, each R can be the same. In one embodiment, each R can be independently selected from the group consisting of hydrogen, an organyl group; or alternatively, a hydrogen and a hydrocarbyl group. In embodiments, each R can independently be H or an organyl group C1 to C20; alternatively, H or an organyl group C1 to C10; or alternatively, H or an Ci to Cs organyl group. In other embodiments, each R can be independently H or a C 1 to C 20 hydrocarbyl group; alternatively, H or a C1 to C10 hydrocarbyl group; or alternatively, H or a C1 to C5 hydrocarbyl group or alternatively H. In one embodiment, R may be a C1 to Ceo organylene group; alternatively, a C 1 to C 50 organylene group; alternatively, organylene group C1 to C40; alternatively, a C 1 to C 30 organylene group; or alternatively, a C 1 to C 20 organylene group. In other embodiments, each R can independently be a C1 to Ceo hydrocarbilene group; alternatively, a C1 to C50 hydrocarbilene group; alternatively, a C1 to C40 hydrocarbilene group; alternatively, a C1 to C30 hydrocarbilene group; alternatively, a C1 to C20 hydrocarbilene group.
[0021] In some embodiments, each R group can independently be an alkyl group. In one embodiment, the alkyl group that can be used as a non-hydrogen R group can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a octyl group, nonyl group, decila group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, or nonadecyl group; or alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. In some embodiments, the alkyl group that can be used as a non-hydrogen R group can be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group -butyl, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, or a neopentyl group; alternatively, a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an iso-propyl group; alternatively, a tert-butyl group; or alternatively, a neopentyl group.
[0022] In one embodiment, each R may independently be an alkylene group alternatively, an alkenylene group. For example, each R can independently be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a group undecylene, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, or a nonadecylene group; or alternatively, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group. In some embodiments, each R can be independently a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group. In other embodiments, each R can be independently a methylene group; alternatively, an ethylene group; alternatively, alternatively, alternatively, alternatively, a propylene group; a pentylene group; a heptylene group; a nonylene group; alternatively, alternatively, alternatively, alternatively, a butylene group; a hexylene group; an octylene group; a decylene group; alternatively, an undecylene group; alternatively, a dodecylene group; alternatively, a tridecylene group; alternatively, a tetradecylene group; alternatively, a pentadecylene group; alternatively, a hexadecylene group; alternatively, a heptadecylene group; alternatively, an octadecylene group; or alternatively, a nonadecylene group. In some embodiments, each R can be independently an et-1,2-ylene group, a prop-1,3-ylene group, a but-1,4-ylene group, a but-2,3-ylene group, a pent-1,5-ylene group, a 2,2-dimethylprop-1,3-ylene group, a hex-1,6-ylene group, or a 2,3-dimethylbut-2,3-yl group; alternatively, et-1,2-ylene group, prop-1,3-ylene group, but-1,4-ylene group, pent-1,5-ylene group, or hex-1,6- ilene; alternatively, an et-1,2-ylene group; alternatively, a prop-1,3-ylene group; alternatively, a but-1,4-ylene group; alternatively, a but-2,3-ylene group; alternatively, a pent-1,5-ylene group; alternatively, a 2,2-dimethylprop-1,3-ylene group; alternatively, a hex-1,6-ylene group; or alternatively, a 2,3-dimethylbut-2,3-ylene group.
[0023] In one embodiment, each R can be independently an ethylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, a group undecenylene, a dodecenylene group, a tridecenylene group, a tetradecenylene group, a pentadecenylene group, a hexadecenylene group, a heptadecenylene group, an octadecenylene group, or a nonadecenylene group; or alternatively, an ethylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group. In some embodiments, each R can be independently an ethylene group, a propenylene group, a butenylene group, or a pentenylene group. In other embodiments, each R can be independently an ethylene group; alternatively, a propenylene group; alternatively, a butenylene group; alternatively, a pentenylene group; alternatively, a hexenylene group; alternatively, a heptenylene group; alternatively, an octenylene group; alternatively, a nonenylene group; alternatively, a decenylene group; alternatively, an undecenylene group; alternatively, a dodecenylene group; alternatively, a tridecenylene group; alternatively, a tetradecenylene group; alternatively, a pentadecenylene group; alternatively, a hexadecenylene group; alternatively, a heptadecenylene group; alternatively, an octadecenylene group; or alternatively, a nonadecenylene group. Generally, the carbon-carbon double bonds of any alkenylene group disclosed herein can be located at any position within the alkenylene group. In one embodiment, the alkenylene group contains a terminal carbon-carbon double bond.
[0024] In one embodiment, each R of the cyclopentadienyl group comprises an alkyl group, alternatively a methyl group. In one embodiment, Z comprises a pentamethylcyclopentadienyl group, here called Cp *. In another embodiment, at least one R of the cyclopentadienyl group comprises an organylene group, alternatively a hydrocarbilene group. In one embodiment the cyclopentadienyl group comprises a group R comprising -C (CH3) 2CH2CH2CH = CH2 and the remaining R groups comprise hydrogen, hereinafter referred to as Cp '. Alternatively the cyclopentadienyl group comprises an R group comprising -CH2CH2CH = CH2 and the remaining R groups comprise hydrogen and is referred to below as Cp ”. Cp ’and Cp” can be prepared using any suitable methodology. For example, suitable preparation methodologies are described in Brieger, et al., J. Org. Chem. 36 (1971) p243; Bochmann, et al., In J. Organmet. Chem. 592 (1999); Theopold, et al., J. Am. Chem. Soc. 111 (1989) p9127; and Fendrick, et al., in Inorg. Synth., 29 (1992) p193, each of which is incorporated by reference in this document in its entirety.
[0025] In a mode R1 and R2 can be different. In other embodiments, R1 and R2 can be the same. In one embodiment, each of R1 and R2 can be independently selected from the group consisting of a halide, an organyl group, or a hydrocarbyl group. In embodiments, each of R1 and R2 can independently be a halide, an organyl group C1 to C20; alternatively, an organyl group C1 to C10; or alternatively, an organyl group C1 to C5. In other embodiments, each of R1 and R2 can independently be a halide, a C1 to C20 hydrocarbyl group; alternatively, a C1 to C10 hydrocarbyl group; or alternatively a C1 to C5 hydrocarbyl group.
[0026] In some embodiments each of R1 and R2 can be independently selected from the group consisting of a halide, an alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, a heteroaryl group , and a substituted heteroaryl group. In other embodiments, each of R1 and R2 can independently be a halide, an alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, or a substituted aryl group; alternatively, a halide; alternatively an alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; or alternatively, a heteroaryl group or a substituted heteroaryl group. In still other embodiments, each of R1 and R2 can independently be a halide, alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, a substituted cycloalkyl group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, a heteroaryl group; or alternatively, a substituted heteroaryl group.
[0027] In one embodiment, each of R1 and R2 can independently be a fluoride, chloride, bromide, or iodide; alternatively, a fluoride or chloride; alternatively, a chloride. In some embodiments, at least two of R1 and R2 are a halide; alternatively, R1 and / or R2 are chloride.
[0028] In one embodiment, the alkyl group that can be used as an R1 and / or R2 group can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a group heptyla, an octyl group, a nonyl group, a decila group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecyl group ; or alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. In some embodiments, the alkyl group that can be used as an R1 and / or R2 group can be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group -butyl, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, or a neopentyl group; alternatively, a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an iso-propyl group; alternatively, a tert-butyl group; or alternatively, a neopentyl group.
[0029] In one embodiment, the cycloalkyl group that can be used as an R1 and / or R2 group can be a cyclobutyl group, a substituted cyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a group substituted cyclohexyl, a cycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group, or a substituted cyclooctyl group. In some embodiments, the cycloalkyl group that can be used as an R1 and / or R2 group can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group. In other embodiments, the cycloalkyl group that can be used as an R1 and / or R2 group can be a cyclobutyl group or a substituted cyclobutyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cycloheptyl group or a substituted cycloheptyl group; or alternatively, a cyclooctyl group, or a substituted cyclooctyl group. In additional embodiments, the cycloalkyl group that can be used as an R1 and / or R2 group can be a cyclopentyl group; alternatively, a substituted cyclopentyl group; a cyclohexyl group; or alternatively, a substituted cyclohexyl group. Substituents for the substituted cycloalkyl group are independently disclosed in this document and can be used without limitation to further describe the substituted cycloalkyl group that can be used as an R1 and / or R2 group.
[0030] In one aspect, the aryl groups that can be used as an R1 and / or R2 group can be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In one embodiment, the aryl groups that can be used as an R1 and / or R2 group can be a phenyl group or a substituted phenyl group; alternatively, a naphthyl group or a substituted naphthyl group; alternatively, a phenyl group or a naphthyl group; or alternatively, a substituted phenyl group or a substituted naphthyl group.
[0031] In one embodiment, the substituted phenyl group that can be used as an R1 and / or R2 group can be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a phenyl 2 group , 4- disubstituted, a 2,6-disubstituted phenyl group, 3,5-disubstituted phenyl group, or a 2,4,6-tri-substituted phenyl group. In other embodiments, the substituted phenyl group that can be used as an R1 and / or R2 group can be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a phenyl 2 group , 6-disubstituted; alternatively, a 3-substituted phenyl group or a 3,5-disubstituted phenyl group; alternatively, a 2-substituted phenyl group or a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively, a 2-substituted phenyl group; alternatively, a 3-substituted phenyl group; alternatively, a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group; alternatively, a 2,6-disubstituted phenyl group; alternatively, 3,5-disubstituted phenyl group; or alternatively, a 2,4,6-tri-substituted phenyl group.
[0032] In one embodiment, each non-hydrogen substituent for the substituted cycloalkyl group, substituted aryl group, or substituted heteroaryl group that can be used as an R1 and / or R2 group can be independently selected from a halide, a hydrocarbyl group C1 to C10, or a hydrocarbon group C1 to C10; alternatively, a C1 to C10 halide or hydrocarbyl group; alternatively, a C1 to C10 halide or hydrocarbon group; alternatively, a C1 to C10 hydrocarbyl group or a C1 to C10 hydrocarbon group; alternatively, a halide; alternatively, a C1 to C10 hydrocarbyl group; or alternatively, a C1 to C10 hydrocarbon group. In some embodiments, each non-hydrogen substituent for the substituted cycloalkyl group, substituted aryl group, or substituted heteroaryl group that can be used as an R1 and / or R2 group can be independently selected from a halide, a C1 hydrocarbyl group to C5, or C1 to C5 hydrocarbon group; alternatively, a C1 to C5 halide or hydrocarbyl group; alternatively, a C1 to C5 halide or hydrocarbon group; alternatively, a C1 to C5 hydrocarbyl group or a C1 to C5 hydrocarbon group; alternatively, a halide; alternatively, a C1 to C5 hydrocarbyl group; or alternatively, a C1 to C5 hydrocarbon group. Specific substituent halides, hydrocarbyl groups, and hydrocarbon groups are independently disclosed herein and can be used without limitation to further describe the substituents for the substituted cycloalkyl group, substituted aryl group, or substituted heteroaryl group that can be used as an R1 and / or R2.
[0033] In one embodiment, any halide substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a fluoride, chloride, bromide, or iodide; alternatively, a fluoride or chloride. In some embodiments, any halide substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.
[0034] In one embodiment, any hydrocarbyl substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), or substituted heteroaryl (general or specific) can be an alkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group; alternatively, an aryl group, or an aralkyl group. Generally, the alkyl, aryl, and aralkyl substituent groups may have the same number of branch carbon atoms as the hydrocarbyl substituent group disclosed herein. In one embodiment, any alkyl substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), heteroaryl (general or specific) can be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl group 1-butyl, a tert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group; alternatively, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a neo-pentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an isopropyl group; alternatively, a tert-butyl group; or alternatively, a neopentyl group. In one embodiment, any aryl substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a phenyl group, a tolyl group, a xylyl group, or a 2,4,6-trimethylphenyl group; alternatively, a phenyl group; alternatively, a tolyl group, alternatively, a xylyl group; or alternatively, a 2,4,6-trimethylphenyl group. In one embodiment, any aralkyl substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be benzyl group.
[0035] In one embodiment, any hydrocarbon substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be an alkoxy group, an aryloxy group, or e an aralkoxy group; alternatively, an alkoxy group; alternatively, an aryloxy group, or an aralkoxy group. Generally, the alkoxy, aryloxy, and aralkoxy substituent groups may have the same number of branch carbon atoms as the hydrocarbon substituent group disclosed herein. In one embodiment, any alkoxy substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a methoxy group, an ethoxy group, an n-propoxy group , an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2- group methyl-1-butoxy, a tert-pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an isopropoxy group; alternatively, a tert-butoxy group; or alternatively, a neo-pentoxy group. In one embodiment, any aroxy substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a phenoxy group, a toloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group; alternatively, a phenoxy group; alternatively, a toloxy group, alternatively, a xyloxy group; or alternatively, a 2,4,6-trimethylphenoxy group. In one embodiment, any aralkoxy substituent of a substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), substituted heteroaryl (general or specific) can be a benzoxy group.
[0036] In one embodiment, a transition metal complex suitable for use in this disclosure comprises Cp * Cr (CH3) 2 (py) branch represented by Formula I. Formula I

[0037] In one embodiment, a transition metal complex suitable for use in this disclosure comprises Cp'Cr (CI) 2 (THF) branch represented by Formula II. Formula II

[0038] In one embodiment, a transition metal complex suitable for use in this disclosure comprises Cp ”Cr (CI) 2 (THF) as represented by Formula III. Formula III

[0039] Alternatively the catalyst system comprises more than one of the transition metal complex.
[0040] A catalyst system for preparing BIP can additionally comprise a support-activator. The present disclosure encompasses several catalyst compositions containing an activator, which can be a support-activator. In one aspect, the activating support comprises a chemically treated solid oxide. Alternatively, the activating support may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a non-layered silicate mineral layered aluminum silicate, a non-layered aluminum silicate mineral, or any rambling thereof.
[0041] Generally, chemically treated solid oxides exhibit increased acidity when compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as a catalyst activator when compared to the corresponding untreated solid oxide. Although the chemically treated solid oxide activates the metallocene (s) in the absence of cocatalysts, it is not necessary to eliminate cocatalysts from the catalyst composition. The activation function of the activator support is evident in the enhanced composition activity of the catalyst as a whole, compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminium compound, aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds, and the like.
[0042] The chemically treated solid oxide may comprise a solid oxide treated with an electron withdrawing anion. Although it is not intended to be linked to the following instruction, it is believed that the treatment of the solid oxide with an electron withdrawing component enlarges or increases the acidity of the oxide. In this way, the activator support exhibits Lewis or Bronsted- acidity, that is, normally greater than the Lewis or Bronsted acid strength of untreated solid oxide, or the activator support has a greater number of acid sites than untreated solid oxide, or both. A method to quantify the acidity of untreated and chemically treated solid oxide materials, comparing the polymerization activities of treated and untreated oxides with acid catalyzed reactions.
[0043] Chemically treated solid oxides of this disclosure are generally formed from an inorganic solid oxide which exhibits acidic Lewis behavior and acidic Bnansted behavior and has a relatively high porosity. The solid oxide is chemically treated with an electron withdrawing component, usually an electron withdrawing anion, to form a support-activator.
[0044] According to one aspect of the present disclosure, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. According to another aspect of the present disclosure, the solid oxide has a pore volume greater than about 0.5 cc / g. According to yet another aspect of the present disclosure, the solid oxide has a pore volume greater than about 1.0 cc / g.
[0045] In one aspect, the solid oxide has a surface area of about 100 to about 1000 m2 / g. In yet another aspect, the solid oxide has a surface of about 200 to about 800 m2 / g. In yet another aspect of the present disclosure, solid oxide has a surface area of about 250 to about 600 m2 / g.
[0046] The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and one or more elements selected from the lanthanide or actinide elements (See: Hawleys Condensed Chemical Dictionary, 11th Ed., John Wiley Sons, 1995; Cotton, FA, Wilkinson, G. , Murillo, CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, inorganic oxide can comprise oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
[0047] Suitable examples of solid oxide materials or compounds that can be used to form chemically treated solid oxide, but are not limited to, AI2O3, B2O3, BeO, BI2O3, CdO, CO3O4, C ^ Os, CuO, Fβ2θ3, Ga2θ3, La2θ3, Mn2θ3, Moθ3, NiO, P2O5, Sb2θs, SÍO2, Snθ2, SrO, Thθ2, TÍO2, V2O5, WO3, Y2O3, ZnO, Z1O2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boron, zinc oxide, mixed oxides thereof, or any combination of these. themselves.
[0048] The solid oxide of this disclosure includes oxide materials such as alumina, compounds of "mixed oxide" thereof such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina, can be in a single phase or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activating support of the present disclosure include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc -aluminate, alumina-boron, silica-boron, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide of this disclosure also encompasses oxide materials such a coated silica-alumina branch, as described in U.S. Patent Publication No. 2010-0076167, the disclosure of which is incorporated herein by reference in its entirety.
[0049] The electron withdrawal component used to treat solid oxide can be any component that increases the Lewis or Bnansted acidity of solid oxide until treatment (when compared to solid oxide, that is, not treated with at least one electron withdrawing anion). According to one aspect of the present disclosure, the electron withdrawing component is an electron withdrawing anion derived from a salt, acid, or other component, such as a volatile organo compound, which serves as a source or precursor for such anion. Examples of anion-withdrawing anion include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacotate, triflate, fluorozirconate, fluorotitanate, phosphor-tungstate including mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for this electron withdrawing anion can also be employed in the present disclosure. It is contemplated that the electron withdrawing anion may be, or may comprise fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and the like, or any combination thereof, in some aspects of this disclosure. In other respects, the electron withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacotate, triflate, fluorozirconate, fluorotitanate, and the like, or any combination thereof.
[0050] Thus, for example, the activating support (for example, chemically treated solid oxide) used in the catalyst branches of the present disclosure (for example, BIP) can be, or can comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, silica-titanium fluorinated coated alumina, sulfated coated silica-alumina, phosphate coated silica-alumina, and the like, or combinations thereof. In one aspect, the activating support may be, or may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated coated silica, sulfated coated silica-alumina, phosphate-coated silica-alumina, and the like, or any combination thereof. In one aspect, the activating support comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluorinated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or alternatively, it comprises fluorinated coated silica-alumina.
[0051] When the electron withdrawing component comprises a salt from an electron withdrawing anion, the counterion or cation of such a salt can be selected in any cation that allows the salt to reverse or decompose back to acid during calcination . Factors that determine the suitability of the specific salt to serve as a source of the electron withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, ion pairing effects between cation and anion, hygroscopic properties, transmitted to the salt by the cation, and the like, and the thermal stability of the anion. Examples of suitable cations in the anion salt. Examples of suitable cations in the electron withdrawing anion salt include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, and the like.
[0052] In addition, combinations of one or more different electron withdrawing anions, in different proportions, can be used to adapt the specific acid of the activating support to the desired level. Combinations of electron withdrawal components can come in contact with the oxide material simultaneously or individually, and in any order that provides the desired acidity of the chemically treated solid oxide. For example, one aspect of this disclosure is employing two or more electron withdrawing anion source compounds in two or more separate contact steps.
[0053] Thus, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides, comes into contact with a first withdrawal anion source compound electron to form a first mixture; this first mixture is calcined and then comes in contact with a second compound from the electron withdrawing anion source to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In this process, the first and second compounds from the electron withdrawing anion source can be both the same or different compounds.
[0054] According to another aspect of the present disclosure, the chemically treated solid oxide comprises a solid iπorganic oxide material, a mixed oxide material, or a combination of iπorgaπicas oxide materials, that is, chemically treated with a withdrawal component electron, and optionally treated with a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of metal or metal ion include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof. Examples of chemically treated solid oxides that contain a metal or metal ion include, but are not limited to, alumina impregnated with dormant zinc, alumina impregnated with fluorinated titanium, alumina impregnated with fluorinated zinc, silica-alumina impregnated with dormant zinc, silica- alumina impregnated with fluorinated zinc, alumina impregnated with sulfated zinc, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, coated silica-alumina treated with hexafluorotitanic acid, coated silica-alumina treated with zinc and then fluorinated, and the like, and the like, and the like or any combination thereof.
[0055] Any method for impregnating the solid oxide material with a metal can be used. The method by which the oxide comes into contact with a metal source, usually a metal-containing salt or compound, may include, but is not limited to, gelation, cogelification, impregnation of one compound into another, and the like. If desired, the metal-containing compound is added to or impregnated with the solid oxide as a solution, and subsequently converted to the supported metal until calcination. Consequently, the solid inorganic oxide can additionally comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc is always used to impregnate solid oxide because it can provide increased catalyst activity at a low cost.
[0056] The solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the electron withdrawing anion. Following any contact method, the contacted mixture of the solid compound, electron withdrawing anion, and the metal ion are normally calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal salt or metal-containing compound come into contact and are calcined simultaneously.
[0057] Several processes are used to form the chemically treated solid oxide useful in the present disclosure. The chemically treated solid oxide may comprise the contact product of one or more solid oxides with one or more electron withdrawing anion sources. The solid oxide is not required to be calcined prior to contact with the electron withdrawing anion source. The contact product is normally calcined both during and after the solid oxide comes into contact with the electron withdrawing anion source. The solid oxide can be calcined or non-calcined. Several processes for preparing the solid oxide activating supports that can be used in this disclosure have been reported. For example, Such methods are described in U.S. Patent Nos. 6,107,230; 6,165,929; 6,294,494; 6,300,271; 6,316,553; 6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987; 6,548,441; 6,548,442; 6,576,583; 6,613,712; 6,632,894; 6,667,274; 6,750,302; 7,226,886; 7,294,599; 7,601,655; and 7,732,542 whose disclosures are incorporated herein by reference in their entirety.
[0058] According to one aspect of the present disclosure, the solid oxide material is chemically treated by contacting it with an electron withdrawing component, usually an electron withdrawing anion source. In addition, the solid oxide material is optionally chemically treated with a metal ion, and then calcined to form a chemically treated solid oxide impregnated with metal or containing metal. According to another aspect of the present disclosure, the solid oxide material and electron withdrawal anion source come into contact and are calcined simultaneously.
[0059] The method by which the oxide comes into contact with the electron withdrawing component, usually a salt or acid from an electron withdrawing anion, may include, but is not limited to, gelation, cogelification, impregnation of an compound in another, and the like. In this way, following any contact method, the contacted mixture of the solid oxide, electron withdrawing anion, and optional metal ion, are calcined.
[0060] The solid oxide support-activator (i.e., chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with a compound (or compounds ) from an anion source of electron withdrawal to form a first mixture; and 2) calcination of the first mixture to form the solid oxide support-activator.
[0061] According to another aspect of the present disclosure, the solid oxide activator support (chemically treated solid oxide) is produced by a process comprising: 3) contact of a solid oxide (or solid oxides) with a first source compound electron withdrawing anion to form a first mixture; 4) calcination of the first mixture to produce a first calcined mixture; 5) contact of the first calcined mixture with a second electron-withdrawing anion source compound to form a second mixture; and 6) calcination of the second mixture to form the solid oxide support-activator.
[0062] According to yet another aspect of the present disclosure, chemically treated solid oxide is produced or formed by contacting the solid oxide with the electron withdrawing anion source compound, where the solid oxide compound is calcined before, during , or after contact of the electron withdrawing anion source, and where there is a substantial absence of aluminoxane, organoboro or organoborate compounds, and ionizing ionic compounds.
[0063] Calcination of the treated solid oxide is generally conducted in an ambient atmosphere, usually in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C, and for a period of about 1 minute the corca 100 hours. Calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, at a temperature of about 400 ° C to about 700 ° C. Calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Calcination is generally conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
[0064] In accordance with one aspect of the present disclosure, the solid oxide material is treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically treated solid oxide as a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chlorinating agent"), a fluoride ion source (called a “Fluorination agent”), or a combination thereof, and calcined to provide the solid oxide activator. Useful acidic support-activators include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, hexafluorotitanic acid-treated alumina, coated hexafluorotitanic acid-coated silica, silica-alumina treated with hexafluorozirconium acid, silica-alumina treated with trifluoroacetic acid , fluorinated boron-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphate alumina or other aluminophosphates optionally treated with sulfate, fluoride, or chloride; or any combination of the above. In addition, any of these activating supports can optionally be treated with a metal ion.
[0065] The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting a solid oxide with a fluorination agent. The fluoride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent such as alcohol or water including, but not limited to, one to three carbon alcohols because of its volatility and low surface tension. Examples of suitable fluorination agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4 ) 2SiFe), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TIFF), ammonium hexafluorotitanic acid ((NH4) 2TiFβ), hexafluorozirconium acid (H2ZrFβ), AIF3, NH4AIF4, combinations of the same and the same. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluorination agent, due to its ease of use and availability.
[0066] If desired, the solid oxide is treated with a fluorination rate during the calcination step. Any fluorination agent capable of completely coming into contact with the solid oxide during the calcination step can be used. For example, in addition to those previously described fluorination agents, volatile organic fluorination agents can be used. Examples of volatile organic fluorination agents useful in this aspect of the disclosure include, but are not limited to, coolants, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. Calcination temperatures should generally be high enough to decompose the compound and release fluoride. Hydrogen gas fluoride (HF) or fluorine itself (F2) can also be used with solid oxide if fluorinated during calcination. Silicon tetrafluoride (SIF4) and compounds containing tetrafluoroborate (BF4 ') can also be used. A convenient method of contacting the solid oxide with the fluorination agent is to vaporize the fluorination agent in a gas stream used to fluidize the solid oxide during calcination.
[0067] Similarly, in another aspect of this disclosure, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. Chlorinated solid oxide is formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming an oxide slurry in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and coming into complete contact with the oxide during the calcination step can be used, such as SiCk, SiMe2Cl2, TiCk, BCI3, and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain coolants, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof. Gaseous hydrogen chloride or chlorine itself can also be used as the solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent is to vaporize the chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
[0068] The amount of fluoride or chloride ion present before calcination of the solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica- alumina, before calcination. According to another aspect of this disclosure, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 1 to about 25% by weight, and according to another aspect of this disclosure, from about 2 to about 20% by weight. According to yet another aspect of this disclosure, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 4 to about 10% by weight. Once impregnated with halide, halide oxide can be dried by any method including, but not limited to, suction filtration followed by evaporation, vacuum drying, evaporative drying, and the like, although it is also possible to start the calcination step immediately without drying the impregnated solid oxide.
[0069] The silica-alumina used to prepare the treated silica-alumina normally has a pore volume of about 0.5 cc / g. According to one aspect of the present disclosure, the pore volume is greater than about 0.8 cc / g, and according to another aspect of the present disclosure, greater than about 1.0 cc / g. In addition, silica-alumina generally has a surface area greater than about 100 m2 / g. According to another aspect of this disclosure, the surface area is greater than about 250 m2 / g. In yet another aspect, the surface area is greater than about 350 m2 / g.
[0070] The silica-alumina used in the present disclosure normally has an alumina content of about 5 to about 95% by weight. According to one aspect of this disclosure, the alumina content of silica-alumina is about 5 to about 50%, or about 8% to about 30%, by weight of alumina. In one aspect, silica-alumina compounds with a high alumina content can be employed, wherein the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80% by weight of alumina. According to yet another aspect of this disclosure, the solid oxide component comprises alumina without silica, and according to another aspect of this disclosure, the solid oxide component comprises silica without alumina.
[0071] The sulfated solid oxide comprises sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with a metal ion so that the calcined sulfated oxide comprises a metal. According to one aspect of the present disclosure, the sulfated solid oxide comprises sulfate and alumina. In some cases, sulfated alumina is formed by a process in which the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process is generally carried out by forming a slurry of alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, one to three carbon alcohols because of their volatility and low surface tension.
[0072] According to one aspect of this disclosure, the amount of sulfate ion present before calcination is about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of the solid oxide. According to another aspect of this disclosure, the amount of sulfate ion present before calcination is from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and further according to another aspect of this disclosure, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any method including, but not limited to, suction filtration followed by evaporation, vacuum drying, evaporative drying, and the like, although it is possible to start the calcination step immediately.
[0073] In accordance with another aspect of the present disclosure, the activator support used in the preparation of catalyst compositions of this disclosure comprises an ion-exchangeable activator support, including but not limited to silicate and aluminosilicate compounds or minerals, both in layered and non-layered structures, and combinations thereof. In another aspect of this disclosure, layered aluminosilicates, subject to ion exchange such as pillar clays, are used as support-activators. When the acid-activating support comprises an ion-exchanging activating support, it can optionally be treated with at least one electron withdrawing anion such as those disclosed in this document, although normally the activating support-exchangeable ion is not treated with an electron withdrawing anion.
[0074] According to another aspect of the present disclosure, the activating support of this disclosure comprises clay minerals having interchangeable cations and layers capable of expanding. Typical clay mineral support-activators include, but are not limited to, layered aluminosilicates, liable to ion exchange such branch clays on pillars. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, but rather it is to be considered an active part of the catalyst composition, due to its close association with the metallocene component.
[0075] According to another aspect of the present disclosure, the clay materials of this disclosure include materials in their natural state or that have been treated with various ions by wetting, ion exchange, or pillaring. Typically, the clay material activator support in this disclosure comprises clays that have been exchanged for ions with large cations, including highly charged, polynuclear metal complex cations. However, the clay material activator support in this disclosure also encompasses clays that have been exchanged for ions with simple salts, including, but not limited to, Al (lll), Fe (ll), Fe (lll) salts, and Zn (ll) w with binders such as halide, acotate, sulfate, nitrate, or nitrite.
[0076] According to another aspect of the present disclosure, the activating support comprises a clay with pillars. The term “pillar clay” is used to refer to clay materials that have been exchanged for ions with highly charged, polynuclear metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, several polyoxometalates, and other large ions. Thus, the term pillarization refers to a simple exchange reaction in which the interchangeable cations in a clay material are replaced with large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the clay interlayer and when calcined they are converted into "pillar" metal oxide, effectively supporting the clay layers as column type structures. In this way, after the clay is dried and calcined to produce the supporting pillars between layers of clay, the expanded expanded structure is maintained and the porosity is reinforced. The resulting pores may vary in shape and size depending on the pillar material and the main clay material used. Examples of pillarization and clay on pillars are found in: Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patents No. 4,452,910; 5,376,611; and 4,060,480; whose disclosures are incorporated herein by reference in their entirety.
[0077] The pillaring process uses clay minerals having interchangeable cations and layers capable of expanding. Any pillar clay that can enhance the polymerization of olefins in the catalyst composition of the present disclosure can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof, such as montmorillonite (bentonite), nontronite, hectorite, or laponite branches; haloisites; vermiculites; micas; fluoromics; chlorites; clay mixing layer; fibrous clays including, but not limited to, sepiolites, atapulgites, and paligorschites; a serpentine clay; illita; laponite; saponite; and any combination thereof. In one aspect, the clay support-activator on pillars comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[0078] Clay on pillars can be pre-treated if desired. For example, a pillar bentonite is pre-treated by drying at about 300 ° C under an inert atmosphere, usually dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pre-treatment is described in this document, it should be understood that pre-heating can be performed at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by the disclosure.
[0079] The support-activator used to prepare the catalyst compositions of the present disclosure can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphate inorganic oxides, and the like. In one aspect, typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boron, thorium, aluminophosphate, aluminum phosphate, silica-titania, silica / titania coprecipitate, mixtures thereof, or any combination thereof.
[0080] According to another aspect of the present disclosure, one or more of the metallocene compounds can be pre-contacted with an olefin monomer and an organoaluminium compound for a first period of time before contacting this mixture with the activating support. Once the mixture of the metallocene compounds, olefin monomer, and organoaluminium compound comes into contact with the activating support, the composition additionally comprising the activating support is called a "post-contacted" mixture. The post-contacted mixture can be allowed to remain in additional contact for a second period of time before being loaded into the reactor where the polymerization process will be carried out.
[0081] In accordance with yet another aspect of the present disclosure, one or more of the metallochlorine compounds can be pre-contacted with an olefin monomer and a support-activator for a first period of time before contacting this mixture with the compound of organoaluminium. Once the mixture of the metallochlorine compounds, olefin monomer, and support-activator is pre-contacted, it comes into contact with the organoaluminium compound, the composition further comprising the organoaluminium is called a "post-contacted" mixture. The post-contacted mixture can be allowed to remain in additional contact for a second period of time before being introduced into the polymerization reactor.
[0082] In one embodiment, the activator or the activator support is present in the catalyst system (ie BIP) in an amount of about 1% by weight to about 90% by weight, alternatively about 5% by weight at about 90% by weight, alternatively from about 10% by weight to about 90% by weight based on the total weight of the catalyst. In one embodiment, the weight ratio of metallocene compounds to the support-activator is in the range of about 1: 1 to about 1: 1,000,000. If more than one support-activator is employed, this ratio is based on the total weight of the support-activator. In another modality, this weight ratio is in a range from 1: 5 to 1: 100,000, or from 1:10 to about 01: 10,000. In yet another aspect, a weight ratio of the metallocene compounds to the support-activator is in the range of about 1:20 to about 1: 1000.
[0083] In one embodiment, a catalyst system of the type disclosed in this document comprises a support-activator (or activator) comprising a chemically treated solid oxide (for example, sulfated alumina). The catalyst system comprising a chemically treated solid oxide can operate as described in this document in the absence of any activators. In one embodiment, a catalyst system of the type described in this document comprises a solid chemically treated oxide as an activator and excludes additional activators. In an alternative embodiment, a catalyst system of the type described in this document comprises a solid oxide chemically treated as an activator and at least one additional activator.
[0084] In one embodiment, the additional activator comprises an aluminoxane compound. As used herein, the term "aluminoxane" refers to aluminoxane compounds, compositions, mixtures, or discrete species, regardless of which branch these aluminoxanes are prepared, formed or otherwise provided. Aluminoxanes are also referred to as poly (hydrocarbyl aluminum oxides) or organoaluminoxanes.
[0085] The aluminoxane compound of this disclosure may be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or mixtures of all three. Cyclic aluminoxane compounds having the formula:
where R is straight or branched alkyl having 1 to 10 carbon atoms, and p is an integer from 3 to 20, are encompassed by this disclosure. The AIRO portion shown in this document also constitutes the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula:
where R is straight or branched alkyl having 1 to 10 carbon atoms, and q is an integer from 1 to 50, are also encompassed by this disclosure. In addition, aluminoxanes suitable for use in this disclosure may have cage structures of the formula R ^ r + aR ^^ AkfOar, where R 'is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a straight or branched alkyl bridge group having 1 to 10 carbon atoms; r is 3 or 4; and α is equal to ΠAI (3) - no (2) + no (4), where ΠAI (3) is the number of three coordinated aluminum atoms, no (2) is the number of two coordinated oxygen atoms, and in (4) is the number of four coordinated oxygen atoms.
[0086] In one embodiment, aluminoxanes that can be used as additional activators in the catalyst compositions of the present disclosure are generally represented by the formulas such as branch (R-AI-O) P, R (R-AI-O) qAIR2, and the like . In these formulas, the R group is usually a straight or branched C1-6 alkyl branch, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxane compounds that can be used in accordance with the present disclosure include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, tert-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoalane, , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane are prepared from trimethylaluminum, triethylalumin, or triisobutylalumin, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide), and poly (isobutyl butyl) aluminum oxide), respectively. It is also within the scope of the disclosure to use an aluminoxane in combination with a trialkylaluminum, as disclosed in U.S. Patent No. 4,794,096, incorporated herein by reference in its entirety.
[0087] The present disclosure contemplates many values of p and q in the formulas of aluminoxane (R-AI-O) P and R (R-AI-O) qAIR2, respectively. In some respects, p and q are at least 3. However, depending on how organoaluminoxane is prepared, stored, and used, the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated in this document.
[0088] In the preparation of a catalyst composition containing an aluminoxane, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of the transition metal complex in the composition is generally between about 1:10 and about 100,000: 1; alternatively, in a range of about 5: 1 to about 15,000: 1. Optionally, aluminoxane can be added to the polymerization zone in ranges of about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or about 1 mg / L to about 50 mg / L.
[0089] In one embodiment, the additional activator comprises an organoboro compound or an organoborate compound. Organoboro or organoborate compounds include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluoro-organo boron compounds and fluoro-organo borate compounds are contemplated.
[0090] Any fluoro-organo boron or fluoro-organo borate compound can be used with the present disclosure. Examples of fluoro-organo borate compounds that can be used in the present disclosure include, but are not limited to, fluorinated aryl borates such as N, N-dimethylanilinium tetraquis- (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] triphenylcarbene borate, and the like, or mixtures of themselves. Examples of fluoro-organo boron compounds that can be used in the present disclosure include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, or mixtures thereof . Although not intended to be linked to the following theory, these examples of fluoro-organo borate and fluoro-organo boron compounds, and related compounds, are oriented to form "poorly coordinated" anions when combined with organometal compounds, a branch disclosed in the Patent US No. 5,919,983, the disclosure of which is incorporated herein by reference in its entirety. Orders also contemplate the use of diboro compounds, or bis-boron compounds, or other bifunctional compounds containing two or more boron atoms in the chemical structure, as disclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the content of which is incorporated into this document by reference in its entirety.
[0091] Generally, any amount of organoboro compound can be used. According to one aspect of this disclosure, the molar ratio of the total moles of the organoboro or organoborate compound (or compounds) to the total moles of the metallocene compound (or compounds) in the catalyst composition is in the range of about 0.1: 1 to about 15: 1. Typically, the amount of the fluoro-organo boron or fluoro-organo borate compound used is about 0.5 mol to about 10 mol of the boron / borate compound per mol of the transition metal complex compound. According to another aspect of this disclosure, the amount of fluoro-organo boron or fluoro-organo borate compound is from about 0.8 mol to about 5 mol of the boron / borate compound per mol of the transition metal complex.
[0092] A catalyst system for preparing BIP can additionally comprise a cocatalyst. In one embodiment, the cocatalyst comprises an organoaluminium compound. Such compounds include, but are not limited to, compounds having the formula: (R1) 3AI; where R1 is an aliphatic group having 2 to 10 carbon atoms. For example, R1 can be ethyl, propyl, butyl, hexyl, or isobutyl.
[0093] Other organoaluminium compounds that can be used in the catalyst compositions disclosed in this document may include, but are not limited to, compounds having the formula: AI (X1) m (X2) 3-m, where X1 is a hydrocarbyl; X2 is an alkoxide or an aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive. In one embodiment, X1 is a hydrocarbyl having from 1 to about 20 carbon atoms; alternatively from 1 to 10 carbon atoms. Non-limiting examples of such hydrocarbons have been previously disclosed in this document. In one embodiment, X2 is an alkoxide or an aryloxide, any one that has 1 to 20 carbon atoms, a halide, or a hydride. In one embodiment, X2 is independently selected from fluorine or chlorine, alternatively, X2 is chlorine. In the formula, AI (X1) m (X2) 3-m, m can be a number from 1 to 3, including, alternatively, m is 3. The value of m is not restricted to being an integer; therefore, this formula includes sesquihalide compounds or other organoaluminium pooling compounds.
[0094] Examples of organoaluminium compounds suitable for use in accordance with the present disclosure include, but are not limited to, trialkylaluminium compounds, dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations of the themselves. Specific non-limiting examples of suitable organoaluminium compounds include trimethylaluminum (TMA), triethylalumin (TEA), tri-n-propylalumin (TNPA), tri-n-butylalumin (TNBA), triisobutylalumin (TIBA), tri-n- hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminium chloride, and the like, or combinations thereof.
[0095] Generally, the weight ratio of the organoaluminium compound to the support-activator is in a range of 10: 1 to about 1: 1000. If more than one organoaluminium compound and / or more than one activator support is used, this ratio is based on the total weight of each respective component. In another embodiment, the weight ratio of the organo-aluminum compound to the activating support is in the range of about 3: 1 to about 1: 100, or about 1: 1 to about 1:50.
[0096] In one embodiment, the catalyst system for preparing BIP of the type described in this document comprises Cp * Cr (CH3) 2 (py), a sulfated alumina support-activator, an optional activator comprising an aluminoxane and an optional cocatalyst comprising an organo-aluminum compound. In one embodiment, the catalyst system for preparing BIP of the type described in this document comprises Cp'Cr (CI) 2 (THF); a sulfated alumina support-activator, an optional activator comprising an aluminoxane and an optional cocatalyst comprising an organoaluminium compound. In one embodiment the catalyst system for preparing BIP of the type described in this document comprises Cp ”Cr (CI) 2 (THF), a sulfated alumina support-activator, an optional activator comprising an aluminoxane and an optional cocatalyst comprising a compound of organoaluminium.
[0097] The catalyst and catalyst systems disclosed in this document are intended for any method of olefin polymerization that can be carried out using different types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing the olefin monomer to produce homopolymers or copolymers. Such homopolymers and copolymers are referred to as resins or polymers.
[0098] Several types of reactors include those that can be referred to as batch, slurry, gas phase, solution, high pressure, tubular or autoclave reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal stepped reactors. Slurry reactors can comprise vertical or horizontal loops. High pressure reactors may comprise tubular or autoclave reactors. Reactor types can include batch or continuous processes. Continuous processes could use continuous or intermittent product discharge. Processes may also include direct total or partial recycling of unreacted monomer, unreacted comonomer, and / or diluent.
[0099] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type. The production of polymers in multiple reactors can include several steps in at least two separate reactor polymerizations interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor in the second reactor. The desired polymerization conditions in one of the reactors may differ from the operating conditions of other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, multiple high pressure reactors or a combination of high pressure with loop reactors and / or gas. The multiple reactors can be operated in series or in parallel.
[00100] According to one aspect of the disclosure, the polymerization reactor system may comprise at least one loop slurry reactor comprising vertical or horizontal loops. Monomer, diluent, catalyst and optionally any comonomer can be fed continuously to a loop reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. The reactor effluent can be flamed to remove the solid polymer from these liquids which comprise the diluent, monomer and / or comonomer. Various technologies can be used for this separation step including, but not limited to, flaming which can include any combination of heat addition and pressure reduction; separation by cyclonic action in both a cyclone and a hydrocyclone; or separation by centrifugation.
[00101] A typical slurry polymerization process (also known as the process particle) is disclosed, for example, in U.S. Patent Nos. 3,248,179; 4,501,885; 5,565,175; 5,575,979; 6,239,235; 6,262,191; and 6,833,415, each of which is incorporated by reference in this document in its entirety.
[00102] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can occur under volume conditions where the diluent is used. One example is the polymerization of the branch propylene monomer disclosed in U.S. Patent No. 5,455,314, which is incorporated by reference in this document in its entirety.
[00103] According to yet another aspect of this disclosure, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back into the reactor. At the same time, the polymer product can be removed from the reactor and the new, fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for multi-stage gas phase polymerization of olefins, in which the olefins are polymerized in at least two independent gas phase polymerization zones during the feeding of a polymer containing catalyst formed in a first zone polymerization to a second polymerization zone. A type of gas phase reactor is disclosed in U.S. Patent No. 5,352,749; 4,588,790; and 5,436,304, each of which is incorporated by reference in this document in its entirety.
[00104] According to yet another aspect of the disclosure, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in the inert gas stream and introduced into a reactor zone. Primers, catalysts, and / or catalyst components can be entrained in the inert gas stream and introduced into a reactor zone. Gas flows can be intermixed by polymerization. Heating and pressure can be used approximately to obtain optimal polymerization reaction rates.
[00105] According to yet another aspect of the disclosure, the polymerization reactor can comprise a solution polymerization reactor in which the monomer comes into contact with the catalyst composition by proper stirring or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer can be presented in the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Stirring can be used to obtain the best temperature control and to keep the polymerization mixes uniform throughout the polymerization zone. Suitable media are used to dissipate exothermic heat from polymerization.
[00106] Polymerization reactors suitable for the present disclosure may additionally comprise any rambling of at least one feedstock feed system, at least one feedstock for catalyst or catalyst components, and / or at least one recovery system polymer. Reactor systems suitable for the present disclosure may additionally comprise systems for purification of the raw material, preparation and storage of catalyst, extrusion, cooling of the catalyst, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis, and control of the process.
[00107] Conditions that are suitable for polymerization efficiency and to provide resin properties include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect the productivity of the catalyst, the molecular weight of the polymer and the molecular weight distribution. The appropriate polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs free energy equation. This usually includes from about 60 ° C to about 280 ° C, for example, and from about 70 ° C to about 110 ° C, depending on the type of the polymerization reactor.
[00108] Appropriate pressures will also vary according to the type of reactor and polymerization. The pressure for liquid phase polymerizations in a loop reactor is usually less than 1000 force-pounds per square inch (psig) meter. The pressure for gas phase polymerization is normally about 200 to about 500 psig. High pressure polymerization in tubular or autoclave reactors is generally carried out at about 20,000 to about 75,000 psig. Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
[00109] The concentration of several reagents can be controlled to produce resins with certain mechanical and physical properties. The proposed end-use product that will be formed by the resin and the method of forming such product determines the desired resin properties. Mechanical properties include tensile strength, bending, impact, creep, tensile relaxation and rigidity tests. Physical properties include density, molecular weight, molecular weight distribution, temperature, glass transition temperature, melting temperature of crystallization melt, density, stereoregularity, increased rupture, long chain branching and rheological measurements.
[00110] The concentrations of monomer, hydrogen, modifiers, and electron donors are important in the production of these resin properties. Hydrogen can be used to control the molecular weight of the product. Modifiers can be used to control product properties and electron donors affect stereoregularity. In addition, the concentration of poisons is minimized because the poisons impact the reactions and properties of the product. In one embodiment, hydrogen is added to the reactor during polymerization. Alternatively, hydrogen is not added to the reactor during polymerization.
[00111] The resin or polymer can be formed into several articles, including, but not limited to, bottles, drums, toys, household containers, utensils, film products, batteries, fuel tanks, tubes, geomembranes, and liners . Various processes can be used to form these articles, including, but not limited to, blow molding, extrusion molding, rotation molding, injection molding, fiber spinning, thermoforming, mold molding and the like. After polymerization, additives and modifiers can be added to the polymer to provide better processing during manufacture and for desired properties in the final product. Additives include surface modifiers such as sliding agents, non-stick agents, taching agents; antioxidants such as primary and secondary antioxidants; pigments; processing aids such as ωmo waxes / oils and fluoroelastomers; special additives such as flame retardants, antistatic agents, scavengers, absorbers, odor enhancers, and degradation agents.
[00112] Catalysts and the catalyst system prepared in accordance with the present disclosure can be used for the polymerization of olefins, for example, alpha-olefins. In one embodiment, a catalyst or catalyst system of the type described in this document enters an olefin in a reaction zone under appropriate reaction conditions (for example, temperature, pressure, etc.) to polymerize the olefins. Linear or branched alpha-olefins having 2 to 30 carbon atoms can be used as raw material for olefins. Specific examples of alpha-olefins can include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, or the like. Such alpha-olefins can be used individually to produce homopolymers. In one embodiment, the catalyst system described herein is used to produce polyethylene, for example, a polyethylene copolymer or homopolymer.
[00113] After polymerization, modifiers and additives can be added to the polymer to provide better processing during manufacture and for desired properties in the final product. Additives include surface modifiers such as glidants, non-stick agents, scavengers; antioxidants such as primary and secondary antioxidants; pigments; processing aids such as waxes / oils and fluoroelastomers; and special additives such as flame retardants, antistatic agents, scavengers, absorbers, odor enhancers, and degradation agents.
[00114] In one embodiment, a catalyst system of the type described in this document when used as a polymerization catalyst can exhibit a catalyst activity in the range of about 10,000 g (PE) / g (Cr) / ha about 5,000. 000 g (PE) / g (Cr) / h; alternatively, from about 20,000 g (PE) / g (Cr) / h to about 4,000,000; alternatively, from about 30,000 g (PE) / g (Cr) / h to about 3,000,000 g (PE) / g (Cr) / h. The catalyst activity is described in terms of polyethylene of grams produced per gram of chromium-catalyst per hour (g (PE) / g Cr / h). In one embodiment, the catalyst activity is independent of the reaction temperature in the range of 60 ° C to about 120 ° C; alternatively from about 70 ° C to about 115 ° C; alternatively from about 80 ° C to about 110 ° C. In this document, "independent of the reaction temperature" refers to a catalyst activity varying by less than about 20%, alternatively less than about 15%; alternatively less than about 10% in the published ranges.
[00115] In one embodiment, the BIP of the type described in this document is a unimodal resin. In this document, the "modality" of a polymer resin refers to the shape of this molecular weight distribution curve, that is, the appearance of this graph of the polymer weight fraction as a function of this molecular weight. The molecular weight fraction refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak can be referred to as a unimodal polymer, a polymer having a curve showing two distinct peaks can be referred to as a bimodal polymer branch, a polymer having a curve showing three distinct peaks can be referred to such as trimodal polymer, etc. Two or more peaks can be referred to as multimodal branches.
[00116] In one embodiment, BIP has an average molecular weight (Mw) of about 10,000 g / mol to about 2,500,000 g / mol, alternatively from about 50,000 g / mol to about 2,000,000 g / mol; or alternatively from about 100,000 g / mol to about 1,500,000 g / mol; or alternatively, from about 140,000 g / mol to about 160,000 g / mol and a number of average molecular weight (Mn) from about 3,000 g / mol to about 150,000 g / mol, alternatively from about 4,000 g / mol mol to about 125,000 g / mol, alternatively from about 5,000 g / mol to about 100,000 g / mol; or alternatively, from about 8,000 g / mol to about 18,000 g / mol. The average molecular weight describes the molecular weight distribution of a polymer composition and is calculated according to equation 1:
where Ni is the number of molecules of molecular weight Mi. All average molecular weights are expressed in grams per mol (g / mol). The average molecular weight number is the average common molecular weights of individual polymers calculated by measuring the molecular weight of polymer molecules n, adding the weights, and dividing by n. 7))

[00117] The molecular weight distribution (MWD) of BIP is the ratio of the average molecular weight (Mw) to the number of average molecular weight (Mn), which is also referred to as the polydispersity index (PDI) or more simply as polydispersity. The BIP composition can be characterized by a wide molecular weight distribution (MWD). More specifically, the BIP composition can have a PDI of about 2 to about 120, alternatively about 3 to about 100, alternatively about 4 to about 80.
[00118] BIP can be characterized by the degree of branching present in the composition. Short chain branch (SCB) is known for these effects on polymer properties such as rigidity, tensile properties, thermal resistance, hardness, permeation resistance, shrinkage, creep resistance, transparency, tensile crack resistance, flexibility, impact resistance, and solid-state properties of semicrystalline polymers, such as polyethylene, although long chain branching (LCB) has its effects on polymer rheology. The BIP composition can contain equal to or less than about one long chain branch (LCB) per about 10,000 total carbon atoms (about 1 / 10,000), alternatively, equal to or less than about one LCB for about 100,000 total carbon atoms (about 1 / 100,000), or alternatively, equal to or less than about one LCB per about 1,000,000 total carbon atoms (about 1 / 1,000,000) . In one aspect, LCB in the BIP can be increased using any suitable methodology such as, for example, by treatment with peroxide. In one aspect, BIP is treated to increase the LCB from more than about 0 to about 0.5, alternatively, from more than about 0 to about 0.25, alternatively, from more than about 0 to about 0.15, or alternatively, about 0.01 to about 0.08.
[00119] In one embodiment, the BIP of the type described in this document is characterized by a density of about 0.946 g / ml to about 0.97 g / ml, alternatively, from about 0.948 g / ml to about 0.968 g / ml, alternatively, from about 0.95 g / ml to about 0.966 g / ml, or alternatively, from about 0.96 g / ml to about 0.966 g / ml as determined according to ASTM D1505. For example, BIP can be a high density polyethylene having a density of more than about 0.945 g / ml, alternatively more than about 0.955 g / ml, alternatively more than about 0.958 g / ml.
[00120] In one embodiment, a BIP produced using a cotalizer of the type described in this document has a melting indicator, Ml, in the range of about 0.01 dg / min. the corca of 5.0 dg / min., alternatively, of corca of 0.05 dg / min. at about 4.0 dg / min., alternatively, around 0.1 dg / min. the corca of 3.0 dg / min, or alternatively, of corca of 0.8 dg / min. the corca of 1.8 dg / min. The melt index (Ml) refers to an amount of a polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 2160 grams in ten minutes at 190 ° C , as determined according to ASTM D 1238.
[00121] In one embodiment, a BIP of the type described in this document has a parameter Carreau Yasuda 'a' in the range of 0.1 to 0.3, alternatively, from 0.5 to about 0, 6, alternatively, from 0.51 to 0.59, alternatively from about 0.54 to about 0.57. The parameter Carreau Yasuda 'a' (CY-a) is defined as the parameter of rheological amplitude. The rheological amplitude refers to the amplitude of the transition region between a power law or Newtonian shear rate for a polymer or dependence on the frequency of the polymer's viscosity. The rheological amplitude is a function of the relaxation time distribution of a resin polymer, which in turn is a function of the molecular resin architecture or structure. The CY-a parameter can be obtained by assuming the Cox-Merz rule and calculated by fitting flow curves generated in dynamic viscoelastic dynamic oscillatory frequency sweeping experiments with a modified Carreau-Yasuda (CY) model, which is represented by equation (3):
where E = viscosity (Pa s) y = shear rate (1 / s) a = rheological amplitude parameter T = relaxation time (s) [describes the time location of the transition region] Eo = zero shear viscosity ( Pa s) [defines the Newtonian plateau] n = power law constant [defines the final slope of the high shear rate region].
[00122] To facilitate model adjustment, the power law constant n is kept at a constant value. Details on the significance and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987), each of which is incorporated by reference into this document in its entirety.
[00123] In one embodiment, a BIP of the type described in this document has a zero shear viscosity (Eo), defined by Equation (3), in the range of about 3.5 x 103 Pa-s to about 7 x 104 Pa-s, alternatively from about 1 x 104 Pa-s to about 6 x 104 Pa-s, alternatively from about 1.5 x 104 Pa-s to about 6 x 104 Pa-s. The zero shear viscosity refers to the viscosity of the polymer composition at a zero shear rate and is indicative of the molecular structure of the materials. In addition, for polymer melts, zero shear viscosity is always a useful indicator of processing attributes such as melt resistance in blow molding and foam technologies and balloon stability in blowing the film. For example, high zero shear viscosity, better melt resistance or balloon stability.
[00124] In one embodiment, a BIP of the type described in this document has a relaxation time (T), defined by Equation (3), in the range of about 0.01 s to about 0.10 s, alternatively, of about from 0.01 s to about 0.03 s, alternatively from about 0.012 s to about 0.08 s, alternatively from about 0.015 s to about 0.05 s. The relaxation rate refers to the viscous relaxation times of the polymer and is indicative of a distribution of relaxation times associated with the broad distribution of molecular weights.
[00125] In one embodiment, a BIP of the type described in this document has a shear viscosity in 100 sec-1 (E100), defined as the indicative of the viscosity of the inlet pressure during extrusion, in the range of about 8 x 102 Pa-s to about 6 x 104 Pa-s, alternatively, from about 8 x 102 Pa-s to about 2 x 103 Pa-s, alternatively, from about 8 x 102 Pa-s to about 1, 2 x 103 Pa-s, alternatively, from about 8.5 x 102 Pa-s to about 1.9 x 103 Pa-s, alternatively, from about 9 x 102 Pa-s to about 1.8 x 103 Pa-s, or alternatively, from about 1 x 104 Pa-s to about 6 x 104 Pa-s. This feature is related to the ease of extrusion during film making and is an indirect comparative measure of the inlet pressure generated by the extrusion of the polymer melt in an extruder. In general, a lower inlet pressure favorable to higher outlet rates, that is, more pounds of material produced per hour of extrusion.
[00126] Polymer resins produced as disclosed in this document can be formed into articles of manufacture or end-use articles using techniques known in the art such as extrusion, blow molding, injection molding, fiber spinning, thermoforming, and casting. For example, a polymer resin can be extruded into a sheet, which is then thermoformed into an end-use article such as a container, cup, tray, pallet, toy, or a component of another product. In one embodiment, polymer resins produced as described in this document (for example, polyethylene) can be formed into films that can be useful in food packaging.
[00127] In one embodiment, the polymer resins of this disclosure are manufactured in a film. The films of this disclosure can be produced by any method and under any condition suitable for the production of these films. In one embodiment, polymer resins are formed into films using a molded film process. In a mold film process, the plastic melt is extruded through a matrix with cracks in a cooled, polished roll to freeze the film. The speed of the roller controls the pull-down ratio and film gauge. The film moves in a second direction by wrapping the roll where cooling is completed. The films formed from the polymer resins of this disclosure (for example, polyethylene) can be of any thickness desired by the user. Alternatively, the polymer resins of this disclosure can be formed into films having a thickness of about 0.3 mil (7 microns) to about 3 mil (76 microns), alternatively, about 0.5 mil (12 microns) at about 2 mils (50 microns), alternatively from about 0.8 mil (20 microns), to about 1.6 mil (40 microns).
[00128] The production of films of the type described in this document can be facilitated by the use of polymeric resins prepared as described in this document. For example, polymeric resins of the type described in this document (ie, BIP) when subjected to the film production process may exhibit enhanced processing characteristics. In one embodiment, polymer resins of the type described in this document can be extruded at a similar extrusion pressure when compared to polymer resins with a similar melt index prepared with a different catalyst system. Such different catalysts can be conventional catalyst systems such as Ziegler Nattum catalysts.
[00129] Additional processing observations that may include similar inlet pressures and engine loads are employed in the manufacturing process with the resins in this disclosure when compared to resins produced using different catalyst systems. Here the inlet pressure refers to the discharge pressure at the end of the extruder while the motor load refers to the extruder power design.
[00130] In one embodiment, BIP comprises a polyethylene homopolymer, which is formed from a film that exhibits increased barrier properties. For example, said films may exhibit a reduced moisture vapor transmission rate (MVTR).
[00131] In one embodiment, particularly a blown film of 1.6 to 1.8 mil thickness produced from polymer resins of this disclosure (ie BIP) has a standardized MVTR indicator in the range of about 0, 30 grams.mil per 100 square inches per day (g.mil/100 in2 / day) at about 0.85 g.mil/100 in2 / day, alternatively about 0.3 g.mil/100 in2 / day at about 0.6 g.mil/100 in2 / day, or alternatively, from about 0.3 g.mil/100 in2 / day to about 0.5 g.mil/100 in2 / day as measured from according to ASTM F 1249. MVTR measurements cross H2O gas through the barrier. MVTR can also be referred to as the water vapor transmission rate (WVTR). Typically, MVTR is measured in a special chamber, vertically divided by the substrate / barrier material. A dry atmosphere is in one chamber, and a moisture atmosphere is in another. A 24-hour test is performed to observe how such moisture passes through the substrate / barrier from a “wet” chamber to a “dry” chamber under conditions that can specify any of the five combinations of temperature and humidity in the “wet” chamber ”. EXAMPLES
[00132] As the subject has been generally described, the following examples are provided as specific modalities of disclosure and to demonstrate the practice and benefits of it. It is understood that the examples are provided by way of illustration and are not intended to limit the description of the following claims in any way. In the following examples, MVTR was measured according to ASTM F-1249. After the resin is extruded into the film, the actual MVTR measurement is performed using a Mocon Permatran machine test system (model 331 W) or equivalent. The Mocon instrument for measuring water permeability was developed by Modem Controls, Inc. To perform the MVTR measurement, a 10 x 10 cm sample is cut from a random area of the film. The sample is then mounted in a sample test cell and placed in the Mocon Permatran W331 unit. In the unit, the test film is exposed to a constant and continuous flow of dry nitrogen gas through one side of the film (exhaust side) and a constant flow of humidity controlled nitrogen gas through the other side (carrier side). The water vapor passes from the side of the test cell to the humidified nitrogen side and through the dry nitrogen side of the test cell. A modulated infrared photodetection system on the exhaust side of the test cell measures the variation in infrared energy absorption caused by the water vapor that has been transmitted through the film. Comparing the amplitude of the output signal obtained from the infrared photodetection system mounted on the test cell with the amplitude of a signal from a reference cell on the same instrument containing a film with a known transmission rate, the rate transmission time of the test film is determined. By convention, the value obtained from MVTR is expressed in grams of water transmitted per 100 square inches by one thousand thickness (one thousandth of an inch) over a 24-hour period (or, in the metric system, grams of water transmitted per meter square per mm of thickness in a 24-hour period). EXAMPLE 1
[00133] Catalyst systems of the type described in this document comprising a half-sandwich chrome transition metal complex, a sulfated alumina support and an optional TIBA cocatalyst were prepared. All manipulations were performed under a purified nitrogen atmosphere using standard Schlenk line or glove box techniques. The THF solvent was distilled from potassium, while anhydrous diethyl ether, heptane, pyridine and toluene (Fisher Scientific Company) were stored on activated alumina. All solvents were released and stored in nitrogen. Chromium (III) trichloride and all organic binders were purchased from Aldrich Chemical Company. Li (η5-C5H4CH2CH2CH = CH2) was prepared by the method described in Brieger, et al., J. Org. Chem. 36 (1971) p243, and Li (η5-C5H4C (Me) 2CH2CH2CH = CH2) was prepared according to the method used by Bochmann, et al. in J. Organmet. Chem. 592 (1999). The (I) complex, Cp * Cr (CH3) 2 (py), was prepared by the procedure described in Theopold, et al. J. Am. Chem. Soc. 111 (1989) p9127.
[00134] The complex (II) that was Cp'Cr (CI) 2 (THF) (Cp '= η5- C5H4CH2CH2CH = CH2) was prepared by a procedure involving adding to a THF solution of CrCh-3THF (1.5 gram, 4.0 mmols) 1 equiv Li (η5-C5H4CH2CH2CH = CH2) (0.5 gram, 4.0 mmols) in THF at 0 ° C. The mixture was stirred at room temperature for 5 hours. After the THF was removed in vacuo, the blue crystal was obtained in a solvent mixture of toluene and heptane at -35 ° C (0.3 gram, yield: 31%). The complex (III) that was Cp "Cr (CI) 2 (THF) (Cp" = η5-CsH4C (Me) 2CH2CH2CH = CH2) was prepared by a procedure involving adding to a THF solution of CrCh-3THF (1, 5 gram, 4.0 mmols) 1 equiv of Li (η5-C5H4C (Me) 2CH2CH2CH = CH2) (0.678 gram, 4.0 mmols) in THF at 0 ° C. The mixture was stirred at room temperature for 5 hours. After the THF was removed in vacuo, the blue crystal was obtained in a heptane mixture solvent at -35 ° C. (0.32 gram, yield: 28%).
[00135] The sulfated solid oxide (SSA) support-activator was prepared with Alumina A, from W.R. Grace Company, which has been impregnated with incipient moisture with an aqueous solution of ammonium sulfate. Typically, alumina had a surface area of about 330 m2 / gram and a pore volume of about 1.3 cc / gram. An amount of ammonium sulphate used was equal to 20% of the starting alumina. The volume of water used to dissolve the ammonium sulfate was calculated from the total pore volume of the initial sample (i.e., 2.6 ml_ of water for each gram of alumina to be treated). Thus, a solution of about 0.08 grams of ammonium sulfate per ml of water was employed. The resulting wet sand was dried in a vacuum oven overnight at 120 ° C, and then selected through a 35 mesh screen. Finally, the material was activated in a 550 ° dry air fluidization flow C for 6 hours. The samples were then stored under nitrogen.
[00136] Catalyst systems comprising complexes (I), (II), or (III), SSA and a cocatalyst were used in the polymerization of ethylene. Generally, all polymerizations were carried out for one hour in a one gallon (3,785 liter) stainless steel autoclave reactor containing two liters of isobutane as a diluent, and hydrogen added from a 325 cc auxiliary vessel. Delta P of hydrogen refers to the pressure drop in the vessel with a starting pressure of 600 psig. Chromium-based half sandwich solutions (Img / ml) were generally prepared by dissolving 20 mg of precursor catalysts in 20 ml of toluene. The reactor was maintained at a desired run temperature by running through an automated heating-cooling system.
[00137] The polymerization process could be carried out using one of the two general protocols. Using protocol 1, under the purging of isobutane a solution of TIBA (25% in heptane) was loaded into a cooled reactor followed by a mixture of chromium-type sandwich complexes and sulfated SSA in toluene. The reactor was closed and 2 liters of isobutane were added. The reactor was heated quickly to within 5 degrees of the run temperature and the ethylene feed was opened, ethylene was fed on demand to maintain the reactor pressure. The hydrogen was then introduced into the reactor during the polymerization process. For copolymerization, 1-hexene was released with the initial charge of ethylene. At the end of an hour, the reactor contents were burned; the reactor was purged with nitrogen, and then opened. The polymer powder was dried overnight at 60 ° C under vacuum. Using Protocol II, under purging of isobutane a mixture of TIBA solution (25% in heptane) and SSA was loaded into a cooled reactor followed by toluene half sandwich chromium compounds. The reactor was closed and 2 liters of isobutane were added. The reactor was heated quickly to within 5 degrees of the run temperature and the ethylene supply opened, ethylene was supplied with demand to maintain the reactor pressure. Hydrogen was then introduced into the reactor during the polymerization process. For copolymerization, 1-hexene was rinsed into the initial ethylene charge. At the end of an hour, the reactor contents were burned; the reactor was purged with nitrogen, and then opened. The polymer powder was dried overnight at 60 ° C under vacuum.
[00138] For samples prepared using Complex (I) and a sulfated SSA activator support, the polymerization process consists of mixing 0.2 mL of TIBA with 0.15 grams of sulfated SSA in a glass tube under nitrogen. After about a minute, the slurry was added to the reactor below at 40oC. 0.001 gram of Cp * Cr (CH3) 2 (py) in 1 ml of toluene was also added to the reactor. The reactor was sealed and 2 L of isobutane were added and stirring started at 700 rpm. As the temperature of the reactor approached 100oC, the addition of H2 (366 psi) and ethylene (555 psi) was started and the control point of 105 ° C was quickly reached. The reactor was kept at 105 ° C for 60 minutes and then the volatile compounds were vented to the flare system. This procedure left the polyethylene solid in the reactor. This yielded 221.4 grams of polyethylene (activity, 1,262,069 g (PE) / g (Cr) / h).
[00139] For samples prepared using Complex (II) and a sulfated SSA support-activator, the polymerization process consisted of adding 0.2 mL of TIBA, 0.3 grams of sulfated SSA, and 0.002 grams of Cp'Cr (CI) 2 (THF) (Cp '= η5-C5H4CH2CH2CH = CH2) in 1 mL of toluene for the reactor respectively under 40oC. The reactor was sealed and 2 L of isobutane were added and stirring started at 700 rpm. As the reactor temperature approached 75oC, the addition of ethylene (550 psi) was initiated and the 80oC control point was then quickly reached. The reactor was kept at 80oC for 60 minutes and then the volatiles were vented to the flare system. This procedure left the polyethylene solid in the reactor. This yielded 358.6 grams of polyethylene (activity, 1,083,455 g (PE) / g (Cr) / h).
[00140] For samples prepared using Complex (III) and a sulfated SSA-activator support, the polymerization process consisted of adding 0.2 mL of TIBA, 0.3 grams of sulfated SSA, and 0.002 grams of Cp "Cr (CI) 2 (THF) (Cp "= η5-C5H4C (Me) 2CH2CH2CH = CH2) in 1mL of toluene to the reactor respectively under 40oC. The reactor was sealed and 2 L of isobutane were added and stirring started at 700 rpm. As the temperature of the reactor approached 85oC, the addition of ethylene (402 psi) was started and the control point of 90oC was then quickly reached. The reactor was maintained at 90oC for 60 minutes and then the volatiles were vented to the flare system. This procedure left the polyethylene solid in the reactor. This yielded 108.1 grams of polyethylene (activity, 366.163 g (PE) / g (Cr) / h).
[00141] A total of 48 samples were prepared and the conditions, components and quantities of components used in each sample, together with the activity of the catalyst are summarized in Table 1. Table 1



[00142] The polymer samples were then subjected to further characterization. The melt index (Ml, g / 10 min) was determined according to condition F of ASTM D1238 at 190 ° C, with a weight of 2,160 grams. The high charge melt index (HLMI, g / 10 min) was determined according to condition E of ASTM D1238 at 190 ° C, with a weight of 21,600 grams. The density of the polymer was determined in grams per cubic centimeter (g / cc) on a molded compression sample, cooled to about 15 ° C per hour, and conditioned for about 40 hours at room temperature according to ASTM D1505 and ASTM D1928, procedure C. Molecular weights and molecular weight distributions were obtained using a PL 220 SEC high temperature chromatography unit (Polymer Laboratories) with trichlorobenzene (TCB) ωmo solvent, with a flow rate of 1 mL / minute at a temperature of 145 ° C. BHT (2,6-di-tert-butyl-4 methylphenol) at a concentration of 0.5 g / L was used as a stabilizer in TCB. An injection volume of 200 pL was used with a nominal polymer concentration of 1.5 mg / ml. The dissolution of the sample in stabilized TCB was performed by heating at 150 ° C for 5 hours, with occasional, gentle agitation. The columns used were three PLgel Mixed A LS columns (7.8x300mm) and were calibrated with a wide linear polyethylene standard (Chevron Phillips Marlex® BHB 5003) so that the molecular weight has been determined. The results of these characterizations are summarized in Table 2. Table 2


[00143] The MWD of samples prepared using the different catalyst systems disclosed in this document is shown in Figure 1, while Figure 2 provides a graphical representation of the radius of rotation as a function of MW. EXAMPLE 2
[00144] Resins produced using a catalyst system of the type described in this document were obtained and tested for film performance. In particular, two sets of BIP samples comprising polyethylene were prepared and designated samples 49 to 52. Samples 49 and 50 were prepared as a first set of BIP samples, while samples 51 and 52 were a second set of BIP samples which were prepared at a later date. Samples 53 to 59 composed of polyethylene resins prepared using different catalyst systems. Specifically, sample 53 was a commercial resin prepared using a Ziegler-Nattum catalyst and having a melt index: 1; sample 54 was commercial resin prepared using a conventional chromium catalyst system and having a melting index: 1; sample 55 was a unimodal commercial resin prepared using a Ziegler Nattum catalyst system and having a melt index of 2; samples 56 and 57 were commercial resins prepared using a modified chromium catalyst system and having a melt index of 2 and 1, respectively; sample 58 was a multimodal resin having a Ml of 2.81 and composed of 60% of a low molecular weight component (LMWH) having a MW = 26 kg / mol and 40% of a high molecular weight component (HMW) having a MW of 220 kg / mol; and sample 59 was a multimodal resin having an Ml of 1.2 and composed of 40% of an LMW component having an MW = 20 kg / mol and 60% of an HMW component having an MW = 220 kg / mol which it had been treated with peroxide to provide an LCB value of 0.05 LCB / 10,000 carbon atoms. GPC was performed on samples from 49 to 52 and a graphic representation of these results is described in figures 3 and 4. The results demonstrate modalities of BIPs of the type disclosed in this document which are unimodal compositions having a wide MWD. Additional results from the GPC analyzes of the 11 samples tested are shown in Table 3. Table 3


[00145] The results demonstrate that samples 49 to 52 had a molecular weight distribution in the range achieved with commercial chromium catalysts (samples 54, 56 and 58), implying that the extrusion facility would be similar to that of these commercial products.
[00146] The rheological behavior of samples 49 to 59 was also evaluated and the results are shown in table 4. Table 4

[00147] The results demonstrate modalities of BIPs of the type described in this document (ie, samples 49 to 52) that have a higher zero shear viscosity without greatly affecting the extrusion viscosity (Eta @ 100) over that of typical bimodal resins such as samples 58 and 59, suggesting that the best blown film has no impact on output rates.
[00148] Barrier properties of the samples were also evaluated and the results are shown in table 5. Table 5

[00149] The results demonstrate that homopolymer samples 51 and 52 achieved the lowest MVTR numbers in a melting index typical of a commercial application for a similar film indicator. In addition, a graphical representation of MVTR as a function of the zero shear viscosity, Figure 5, indicates that the samples would have a blown film bubble stability similar to some of the commercial resins, maintaining the advantage of MVTR.
[00150] Although the modalities of the invention have been shown and described, their modifications can be made by one skilled in the art without departing from the teachings and spirit of the invention. The modalities described here are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed in this document are possible and are within the scope of the invention. Numerical limitations or ranges are expressly established, such limitations or expressed ranges should be understood as including branches or iterative ranges of such magnitude being within the limitations or ranges expressly established (for example, from about 1 to about 10 includes, 2, 3 , 4, etc .; more than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a numerical range varies with a lower limit, RI, and an upper limit, Ru, is disclosed, any number within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R = RI + k * (Ru-RI), where k is a variable range from 1 percent to 100 percent with an increase of 1 percent, that is , k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent 50 percent, 51 percent, 52 percent 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. In addition, any numerical range defined by two numbers of R as defined above is also specifically disclosed. The use of the term, optionally, in relation to any element of a claim is intended to mean that the matter is of a required element, or alternatively, is not necessary. Both alternatives are intended to be within the scope of the claim. The use of broader terms, such ωmo comprises, includes, having, etc., is to be understood to provide support for more restricted terms such as consisting, consisting essentially of, substantially composed of, etc.
[00151] In this sense, the scope of protection is not limited by the above description, but is limited by the following claims, in that scope, including all equivalents of the subject of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Accordingly, the claims are an additional description and are a complement to the embodiments of the present invention. The discussion of one here is not an admission that is state of the art for the present invention, especially any reference that may have a publication date after the priority date of this application. Disclosures of all patents, patent applications, and publications cited in this document hereby are incorporated by reference, insofar as they provide examples, procedures or other details complementary to those set out in this document.

权利要求:
Claims (14)
[0001]
1. Unimodal polyethylene homopolymer resin characterized by having a density of 0.946 g / ml to 0.97 g / ml, as determined according to ASTM D1505, and the zero cut viscosity of 8 x 102 Pa-s to 6 x 104 Pa-s, a CY-a parameter of 0.5 to 0.6, a relaxation time of 0.01 s to 0.10 s, a polydispersity index of 3 to 120, a long chain branch (LCB) in an amount of 0.01 to 0.5 and an average molecular weight (Mw) of 140,000 g / mol to 160,000 g / mol.
[0002]
2. Resin according to claim 1, characterized by having an average molecular weight (Mn) number from 3,000 g / mol to 150,000 g / mol.
[0003]
Resin according to claim 1, characterized by having a melting index of 0.01 g / 10 min. at 5.0 g / 10 min as determined according to ASTM D1238.
[0004]
4. Resin according to claim 1, characterized by having an E100 of 8 x 102 Pa-s to 2 x 103 Pa-s.
[0005]
Resin according to claim 1, characterized in that it has a density greater than 0.955 g / ml as determined according to ASTM D1505.
[0006]
Resin according to claim 1, characterized in that it has an LCB content of 0.01 to 0.25.
[0007]
Resin according to claim 1, characterized by having a polydispersity index of 4 to 80.
[0008]
8. Film characterized by being produced from the resin as defined in claim 1.
[0009]
9. Film according to claim 8, characterized by having a thickness of 7.62 x 10 '3 mm to 7.62 x 10' 2 mm (0.3 mils to 3.0 mils).
[0010]
10. Film, according to claim 8, characterized by having a moisture vapor transmission rate from 1.18 x 10'7 kg / m / day to 3.35 x 10'7 kg / m / day (0 , 3 g.mil/100 inch / day at 0.85 g.mil/100 inch / day) as determined according to ASTM F-1249.
[0011]
11. Method characterized by comprising: (a) providing a catalyst system comprising a half-sandwich transition metal complex; (b) contacting the catalyst system with an olefin to form a unimodal polyethylene homopolymer resin at a polymerization temperature of 90 to 105 ° C; and (c) recovering the resin as defined in claim 1.
[0012]
12. Method according to claim 11, characterized in that it also comprises contacting the polyethylene with peroxide after recovering the resin.
[0013]
13. Method according to claim 11, characterized in that a film formed by polyethylene has a moisture vapor transmission rate of 1.18 x 10-7 kg / m / day at 3.35 x 10'7 kg / m / day (0.3 g.mil/100 in2 / day at 0.85 g.mil/100 in2 / day) as determined according to ASTM F-1249.
[0014]
14. Method according to claim 13, characterized in that the film has a thickness of 7.62 x 10-3 mm to 7.62 x 10'2 mm (0.3 mils to 3.0 mils).

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-01-28| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2020-09-08| B09A| Decision: intention to grant|

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2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/890,448|2010-09-24|

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US12/890,448|US8828529B2|2010-09-24|2010-09-24|Catalyst systems and polymer resins having improved barrier properties|

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PCT/US2011/052261|WO2012040144A1|2010-09-24|2011-09-20|Novel catalyst systems and polymer resins having improved barrier properties|

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