POLYURETH COMPOSITION AND SEALED OPENING WITH SEALANT

专利摘要:
composition and opening sealed with sealant, polyurea compositions comprising reaction products of a polyformalisocyanate prepolymer and a curing agent comprising amine are described. the compositions are useful as sealants in aerospace applications.
公开号:BR112013023776B1
申请号:R112013023776-7
申请日:2012-03-16
公开日:2020-03-10
发明作者:Stephen J. Hobbs；Juexiao Cai；Marfi Ito；Renhe Lin
申请人:Prc-Desoto International, Inc.；
IPC主号:

专利说明:

"POLYURETH COMPOSITION AND SEALED SEALED OPENING" Field of the invention [0001] The present invention relates to polyurea compositions and methods for using polyurea compositions.
Background of the invention [0002] Sulfur-containing polymers with thiol termination are well known as suitable for use in various applications, such as aerospace sealant compositions, due in large part to their resistance to fuel. Other desirable properties for aerospace sealant compositions include low temperature flexibility, short curing time (the time required to achieve predetermined strength) and high temperature resistance, among others. Sealing compositions which exhibit at least some of these characteristics and which contain thiol-terminated sulfur-containing polymers are described, for example, in U.S. Pat. 2,466,963, 4,366,307, 4,609,762, 5,225,472, 5,912,319, 5,959,071, 6,172,179, 6,232,401, 6,372,849 and 6,509,418. Polysulfides are also used in aerospace sealant compositions, providing high tensile strength, high shear strength, high temperature resistance, and fuel resistance, as described, for example, in U.S. Patent No. 7,638,162 and American Patent Publication No. 2005/0245695.
[0003] Polythioethers, which are liquid at ambient temperature and pressure and have excellent low temperature flexibility and excellent fuel resistance, as described in U.S. Patent No. 6,172,179, are also useful in aerospace sealant compositions. Diffunctional polythioethers with terminal hydroxyl groups prepared by reacting a hydroxyl compound with an aldehyde are described, for example, in GB 850,178, U.S. Pat. 3,959,227 and 3,997,614. Difunctional polyethers finished or capped with isocyanates are also well known, for example in GB 850,178 patents, and US patents Nos. 3,290,382, 3,959,227 and 3,997,614. The difunctional linear polythioethers, however, often swell upon prolonged exposure to hydrocarbon fuel and other lubricants. On the other hand, sealants prepared with polyfunctional polyethers, can exhibit good fuel resistance, good hardness and flexibility, but often with compromised elongation.
[0004] It is desirable to provide compositions that are useful as fuel resistant and water resistant sealants, with improved tensile strength and elongation.
Summary of the invention [0005] Polyurea compositions for use as sealants containing improved properties useful for aerospace sealant applications are provided.
[0006] In a first aspect of the present invention, compositions are provided that comprise a polyform-isocyanate prepolymer comprising reaction products of reagents comprising a polyform polyol and a first diisocyanate; and a curing agent comprising an amine. [0007] In a second aspect of the present invention, compositions are provided comprising the reaction products of reagents comprising a polyform-isocyanate prepolymer comprising the reaction products of a polyform polyol and a first aliphatic diisocyanate; a polythio-isocyanate prepolymer comprising the reaction products of a polythioether polyol and a second aliphatic diisocyanate; and an aromatic diamine.
[0008] In a third aspect of this report, sealed openings are provided with compositions comprising sealants provided by the present invention.
[0009] The present invention is also directed, among other things, to methods for preparing such polyurea compositions, and sealants, including aerospace sealants, comprising such polyurea compositions.
Brief description of the drawings [0010] Those skilled in the art understand that the drawings described here are for illustration purposes only. The drawings are not intended to restrict the scope of the present invention.
[0011] Figure 1 shows an example of a reaction to prepare a thiodiglycol-polyformal-isocyanate prepolymer with 4,4'-methylene dicyclohexyl (H12-MDI) diisocyanate termination.
Detailed description Definitions [0012] A dash ("-") that is not between two letters or symbols, is used to indicate a point of attachment for a substituent or between two atoms. For example, -CONH2 is linked via the carbon atom.
[0013] "Aldehyde" refers to a compound of the formula CH (O) R where R is hydrogen or a hydrocarbon group, such as an alkyl group, as defined herein. In certain embodiments, the aldehyde is C1-C10 aldehyde, C1-4 aldehyde, C1-3 aldehyde, and in certain embodiments, C1-2 aldehyde. In certain embodiments, the aldehyde is formaldehyde. In certain embodiments of the aldehyde, R is selected from hydrogen, C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, aryl C6-12 and aryl C6-12 substituted.
[0014] "Alcanodiila" refers to a diradical of a branched or straight chain saturated acyclic hydrocarbon group, having, for example, from 1 to 18 carbon atoms (C1-18), from 1-14 carbon atoms ( C1-14), 1-6 carbon atoms (C1-6), 1 to 4 carbon atoms (C1-4) or 1 to 3 hydrocarbon atoms (C1-3). In certain embodiments, the alkanediyl is C2-14 alkanediyl, C2-10 alkanediyl, C2-8 alkanediyl, C2-6 alkanediyl, C2-4 alkanediyl, and in certain embodiments, C2-3 alkanediyl. Examples of alkanodiyl groups include methane-diyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl and isopropane-1,2-diyl (ex: -CH2CH2CH2- and - CH (CH3) CH2-), butane-1,4-diyl (-CH2CH2CH2CH2-), pentane-1,5-diyl [0015] (-CH2CH2CH2CH2CH2-), hexane-1,6-diyl (- CH2CH2CH2CH2CH2CH2), heptane -1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, dodecane-1,12-diyl, and the like.
[0016] "Alkoxy" refers to an -OR group, where R is alkyl, as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. In certain embodiments, the alkoxy group is C1-8 alkoxy, C1-6 alkoxy, C1-4 alkoxy, and in certain embodiments, C1-3 alkoxy.
[0017] "Alkyl" refers to a monoradical of a branched or straight chain saturated acyclic hydrocarbon group containing, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 atoms of carbon, from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like. In certain embodiments, the alkyl group is C2-6 alkyl, C2-4 alkyl and in certain embodiments, C2-3 alkyl.
[0018] "Arila" refers to a monovalent aromatic hydrocarbon radical derived by the removal of a hydrogen atom from a simple carbon atom from a parental aromatic ring system. Arila comprises aromatic carbocyclic rings of 5 and 6 members, for example, benzene; bicyclic ring systems, where at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems, where at least one ring is carbocyclic and aromatic, for example, fluorene. Arila encompasses multiple ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring. For example, aryl includes aromatic carbocyclic rings of 5 and 6 members fused to 5- to 7-membered heterocycloalkyl ring containing one or more heteroatoms selected from N, O and S. For these fused bicyclic ring systems, where only one of the rings is a aromatic carbocyclic ring, the point of attachment can be on the carbocyclic aromatic ring or on the heterocycloalkyl ring. Examples of aryl groups include acenatrylene, acenaphthene, acefenantrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafen, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octafen , octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinafthalene, and the like. In certain embodiments, the aryl group may have 6 to 20 carbon atoms, and in certain embodiments, 6 to 12 carbon atoms, and in certain embodiments, 6 to 10 carbon atoms. Aryl, however, does not encompass or overlap in any way with heteroaryl, defined separately in the present invention. Thus, a multiple ring system in which one or more carbocyclic aromatic rings is fused to a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein. In certain embodiments, an aryl group is phenyl.
[0019] "Arylalkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced with an aryl group. In certain embodiments of an arylalkyl group, a hydrogen atom at the terminal carbon atom of an alkyl group is replaced with an aryl group. In certain embodiments of arylalkyl, the aryl group is a C6-12 aryl group, in certain embodiments, a C6-10 aryl group, and in certain embodiments, a phenyl or naphthyl group. In certain embodiments, the alkanediyl portion of an arylalkyl group can be, for example, C1-10 alkanodiyl, C1-16 alkanodiyl, C1-4 alkanodiyl, C1-13 alkanodiyl, propane-1,3-diyl, ethane-1,2 -diyl, or methane-diyl. In certain embodiments, the arylalkyl group is C7-18 arylalkyl, C7-16 arylalkyl, C7-12 arylalkyl, C7-10 arylalkyl, or C7-9 arylalkyl. For example, C7-9 arylalkyl may include a C1-3 alkanediyl group attached to a phenyl group.
[0020] "Cycloalkylalkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced with a cycloalkyl group. In certain embodiments of the cycloalkylalkyl group, a hydrogen atom on a terminal carbon atom of an alkyl group is replaced with a cycloalkyl group. In certain embodiments of cycloalkylalkyl, the cycloalkyl group is a C3-6 cycloalkyl group, in certain embodiments, a C5-6 cycloalkyl group, and in certain embodiments, a cyclopropyl group, a cyclobutyl, a cyclopentyl, or a cyclohexyl. In certain embodiments, the alkanediyl portion of a cycloalkylalkyl group can be, for example, C1-10 alkanediyl, C1-6 alkanediyl, C1-4 alkanediyl, C1-3 alkanediyl, propane-1,3-diyl, ethane-1,2 -diyl, or methane-diyl. In certain embodiments, the cycloalkylalkyl group is C4-16 cycloalkylalkyl, C4-12 cycloalkylalkyl, C4-10 cycloalkylalkyl, C6-12 cycloalkylalkyl, C4-9 cycloalkylalkyl. For example, C6-9 cycloalkylalkyl includes a C1-3 alkanoodiyl group attached to a cyclopentyl or cyclohexyl group.
[0021] "Alcanocycloalkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanodiyl groups and one or more alkyl and / or alkanodiyl groups, where cycloalkyl, cycloalkanodiyl, alkyl and alkanodiyl are defined herein. In certain embodiments, each cycloalkyl and / or cycloalkanodiyl group (s) is C3-6, C5-6, and in certain embodiments, cyclohexyl or cyclohexanediyl. In certain embodiments, each alkyl and / or alkanediyl group (s) is C1-6, C1-4, C1-3 and in certain embodiments, methyl, methanodiyl, ethyl, or ethane-1,2-diyl. In certain embodiments, an alkanocycloalkane group is C4-18 alkanocycloalkane, C4-16 alkanocycloalkane, C4-12 alkanocycloalkane, C4-12 alkanocycloalkane, C6-10 alkanocycloalkane, and in certain embodiments, C6-9 alkanocycloalkane. Examples of alkanocycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.
[0022] "Alcanocycloalkanodiyl" refers to a diradical of an alkanocycloalkane group. In certain embodiments, an alkanocycloalkanodiyl group is C4-18 alkanocycloalkanodiyl, C4-16 alkanocycloalkanodiyl, [0023] C4-12 alkanocycloalkanodiyl, C4-12 alkanocycloalkanodiyl, C6-12 alkanocycloalkyl, 6-alkanocycloalkyl, 6-alkanocycloalkyl, 6-alkanocycloalkyl, 6-alkanocycloalkyl, 6-alkalkylalkyl-6 . Examples of alkanocycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.
[0024] "Cycloalkanediyl" refers to a saturated monocyclic or polycyclic diradical hydrocarbon group. In certain embodiments, the cycloalkanediyl group is C3-12 cycloalkanediyl, C3-8 cycloalkanediyl, C3-6 cycloalkanediyl, and in certain embodiments, C5-6 cycloalkanediyl. Examples of cycloalkanodiyl include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl and cyclohexane-1,2-diyl.
[0025] "Cycloalkyl" refers to a monocyclic or polycyclic saturated monoradical hydrocarbon group. In certain embodiments, the cycloalkyl group is C3-12 cycloalkyl, C3-8 cycloalkyl, C3-6 cycloalkyl, and in certain embodiments, C5-6 cycloalkyl.
[0026] "Heteroalkyl" refers to an alkyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S or P. In certain embodiments of heteroalkyl, the heteroatom is selected from N it's the.
[0027] "Heteroaryl" refers to a monovalent heteroaromatic radical derived by removing a hydrogen atom from a single atom in a parental heteroaromatic ring system. Heteroaryl encompasses multiple ring systems having at least one heteroaromatic ring fused to at least one other ring, which can be aromatic or non-aromatic. Heteroaryl comprises aromatic monocyclic rings of 5 to 7 members, containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3, heteroatoms selected from N, O, S and P with the remaining ring atoms being carbon; and bicyclic heterocycloalkyl rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3 heteroatoms selected from N, O, S and P, with the remaining ring atoms being carbon and at least a heteroatom is present in an aromatic ring. For example, heteroaryl includes a 5- to 7-membered heteroaromatic ring fused to a 5- to 7-membered cycloalkyl ring. For such fused bicyclic heteroaryl ring systems, where only one of the rings contains one or more heteroatoms, the point of attachment may be on the heteroaromatic ring or the cycloalkyl ring. In certain embodiments, where the total number of N, O, S and P atoms in the heteroaryl group exceeds one, the heteroatoms are not adjacent to each other. In certain embodiments, the total number of N, O, S and P atoms in the heteroaryl group is not greater than two. In certain embodiments, the total number of N, O, S and P atoms in the aromatic heterocycle is not greater than one. Heteroaryl does not cover or overlap with aryl as defined herein. Examples of heteroaryl groups include groups derived from acridine, arsindol, carbazole, α-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isothiazole, isoxidine, isoxidine, naxidine, naxidine, naxidine oxadiazole, oxazole, perimidine, phenanthridine, phenatroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline, thiouzoline, thiazoline, tetrazoline, thiazine xanthene, and the like. In certain embodiments, the heteroaryl group is C5-20 heteroaryl, C5-12 heteroaryl, C5-10 heteroaryl, and in certain embodiments, C5-6 heteroaryl. In certain embodiments, heteroaryl groups are those derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole or pyrazine. "Ketone" refers to a compound of the formula CO (R) 2, where each R is a hydrocarbon group. In certain embodiments of a ketone, each R is independently selected from C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, and substituted C6-12 cycloalkylalkyl. In certain embodiments of the ketone, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, the ketone is selected from propan-2-one, butan-2-one, pentan-2-one, and pentan-3-one. In certain embodiments of the ketone, each R is independently selected from C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, aryl C6-12, and aryl C6-12 substituted.
[0028] "Phenylalkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced with a phenyl group. In certain embodiments of the phenylalkyl group, one of the hydrogen atoms of the terminal carbon atom of an alkyl group is replaced with a phenyl group. In certain embodiments, the phenylalkyl group is phenylalkyl C7-12, phenylalkyl C7-10, phenylalkyl C7-9, and in certain embodiments, benzyl.
[0029] "Substituted" refers to a group in which one or more hydrogen atoms are each independently substituted with the same or different substituents. In certain embodiments, the substituent is selected from halogen, -S (O) 2OH, -S (O) 2, -SH, -SR, where R is C1-6 alkyl, -COOH, -NO2, -NR2, where each R is independently selected from hydrogen and C1-3 alkyl, -CN, = O, C1-6 alkyl, C1-3 alkyl, -CF3, -OH, phenyl, C2-6 heteroalkyl, C5-6 heteroaryl, C1-6 alkoxy , and -COR, where R is C1-6 alkyl. In certain embodiments, the substituent is selected from -OH, -NH2 and C1-3 alkyl.
[0030] Unless stated otherwise, a polymer comprises one or more types of polymers. For example, the reference to a polyform polyol includes a simple type of polyform polyol such as polyiodiform tiodiglycol polyol, and a mixture of different types of polyform polyols. Similarly, unless otherwise stated, reference to a compound such as, for example, a compound of specific formula or a diisocyanate, refers to a simple type of compound or diisocyanate and more than one type of compound or diisocyanate.
[0031] For the purposes of the following detailed description, it is understood that the embodiments provided by this report may assume variations and alternative step sequences, unless expressly specified otherwise. In addition, except in any operational example, the quantities of ingredients used in the report and in the claims must be understood as modified, in all cases, by the term “about”. Consequently, unless otherwise stated, the numerical parameters established in the report and in the attached claims are approximations that may vary, depending on the desired properties to be obtained by the present invention. At least and not for the purpose of restricting the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must be interpreted at least in the light of the number of significant digits reported and applying normal rounding techniques.
[0032] Although the ranges and numerical parameters established for the broad scope of the invention are approximate, the numerical values established in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective test measurements.
[0033] Likewise, it should be understood that any numerical range mentioned here intends to include all the sub-ranges included therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and inclusive) the minimum quoted value of 1 and the maximum quoted value of 10, that is, having a minimum value equal to or greater than 1 and a value maximum equal to or less than 10.
[0034] Reference is now made in detail to certain embodiments of compounds, compositions and methods. The described embodiments are not intended to restrict the claims. On the contrary, the claims are intended to cover all alternatives, modifications and equivalents. [0035] Polyurea Compositions [0036] In certain embodiments, the compositions provided by the present invention comprise a polyform-isocyanate prepolymer and a curing agent comprising an amine, where the polyform-isocyanate prepolymer comprises the products of reaction of reagents comprising a polyform polyol and a first diisocyanate.
[0037] In certain embodiments, the polyform polyol comprises a polyform polyol selected from a polyform diol, a polyform polyol having at least three hydroxyl groups per poliform molecule and a combination thereof. In certain embodiments, the polyform polyol comprises a polyform polyol selected from a polyform diol, a polyform triol and a combination thereof. In certain embodiments, the polyform polyol comprises a combination of a polyform diol and a polyform triol. [0038] In certain embodiments, a polyform polyol comprises: (i) reagent reaction products comprising a sulfur-containing diol; and a reagent selected from an aldehyde, a ketone, and a combination thereof; (ii) reagent reaction products comprising a sulfur-containing diol; a polyol containing at least three hydroxyl groups per polyol molecule; and a reagent selected from an aldehyde, a ketone, and a combination thereof; and (iii) a combination of (i) and (ii).
[0039] In certain embodiments of reaction (i), the sulfur-containing diol comprises a simple type of sulfur-containing diol, and in certain embodiments, it comprises a combination of sulfur-containing diols.
[0040] In certain embodiments, the polyform polyol comprises the reaction products of a sulfur-containing diol; and a reagent selected from an aldehyde, a ketone, and a combination thereof. In certain embodiments of the reaction, the sulfur-containing diol comprises a diol of Formula (1): where each R is independently selected from C2-6 alkanediyl. In certain embodiments of a sulfur-containing diol of Formula (1), each R3 is the same and in certain embodiments, each R is different. In certain embodiments, each R is selected from C2-5 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl and in certain embodiments, each R is ethane-1,2-diyl. In certain embodiments of the reaction, the sulfur-containing diol comprises a sulfur-containing diol selected from 2,2'-thiodiethanol, 3,3'-thiobis (propan-1-ol), 4,4'-thiobis (butan-1-ol ), and a combination of any of the above. In certain embodiments of the reaction, the sulfur-containing diol comprises 2,2'-thiodiethanol.
[0041] In certain embodiments of reaction (i), the reagent is an aldehyde. In certain embodiments in which the reagent is an aldehyde, the aldehyde comprises a C1-6 aldehyde, C1-4 aldehyde, a C1-3 aldehyde and in certain embodiments, a C1-2 aldehyde. In certain embodiments, the aldehyde is formaldehyde. In certain embodiments, in which the reagent is formaldehyde, formaldehyde is provided as paraformaldehyde.
[0042] In certain reaction embodiments (i), the reagent is a ketone. In certain embodiments in which the reagent is a ketone, the ketone has the formula COR2, where each R is independently selected from C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, C6-12 cycloalkylalkyl substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl. In certain embodiments of a ketone, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, a ketone is selected from propan-2-one, butan-2-one, pentan-2-one, and pentan-3-one.
[0043] In certain reaction embodiments (i), the polyform polyol comprises the reaction product of reagents comprising 2,2'-thiodiethanol and formaldehyde, and is referred to herein as polyform tiodiglycol.
[0044] In certain embodiments, a polyform polyol has a numerical average molecular weight of 200 to 6,000 Daltons, from 500 to 5,000 Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4,000 Daltons, and in certain embodiments, from 2,000 to 3,600 Daltons .
[0045] In certain embodiments, the polyform polyols provided by the present invention comprise: (ii) reaction products comprising a sulfur-containing diol; a polyol containing at least three (3) hydroxyl groups per polyol molecule; and a reagent selected from an aldehyde, a ketone, and a combination thereof. The reagents may comprise one or more types of sulfur-containing diol, one or more types of polyol and / or one or more types of aldehyde and / or ketone.
[0046] In certain reaction embodiments (ii), the sulfur-containing diol comprises a diol of Formula (1), where each R is independently selected from C2-6 alkanediyl. In certain embodiments of reaction (ii), the sulfur-containing diol comprises a sulfur-containing diol selected from 2,2'-thiodiethanol, 3,3'-thiobis (propan-1-ol), 4,4'-thiobis (butan- 1-ol), and a combination of any of the above. In certain embodiments of the reaction, the sulfur-containing diol comprises 2,2'-thiodiethanol.
[0047] In certain reaction embodiments (ii), the sulfur-containing diol comprises a simple type of sulfur-containing diol, and in certain embodiments, it comprises a combination of sulfur-containing diols.
[0048] In certain reaction embodiments (ii), a polyol contains at least three hydroxyl groups per polyol molecule. For example, a polyol can contain three to ten hydroxyl groups per polyol molecule, three to eight hydroxyl groups per polyol molecule, three to six hydroxyl groups per polyol molecule, and in certain embodiments, three to four groups hydroxyl per polyol molecule. In certain embodiments, a polyol contains four hydroxyl groups per polyol molecule, and in certain embodiments, a polyol contains three hydroxyl groups per polyol molecule. The polyol can be a simple type of polyol or it can be a combination of different polyols having the same or different number of hydroxyl groups per molecule.
[0049] In certain embodiments, a polyol has the formula E (OH) z, where z is an integer from 3 to 6, and E represents the core of the z-valent polyol. In certain embodiments, a polyol comprises a triol (z is 3) of Formula (2): where each R11 is independently C1-6 alkanediyl; and in certain embodiments, a polyol comprises a triol of Formula (3): where each R11 is independently C1-6 alkanediyl. In certain embodiments of a Formula (2) and Formula (3) polyol, each R11 can be independently selected from C1-4 alkanediyl, and in certain embodiments, from C1-3 alkanediyl. In certain embodiments, of a Formula (2) and Formula (3) polyol, each R11 can be the same and in certain embodiments, each R11 can be different. In certain embodiments of a Formula (2) and Formula (3) polyol, each R11 is selected from methanediyl, ethane-1,2-diyl, propane-1,3-diyl, and in certain embodiments, butane-1, 4-diyl.
[0050] In certain embodiments of reaction (ii), the reagent is aldehyde. In certain embodiments in which the reagent is an aldehyde, the aldehyde comprises a C1-6 aldehyde, a C1-4 aldehyde, a C1-3 aldehyde, and in certain embodiments, a C1-2 aldehyde. In certain embodiments, the aldehyde comprises an alkyl and is selected from acetaldehyde, propionaldehyde, isobutyraldehyde, and butyraldehyde. In certain embodiments, the aldehyde is formaldehyde. In certain embodiments in which the reagent is formaldehyde, formaldehyde is provided as paraformaldehyde. [0051] In certain embodiments of reaction (ii), the reagent is a ketone. In certain embodiments in which the reagent is a ketone, the ketone has the formula C (O) R2, where each R is independently selected from C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl. In certain embodiments of a ketone, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, a ketone is selected from propan-2-one, butan-2-one, pentan-2-one, pentan-3-one, and 3-methylbutan-2-one.
[0052] In certain reaction embodiments (ii), a polyform polyol comprises the reaction product of reagents comprising 2,2'-thiodiethanol, a polyol and formaldehyde. In certain embodiments of reaction (ii), a polyform polyol comprises the reaction product of reagents comprising 2,2'-thiodiethanol, a triol, and formaldehyde. In certain embodiments, a polyform polyol provided by the present invention comprises the reaction product comprising 2,2'-thiodiethanol, formaldehyde, and a triol of Formula (2). In certain embodiments, a polyform polyol provided by the present invention comprises the reaction product of reagents comprising 2,2'-thiodiethanol, formaldehyde, and a triol of Formula (3).
[0053] In embodiments in which the one or more polyols used to form polyform polyols provided by the present invention have the same number of hydroxyl groups, the polyform polyol will have a hydroxyl functionality approximately equivalent to that of the one or more polyols. For example, when a polyol having a hydroxyl functionality of three or a combination of polyols, in which each of the polyols in the combination has a hydroxyl functionality of three, it is used in the preparation of a polyform polyol, the polyform polyol may have a functionality average hydroxyl of three, four, five and in certain embodiments, six. [0054] When polyols containing different hydroxyl functionalities are used for the preparation of polyformal polyols, polyformal polyols can exhibit a range of functionalities. For example, the polyform polyols provided by the present invention can have an average hydroxyl functionality of 3 to 12, 3 to 9, 3 to 6, 3 to 4, and in certain embodiments, from 3.1 to 3.5. In certain embodiments, a polyform polyol having an average hydroxyl functionality of three to four can be prepared by reacting a combination of one or more polyols having a hydroxyl functionality of three and one or more polyols having a hydroxyl functionality of four.
[0055] In certain embodiments, the polyform polyols provided by the present invention have a hydroxyl index of 10 to 100, 20 to 80, 20 to 60, 20 to 50, and in certain embodiments, 20 to 40. The hydroxyl index is the hydroxyl content of the polyform polyol, and can be determined, for example, by acetylating the hydroxyl groups and titrating the resulting acid against potassium hydroxide. The hydroxyl index is the weight of potassium hydroxide in milligrams that neutralizes the acid of one gram of the polyform polyol.
[0056] In certain embodiments, a polyform polyol provided by the present invention has a numerical average molecular weight of 200 to 6,000 Daltons, from 500 to 5,000 Daltons, from 1,000 to 4,000 Daltons, from 1,500 to 3,500 Daltons and, in certain embodiments, from 2,000 Daltons to 3,000 Daltons.
[0057] In certain embodiments, a polyform polyol comprises a polyform polyol selected from a polyform polyol of Formula (4), a polyform polyol of Formula (5), and combinations thereof: [0058] where w is selected from an integer number of 1 to 50; z is selected from an integer from 3 to 6; each R is independently selected from C2-6 alkanediyl; each R4 is independently selected from hydrogen, C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl , and substituted C6-i2 aryl; and E represents the nucleus of a parent z-valent E (OH) z polyol.
[0059] In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R5 is ethane-i, 2-diyl and each R4 is hydrogen.
[0060] In certain embodiments, a polyform polyol has the structure of Formula (4) and / or Formula (5), where w is selected from an integer from i to 50; each R is independently C2-6 alkanediyl; and each R4 is independently selected from hydrogen, C1-6 alkyl, C7-i2 phenylalkyl, substituted C7-i2 phenylalkyl, C6-i2 cycloalkylalkyl, substituted C6-i2 cycloalkylalkyl, substituted C3-i2 cycloalkyl, C3-i2 cycloalkyl, C6- i2 and substituted C6-i2 aryl.
[006i] In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R3 is independently selected from C2-6 alkanediyl, C2-4 alkanediyl, C2-3 alkanodiyl, and in certain embodiments, ethane-i, 2-diyl. In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R3 is ethane-1,2-diyl.
[0062] In certain embodiments of the polyform polyol of Formula (4) and / or Formula (5), each R4 is independently selected from hydrogen, C1-6 alkyl, C1-4 alkyl, C1-3 alkyl, and in certain embodiments, C1-2 alkyl. In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R4 is hydrogen, in certain embodiments, methyl and in certain embodiments, ethyl.
[0063] In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R3 is the same and is selected from a C2-3 alkanediyl, such as ethane-1,2-diyl and propane-1 , 3-diyl; and each R4 is the same and is selected from hydrogen and C1-3 alkyl, such as methyl, ethyl and propyl. In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R3 is ethane-1,2-diyl. In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), each R4 is hydrogen. In certain embodiments of a Formula (4) and / or Formula (5) polyform polyol, each R3 is ethane-1,2-diyl, and each R4 is hydrogen.
[0064] In certain embodiments of a polyform polyol of Formula (4) and / or Formula (5), w is an integer from 1 to 50, an integer from 2 to 40, an integer from 4 to 30, and in certain embodiments, w is an integer from 7 to 30. [0065] In certain embodiments, a polyform polyol of Formula (4) and / or Formula (5) has a numerical average molecular weight of 200 to 6,000 Daltons, 500 to 5,000 Daltons, 1,000 to 5,000 Daltons, 1,500 to 4,000 Daltons, and in certain embodiments, 2,000 to 3,600 Daltons.
[0066] In certain embodiments of a polyform polyol of Formula (5), z is 3, z is 4, z is 5, and in certain embodiments, z is 6.
[0067] In certain embodiments of a polyform polyol of Formula (5), where z is 3, the parent polyol E (OH) z is a triol of Formula (2): where each R11 is independently C1-6 alkanediyl, and in certain embodiments, a triol of Formula (3): where each R11 is independently C1-6 alkanediyl.
Consequently, in these embodiments, E has the structure: respectively, where each R11 is independently C1-6 alkanediyl.
[0068] A polyform-isocyanate prepolymer can be formed by reacting a diisocyanate with a polyformal polyol. In certain embodiments, the molar ratio of the diisocyanate to the polyform polyol is greater than 2 to 1, greater than 2.3 to 1, greater than 2.6 to 1, and in certain embodiments, greater than 3 to 1.
[0069] Polyform-isocyanate prepolymers can be formed by first reacting a polyform polyol with a diisocyanate to form a polyform polyol diisocyanate adduct. The adduct can then be oligomerized by reaction with additional polyform polyol and diisocyanate to provide a diisocyanate terminated polyform oligomer. In certain embodiments, the polyiform-isocyanate prepolymer comprises a combination of unreacted diisocyanate, the 2: 1 adduct of diisocyanate-polyform polyol, and the diisocyanate-terminated polyform oligomer. An example of a reaction sequence using polyformal thiodiglycol and H12MDI to form a polyformal isocyanate thiodiglycol prepolymer with H12MDI termination is shown in Figure 1, where w is an integer from 1 to 50, and y is an integer from 2 to 15.
[0070] The reaction used in the preparation of a polyformal polyol can occur in the presence of an acid catalyst, such as sulfuric acid, sulfonic acid, or a combination thereof. In certain embodiments, a sulfonic acid can be used. Examples of sulfonic acids include alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, ter-butane sulfonic acid, 2-propane sulfonic acid, and cyclohexyl sulfonic acid; alkene sulfonic acids, such as α-olefin sulfonic acid, dimerized α-olefin sulfonic acid, and 2-hexenesulfonic acid; aromatic sulfonic acids, such as para-toluene sulfonic acid, benzene sulfonic acid, and naphthalene sulfonic acid; and polymer-supported sulfonic acids, such as AMBERLYST ™ sulfonic acid catalysts from Dow Chemical.
[0071] In certain embodiments, a polyiform isocyanate prepolymer comprises the reaction products of a polyform polyol and an aliphatic diisocyanate.
[0072] Examples of aliphatic diisocyanates suitable for reacting with a polyform polyol include 1,6-hexamethylene diisocyanate, 1,5-diisocyanate-2-methylpentane, methyl-2,6-diisocyanatohexanoate, bis (isocyanatomethyl) cyclohexane, 1,3 -bis (isocyanatomethyl) cyclohexane, 2,2,4-trimethylhexane, 1,6-diisocyanate, 2,4,4-trimethylhexane, 1,6-diisocyanate, 2,5 (6) -bis (isocyanatomethyl) cycle [2.2. 1] heptane, 1,3,3-trimethyl-1- (isocyanatomethyl) -5-isocyanatocyclohexane, 1,8-diisocyanate-2,4-dimethyloctane, octahidro-4,7-methane-1H-indenodimethyl diisocyanate and 1, 1'-methylenebis (4-isocyanatocyclohexane), and 4,4'-methylene dicyclohexyl diisocyanate (H12-MDI).
[0073] Examples of alicyclic aliphatic diisocyanates suitable for reacting with a polyformal polyol include isophorone diisocyanate (IPDI), cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) 2-propane, bis (isocyanatocyclohexyl) -1,2-ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl ) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3- isocyanatopropyl ) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane and 2-isocyanatoethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicycle [2.2.1] - heptane.
[0074] In certain embodiments, a polyform-isocyanate prepolymer comprises the reaction products of a polyform polyol and an aliphatic diisocyanate selected from IPDI, an HDI trimer, H12 MDI, and a combination of any of the above. Examples of HDI trimers include, for example, 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (6-isocyanatohexyl), DESMODUR® N3300, DESMODUR® N3368, DESMODUR® N3386, DESMODUR® N3390, DESMODUR® N3600, DESMODUR® N3800, DESMODUR® XP2731, DESMODUR® XP2742, DESMODUR® XP2675 and DESMODUR® N2714.
[0075] In certain embodiments, a polyform-isocyanate prepolymer comprises the reaction products of a polyform polyol and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI).
[0076] In certain embodiments, an amine comprises a polyamine, such as a diamine. In certain embodiments, an amine curing agent comprises an aromatic diamine, such as, for example, dimethyltiotoluenediamine, diettyltoluenediamine or a combination thereof. In certain embodiments, an aromatic diamine comprises dimethyltiotoluene diamine, such as ETHACURE® 300, which comprises 95% -97% of dimethylthiotoluene diamine, 2% -3% monomethylthiotoluene diamine, where dimethylthiotoluene diamine comprises a combination of 3,5-dimethylthio-2 , 6-toluene diamine, and 3,5-dimethylthio-2,4-toluene diamine as the main isomer. In certain embodiments, an aromatic diamine comprises diethyltiotoluenediamine such as ETHACURE®100, which comprises 75% -81% diethyltoluene-2,4-diamine and 18% -20% 3,5-diethyltoluene-2,6-diamine. In certain embodiments, the composition comprises excess molar equivalent of isocyanate to amine, such as, for example, excess molar equivalent of 1.01 to 1.2, 1.02 to 1.1, 1.02 to 1.08, from 1.03 to 1.07 and in certain embodiments, 1.05.
[0077] In certain embodiments, a composition provided by the present invention comprises a polyform-isocyanate prepolymer comprising the reaction products of reagents comprising a polyform polyol and a first diisocyanate, a polythio-isocyanate prepolymer comprising the products of reaction of reagents comprising a polythioether polyol and a second diisocyanate, and a curing agent comprising an amine. [0078] In certain embodiments, a polyether polyether comprises a polyether polyether selected from a polyether diol, a polyether polyol and a combination thereof. In certain embodiments, a polythioether polyol comprises a combination of a polyol ether diol and polyether polyether.
[0079] A polythioether polyol refers to a polythether with hydroxyl group terminals. As used herein, the term "polythioether" refers to a compound containing at least two thioether bonds, that is "-CR2-S-CR2" groups. In certain embodiments, such compounds are polymers. As used herein, "polymer" refers to oligomers, as well as homopolymers and copolymers. Unless otherwise stated, molecular weights are the numerical average molecular weights for polymeric materials, indicated as "Mn" as can be determined, for example, through gel permeation chromatography using a polystyrene standard recognized in the prior art.
[0080] In certain embodiments, the polyether polyol comprises a polyol selected from a polyether polyether of Formula (6); a polythioether polyol of Formula (7) and a combination thereof: where each R1 is independently selected from C2—6 alkanodiyl, C6—8 cycloalkanediyl, C6—10 alkanocycloalkanediyl, [0081] - [(- CH2—) p — X— ] q - (- CH2 -) r—, and - [(- CH2—) p — X—] q (—CH2—) r—, where at least one —CH2— group is replaced with a methyl group 2; each R is independently selected from C2—6 alkanodiyl, C6—8 cycloalkanodiyl, C6—10 alkanocycloalkanodiyl, - [(- CH2—) p — X—] q - (- CH2—) r—; X is selected from -O—, —S— and -NR10—, where R10 is selected from hydrogen and methyl;
[0082] Z represents the nucleus of a functionalizing agent 88 z — valiant B (R) z, where each R is selected from a group that is reactive with a -SH group and / or a -CH = CH2 terminal group; each m is independently selected from a rational number from 0 to 10; each n is independently selected from an integer from 1 to 60; each p is independently selected from an integer from 2 to 6; each q is independently selected from an integer from 0 to 5; each r is independently selected from an integer from 2 to 10; and z is selected from an integer from 3 to 6. In certain embodiments, B represents the nucleus of a polyfunctionalizing agent such as those described in U.S. Patent Nos. 4,366,307; 4,609,762; and 5,225,472, where a polyfunctionalizing agent refers to a compound having three or more moieties that are reactive with terminal -SH and / or -CH = CH2 groups.
[0083] The polyether polyols of Formula (6) and Formula (7) are generally described, for example, in U.S. Patent No. 6,172,179, incorporated herein by reference in their entirety.
[0084] A polythioether polyol may comprise a polyol ether diol, a polyether polyether, a polyether polyether having a functionality of 4 to 6, or a combination of any of the above. In certain embodiments, a polyether polyol comprises a combination of a polyether diol and a polyether polyol. For example, in certain embodiments, a polythioether polyol comprises a combination of a polythioether diol of Formula (9): HO- (CH2) 4-O- (CH2) 2- [S- {(CH2) 2-O} 2- (CH2) 2-S- {(CH2) 2-O} 3- (CH2) 2-] n "S- {(CH2) 2-O} 2- (CH2) 2-S- (CH2) 2-O - (CH2) 4-OH (9) and a polyethylene triol of Formula (10): where each A is a portion of Formula (11): HO- (CH2) 4-O- (CH2) 2-S- {( CH2) 2-O} 2- (CH2) 2-S- {(CH ..) ..- O} .- (CH2) 2 "-S- {(CH2) 2-O} 2- (CH2) 2 -S-] n- <CH2> 2 (11) where n is selected from an integer from 1 to 60, and in certain embodiments, an integer from 7 to 30.
[0085] In certain embodiments, polyether polyols comprise a structure having Formula (12): -R1- [-S- (CH2) 2-O- [-R2-O-] m- (CH2) 2-S- R1-] n (12) where: each R1 is independently selected from C2-6 alkanodiyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkanodiyl, - [(- CH2-) p- X-] q - (- CH2-) r - e - [(- CH2-) pX-] q - (- CH2-) r-, where at least one -CH2- group is replaced with a methyl group; 2 each R is independently selected from C2-6 alkanediyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkanediyl, - [(- CH2-) p-X-] q - (- CH2-) r-; each X is selected from -O-, -S- and -NR10-, where R10 is selected from hydrogen and methyl; each m is independently selected from a rational number from 0 to 10; each n is independently selected from an integer from 1 to 60; each p is independently selected from an integer from 2 to 6; each q is independently selected from an integer from 0 to 5; each r is independently selected from an integer from 2 to 10.
In certain embodiments, a polythioether polyol comprises a polythioether polyol of Formula (13): R4- [R3] y-A- [R3] y-R4 (13) [0086] where: A has the structure of Formula (12); each y is independently selected from 0 and 1; 33 each R is a single bond where y is 0; or each R is independently -S- (CH2) 2 - [- O-R-] m-O-, where y is 1; each R4 is independently -S- (CH2) 2 + 5-O-R5, where y is 0; or each R4 is independently - (CH2) 2-S-R5, where y is 1; each m is independently selected from a rational number from 0 to 10; each s is independently selected from an integer from 0 to 10; and each R5 is independently - (CH2) t-OH, where each t is independently selected from an integer from 1 to 6. In certain embodiments, a polyether polyol comprises a polyether polyether of Formula (14): B- (A- [R3] y-R4) z (14) [0087] where: each A independently has the structure of Formula (12); each y is independently selected from 0 and 1; 33 each R is a single bond where y is 0; or each R is independently -S- (CH2) 2 - [- O-R -] m-O- where y is 1; each R4 is independently -S- (CH2) 2 + s-O-R5 where y is 0; or each R4 is independently - (CH2) 2-S-R5, where y is 1; each R5 is independently - (CH2) t-OH, where each t is independently selected from an integer from 1 to 6; each m is independently selected from a rational number from 0 to 10; each s is independently selected from an integer from 0 to 10; z is independently selected from an integer from 3 to 6; and B is a z-valent residue of a polyfunctionalizing agent B (R) z, where each R is a moiety that is reactive with a -SH terminal and / or -CH = CH2 terminal group.
[0088] In certain embodiments, a polyethyl polyol of Formula (13) and a polyethyl polyol of Formula (14).
[0089] In certain embodiments, a polyether polyol comprises the reaction products of a thiol terminated polyether and a vinyl ether with hydroxy functionality. The preparation of thiol-terminated polyethers is described, for example, in U.S. Patent No. 6,172,179.
[0090] For example, in certain embodiments, a thiol-terminated polythether can be prepared by reacting (n + 1) moles of one or more dithols of Formula (15);
HS-R1-SH (15) where R1 is defined as for Formula (12); with (n) moles one the most divinyl ethers of Formula (16); CH2 = CH-O- [-R2-O-] m-CH = CH2 (16) where R2 and m are defined as for Formula (12); in the presence of an appropriate catalyst. In certain embodiments, the thiol-terminated polythether comprises the products of the aforementioned reaction.
[0091] The compounds of Formula (15) are dithiols. In certain embodiments of a dithiol, R1 is a C2-6 n-alkanediyl such as, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol and 1,6-hexanedithiol.
[0092] In certain embodiments of a Formula (15) dithiol, R1 is a branched C3-6 alkanodiyl group, having one or more pendant groups which can be, for example, methyl or ethyl groups. In certain embodiments of a dithiol in which R1 is branched alkanediyl, the dithiol is selected from 1,2-propanedithiol, 1,3-butanedithiol, 2,3-butanedithiol, 1,3-pentanedithiol and 1,3-dithio-3- methylbutane. Other suitable dithiols include compounds of Formula (15) where R1 is a C6-8 cycloalkanediyl or C6-10 alkylcycloalkanediyl, for example, dipentenodimercaptan or ethylcyclohexilditiol (ECHDT).
[0093] In certain embodiments, a dithiol includes one or more hetero atom substituents on the main carbon chain, for example, dithiols where X is a hetero atom such as O, S or another divalent hetero atom; a secondary or tertiary amine group, that is, -NR6-, where R6 is hydrogen or methyl; or another substituted trivalent heteroatom. In certain embodiments of a dithiol, X is O or S, so that R1 is, for example, - [(- CH2-) pO-] q - (- CH2-) r-or - [(- CH2-) pS -] q - (- CH2-) r-. In certain embodiments of a dithiol, p and r are the same, in certain embodiments, each p and r is 2. In certain embodiments, a dithiol is selected from dimercaptodiethylsulfide (DMDS), dimercaptodioxaoctane (DMDO), and 1,5-dithia-3-oxapentane. In certain embodiments of a dithiol, the dithiol includes heteroatom substituents on the main carbon chain and includes pendant alkyl groups, such as a methyl group. In certain embodiments, a dithiol is selected from DMDS substituted with methyl, such as HS-CH2CH (CH3) -S-CH2CH2-SH, HS-CH (CH3) CH2-S-CH2CH2-SH, and DMDS substituted with dimethyl as HS-CH2CH (CH3) -S-CH (CH3) CH2-SH and HS-CH (CH3) CH2-S-CH2CH (CH3) -SH.
[0094] The Compounds of Formula (16) are divinyl ethers. The divinyl ether itself (m is 0) can be used. In certain embodiments, divinyl ethers include compounds having at least one oxyalkanediyl group, and in certain embodiments, from 1 to 4 oxyalkanediyl groups (i.e., compounds in which m is selected from an integer from 1 to 4). In certain embodiments of a compound of Formula (16), m is selected from an integer from 2 to 4. It is also possible to use commercially available mixtures of divinyl ether in the production of polyethers according to the present invention. Such mixtures can be characterized by a non-integral average value for the number of alkoxy units per molecule. Thus, m in Formula (16) can also employ non-integral rational values between 0 and 10, in certain embodiments, between 1 and 10, in certain embodiments, between 1 and 4, and in certain embodiments, between 2 and 4.
Examples of suitable divinyl ethers include compounds in which R is C2-6 alkanodiyl such as, for example, ethylene glycol divinyl ether (EG-DVE); butanediol divinyl ether (BD-DVE); hexanediol divinyl ether (HD-DVE); diethylene glycol divinyl ether (DEG-DVE); triethylene glycol divinyl ether; and tetraethylene glycol divinyl ether. Suitable divinyl ether mixtures include mixtures of the PLURIOL® type, such as divinyl ether PLURIOL® E-200 (marketed by BASF) and polymeric DPE mixtures such as DPE-2 and DPE-3 (from International Specialty Products, Wayne, NJ). In certain embodiments, a divinyl ether of Formula (16) is selected from DEG-DVE and PLURIOL®E-200. Divinyl ethers in which R2 is C2-6 branched alkanediyl can be prepared by reacting a polyhydroxy compound with acetylene. Examples of such divinyl 2 ethers include compounds in which R is an alkyl-substituted methylene group, such as -CH (CH3) - and an alkyl-substituted ethylene, such as -CH2CH (CH3) -.
[0096] In certain embodiments, a thiol-terminated polythioether can be prepared by reacting (n + 1) moles of a compound of one or more divinyl ethers of Formula (16); and (n) moles of one or more dithiols of Formula (15); in the presence of an appropriate catalyst. In certain embodiments, a thiol-terminated polythether comprises the products of the aforementioned reaction.
[0097] In certain embodiments, a thiol-terminated polythether can be prepared by reacting (n + 1) moles of a compound of one or more dithols of Formula (15); and (n) moles of one or more divinyl ethers of Formula (16); in the presence of an appropriate catalyst. In certain embodiments, a thiol-terminated polythether comprises the products of the aforementioned reaction.
[0098] Polyfunctional polyethers with thiol termination can be prepared, for example, by reacting (n + 1) moles of one or more dithols of Formula (15); (n) moles of one or more divinyl ethers of Formula (16); and one or more z-valent polyfunctionalizing agents; in the presence of a suitable catalyst. In certain embodiments, a polyfunctional polythioether with thiol termination comprises the products of the aforementioned reaction.
[0099] A polyfunctionalizing agent is a compound that has more than two portions, such as 3 to 6 portions, which are reactive with terminal -SH and / or -CH = CH2 groups. A polyfunctionalizing agent can be represented by Formula (17): B- (R8) z (17) where each R is independently selected from a group that is reactive with terminal -SH and / or -CH = CH2 groups, and z is selected from an integer from 3 to 6. Examples of polyfunctionalizing agents include trialylcyanurate (TAC) and 1,2,3-propanotriol. Other suitable polyfunctionalizing agents include trimethylolpropane, trivinyl ether, and the polythioles described in U.S. Pat. 4,366,307, 4,609,762, 5,225,472 and 6,172,179.
[0100] In certain embodiments, polyfunctional polyethers with thiol termination can also be prepared by reacting (n) moles of one or more Formula 915 dithols); (n + 1) moles of one or more divinyl ethers of Formula (16); and one or more z-valent polyfunctionalizing agents; in the presence of a suitable catalyst. In certain embodiments, a thiol-terminated polythether comprises the products of the aforementioned reaction.
[0101] In certain embodiments, the thiol-terminated polythether can be prepared by reacting one or more dithiols of Formula (15); one or more divinyl ethers of Formula (16); and one or more polyfunctionalizing agents; in the presence of an appropriate catalyst, at a temperature, for example, from 30 ° C to 120 ° C for 2 hours to 24 hours. In certain embodiments, a thiol-terminated polythether comprises the products of the aforementioned reaction.
[0102] A thiol-terminated polythioether can then be reacted with a vinyl ether with hydroxy functionality to provide a polyol polyether. Examples of suitable vinyl ethers with hydroxy functionality useful for reacting with thiol-terminated polyethers include triethylene glycol monovinyl ether, 1,4-cyclohexane dimethylol monovinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and a combination of any of the above. In certain embodiments, vinyl ether with hydroxy functionality is 4-hydroxybutyl vinyl ether.
[0103] In certain embodiments, the polyether polyol comprises from 60% to 95% of a polyether ether, and from 5% to 40% of a polyether polyol, where the percentage refers to the molar percentage. In certain embodiments, the polyether polyol comprises 70% to 90% of a polyether ether and 10% to 30% of a polyether polyol, where the percentage refers to the molar percentage. In certain embodiments, the polyether polyol comprises from 75% to 85% of a polyether ether, and from 15% to 25% of a polyether polyol, where the percentage refers to the molar percentage. In certain embodiments, the polythioether polyol comprises 80% of a polyether ether diol, and 20% of a polyethylene triol, where the percentage refers to the molar percentage.
[0104] In certain embodiments, the polyethylene polyol comprises from 60% to 95% of a Formula polyethylene diol (10), and from 5% to 40% of a polyethylene triol of Formula (11), where the percentage refers to the molar percentage. In certain embodiments, the polythioether polyol comprises 70% to 90% of a Formula (10) polythioether diol and 10% to 30% of a Formula (11) polyethylene triol where the percentage refers to the molar percentage. In certain embodiments, the polythioether polyol comprises 75% to 85% of a Formula (10) polythioether diol, and 15% to 25% of a Formula (11) polyethylene triol, where the percentage refers to the molar percentage . In certain embodiments, the polythioether polyol comprises 80% of a Formula (10) polyol ether diol and 20% of a Formula (11) polythioether, where the percentage refers to the molar percentage.
[0105] In certain embodiments, the polyether polyols provided by the present invention have a hydroxyl index of 10 to 100, 20 to 100, 20 to 80, 20 to 60, and in certain embodiments, 20 to 40. The hydroxyl index is the hydroxyl content of the polythioether polyol, and can be determined, for example, by acetylating the hydroxyl groups and titrating the resulting acid against potassium hydroxide. The hydroxyl index is the weight of potassium hydroxide in milligrams that will neutralize the acid of one gram of the polythioether polyol.
[0106] In certain embodiments, the polyether polyols provided by the present invention have a numerical average molecular weight of 200 to 6,000 Daltons, from 500 to 5,000 Daltons, from 1,000 to 4,000 Daltons, from 1,500 to 3,500 Daltons, and in certain embodiments, from 2,000 Daltons to 3,000 Daltons. A polyol polyether provided by the present invention may comprise from 50% to 90% of a polyol ether and from 10% to 50% of a polyethyl triol, and in certain embodiments, from 70% to 90% of a polyol ether and 10% to 30% of a polythio triol. In certain embodiments, the polyether polyol comprises a combination of polyether polyols comprising 70% to 90% of a Formula (6) polyethylene diol and 10% to 30% of a Formula (7) polyethylene triol, where the percentage in weight is based on the full functionality of polythioether polyol. In certain embodiments, the polyether polyol comprises a combination of polyether polyols comprising 70% to 90% of a Formula (10) polyethylene diol and 10% to 30% of a Formula (11) polyethylene triol, where the percentage in weight is based on the full functionality of the polyether polyol.
[0107] In certain embodiments, a polyether polyol comprises a combination of polyether polyols and the average functionality of the polyether polyether combination is 2.1 to 4, 3 to 4, 2.5 to 3.5 and in certain embodiments , from 2.1 to 2.5.
[0108] A polythio-isocyanate prepolymer can be formed by reacting a diisocyanate with a polyethyl polyol. In certain embodiments, the molar ratio of diisocyanate to polythioether polyol is greater than 2 to 1, greater than 2.3 to 1, greater than 2.6 to 1, and in certain embodiments, greater than 3 to 1.
[0109] In certain embodiments, a polythio-isocyanate prepolymer comprises the reaction products of a polyol polyether and an aliphatic diisocyanate.
[0110] Examples of aliphatic diisocyanates suitable for reacting with a polyether polyether include 1,6-hexamethylene diisocyanate, 1,5-diisocyanate-2-methylpentane, methyl-2,6-diisocyanatohexanoate, bis (isocyanatomethyl) cyclohexane, 1,3 -bis (isocyanatomethyl) cyclohexane, 2,2,4-trimethylhexane, 1,6-diisocyanate, 2,4,4-trimethylhexane, 1,6-diisocyanate, 2,5 (6) -bis (isocyanatomethyl) cycle [2.2. 1] heptane, 1,3,3-trimethyl-1- (isocyanatomethyl) -5-isocyanatocyclohexane, 1,8-diisocyanate-2,4-dimethyloctane, octahidro-4,7-methane-1H-indenodimethyl diisocyanate and 1, 1'-methylenebis (4-isocyanatocyclohexane), and 4,4'-methylene dicyclohexyl diisocyanate (H12-MDI).
[0111] Examples of alicyclic aliphatic diisocyanates suitable for reacting with a polyol polyether ether include isophorone diisocyanate (IPDI), cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatoxylate) 2-propane, bis (isocyanatocyclohexyl) -1,2-ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl ) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3- isocyanatopropyl ) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3 - isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane and 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicycle [2.2.1] -heptane.
[0112] In certain embodiments, a polythio-isocyanate prepolymer comprises the reaction products of a polyol polyether and an aliphatic diisocyanate selected from IPDI, an HDI trimer, H12 MDI, and a combination of any of the above.
[0113] In certain embodiments, a polythio-isocyanate prepolymer comprises the reaction products of a polythioether polyol and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI). In certain embodiments, a polythio-isocyanate prepolymer comprises the reaction products of a combination of 80 wt% to 20 wt% of a Formula (10) polythioether diol and a Formula (11) polyethio triol and of 4,4'-methylene dicyclohexyl diisocyanate (H12MDI). In certain embodiments, a polythio-isocyanate prepolymer comprises the reaction products of the 2: 1 thio-ene adduct of 4-hydroxybutyl vinyl ether and a combination of 80% by weight / 20% by weight of a polyethylene diol of Formula (10) and a polyethylene triol of Formula (11) and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI).
[0114] The first and second diisocyanates can be the same or different. In certain embodiments, the first and second diisocyanates comprise one or more aliphatic diisocyanates. In certain embodiments, the first and second diisocyanates are selected from IPDI, an HDI trimer, H12MDI and a combination of any of the above. In certain embodiments, both the first and the second diisocyanate comprise 4,4'-methylene disiclohexyl diisocyanate (H12MDI) [0115] Polythioether polyols can be prepared, for example, by reacting thiol-terminated polyether with an ether vinyl with functionality hydroxy to provide a polyether polyol. In certain embodiments, the thiol-terminated polythioether may comprise a thiol-terminated polythioether selected from a dithiol polythioether, a trithiol polythioether, and a combination thereof. In certain embodiments, the thiol-terminated polythether is any of the thiol-terminated polyethers or combinations thereof, described in U.S. Patent No. 6,172,179, hereby incorporated by reference in their entirety. In certain embodiments, the thiol-terminated polythether is a combination of polythio dithols and polythether trietols, such as, for example, Permapol® 3.1E (from PRC-DeSoto International). In certain embodiments, the thiol-terminated polythioether comprises the reaction product of one or more Formula 15 dithiols; one or more divinyl ethers of Formula (16); and one or more polyfunctionalizing agents. The polythioether polyol can then be reacted with a diisocyanate, such as 4,4'-methylene dicyclohexyl diisocyanate (H12MDI) to provide the polythioether isocyanate prepolymer.
[0116] In certain embodiments, the compositions provided by the present invention comprise a catalyst, such as an amine catalyst, an organometallic catalyst, or an acid catalyst. Examples of suitable amine catalysts include, for example, triethylenediamine (1,4-diazabicyclo [2.2.2] octane, DABCO), dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA), bis- (20dimethylaminoethyl) ether, N-ethylmorpholine, triethylamine , 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), pentamethyldiethylenetriamine (PMDETA), benzildimethylamine (BDMA), N, N, N'-trimethyl-N'-hydroxyethyl-bis (aminoethyl) ether, and N '- (3-dimethylamino) propyl) -N, N-dimethyl-1,3-propanediamine. Examples of suitable organometallic catalysts include, for example, mercury, lead, tin (dibutyltin dilaurate, dibutyltin oxide, mercapto dioctyltin), and bismuth (bismuth octanoate). In certain embodiments, the compositions provided by the present invention comprise a carboxylic acid catalyst, such as, for example, formic acid (metanoic acid), acetic acid (ethanoic acid), propionic acid (propanoic acid), butyric acid (butanoic acid) , valeric acid (pentanoic acid), capranoic acid (hexanoic acid), enanthic acid (heptanoic acid), caprylic acid (heptanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid), or a combination of any of the previously mentioned. In certain embodiments, the compositions provided by the present invention comprise pelargonic acid.
[0117] In certain embodiments, a composition comprises the reaction products of reagents comprising a polyform isocyanate prepolymer comprising the reaction products of a polyform polyol and a first aliphatic diisocyanate; a polythio-isocyanate prepolymer comprising the reaction products of a polythioether polyol and a second aliphatic diisocyanate; and an aromatic diamine. In certain embodiments, the first diisocyanate and the second diisocyanate comprise H12MDI, and in certain embodiments, the aromatic diamine comprises dimethyltiotoluenediamine.
[0118] In certain embodiments, a composition comprises the reaction products of reagents comprising (a) a polythio-isocyanate prepolymer comprising the reaction products of a polyether polyether and H12MDI, where the polyether polyether comprises the reaction products of Permapol® P3.1E and hydroxybutyl vinyl ether; and the molar ratio of H12MDI to polythioether polyol is greater than 2 to 1; (b) a polyform-isocyanate prepolymer comprising the reaction products of a polyformal diol of formula (18) and H12MDI; 3 where w is selected from an integer from 1 to 50; each R is ethane-1,2-diyl; and the molar ratio of H12MDI to the polyformal diol is greater than 2 to 1; and (c) an aromatic diamine selected from diethyltoluenediamine, dimethyltiotoluenediamine, and a combination thereof.
[0119] In certain embodiments of the above composition, w in a polyform diol of Formula (18) can be from 7 to 30. In certain embodiments of the above composition, the composition comprises from 70% by weight to 90% by weight of the pre- polythio-isocyanate polymer and 10% by weight to 30% by weight of the polyiform-isocyanate prepolymer, where the weight percentage is based on the total weight percentage of the prepolymers in the composition. In certain embodiments of the above composition, the composition comprises from 45% by weight to 85% by weight of the polythio-isocyanate prepolymer and from 15% by weight to 55% by weight of the polyform-isocyanate prepolymer, where the weight percentage is based on the total weight of the polythio-isocyanate prepolymer and the polyformal-isocyanate prepolymer in the composition. In certain embodiments of the above composition, the composition comprises from 55% by weight to 75% by weight of the polythio-isocyanate prepolymer and from 25% by weight to 45% by weight of the polyform-isocyanate prepolymer, where the % by weight is based on the total weight of the polythio-isocyanate prepolymer and the polyformal-isocyanate prepolymer in the composition. In certain embodiments of the above composition, the aromatic diamine comprises dimethyltiotoluenediamine such as ETHACURE®300.
[0120] In certain embodiments, the compositions provided by the present invention comprise from 45% by weight to 85% by weight of a polythio-isocyanate prepolymer and from 15% by weight to 55% by weight of a prepolymer of polyformal-isocyanate, where the weight percentage is based on the total weight of the polythio-isocyanate prepolymer and the polyformal-isocyanate prepolymer in the composition. In certain embodiments, the compositions provided by the present invention comprise from 55% by weight to 75% by weight of polythio-isocyanate prepolymer and from 25% by weight to 45% by weight of a polyformal-isocyanate prepolymer, where the weight% is based on the total weight of the polythio-isocyanate prepolymer and the polyformal-isocyanate prepolymer in the composition.
[0121] In certain embodiments, the compositions provided by the present invention comprise at least one filler, such as a filler that is effective in reducing the specific gravity of the composition. In certain embodiments, the specific gravity of a composition is 0.8 to 1, 0.7 to 0.9, 0.75 to 0.85 and in certain embodiments, it is 0.8. Suitable fillers to reduce the specific gravity of the composition include, for example, hollow microspheres such as Expancel microspheres (from AkzoNobel) or DUALITE® low density polymer microspheres (from Henkel).
Composition Properties [0122] In certain embodiments, the polythio-isocyanate prepolymers and the polyformal-isocyanate prepolymers provided by the present invention are liquid at room temperature. In certain embodiments, prepolymers have a viscosity, at 100% solids, of no more than about 500 poises, such as 30 to 300 poises, or, in some cases, 100 to 200 poises, at a temperature of 25 ° C and a pressure of 7 60 mmHg determined according to ASTM D-2849 §79-90 using a Brookfield CAP 2000 viscometer.
Uses [0123] The compositions provided by the present invention can be used as sealants, coatings and / or compositions for electrical inlay. A sealing composition refers to a composition capable of producing a film with the ability to withstand atmospheric conditions, such as humidity and temperature, and to block at least partially the transmission of materials, such as water, fuel and other liquids or gases. In certain embodiments, the sealing compositions of the present invention are useful, for example, as aerospace sealants and coatings for fuel tanks.
[0124] In certain embodiments, the compositions provided by the present invention comprise from 10% by weight to 90% by weight of polythio-isocyanate prepolymer and of a 20% polyform-isocyanate prepolymer provided by the present invention. by weight to 80% by weight, from 30% by weight to 70% by weight, and in certain embodiments, from 40% by weight to 60% by weight, where% by weight is based on the total weight of all components non-volatile composition (ie dry weight). In certain embodiments, the compositions provided by the present invention comprise from 10% by weight to 90% by weight of a polythio-isocyanate prepolymer and of a polyformal-isocyanate prepolymer provided by the present invention, of 20% by weight to 90% by weight, from 30% by weight to 90% by weight, from 40% by weight to 90% by weight, from 50% by weight to 90% by weight, from 60% by weight to 90% by weight, from 70% by weight to 90% by weight, and in certain embodiments, from 80% by weight to 90% by weight, where the% by weight is based on the total weight of all non-volatile components of the composition (i.e., the dry weight).
[0125] The compositions provided by the present invention can comprise one or more different types of filler. Suitable fillers include those commonly known in the art, including inorganic fillers, such as carbon black and calcium carbonate (CaCO3) and light fillers. Suitable light loads include, for example, those described in U.S. Patent No. 6,525,168. In certain embodiments, a composition includes from 5% by weight to 60% by weight of the charge or combination of charges, 10% by weight to 50% by weight, and in certain embodiments, from 20% by weight to 40% by weight, based on the total dry weight of the composition.
[0126] As can be appreciated, polythio-isocyanate prepolymers, polyformal-isocyanate prepolymers, amines and fillers used in a composition, as well as any additives, can be selected to be compatible with each other.
[0127] The compositions provided by the present invention can include one or more dyes, thixotropic agents, accelerators, retardants, adhesion promoters, solvents, masking agents, or a combination of any of these. [0128] As used herein, the term "dye" means any substance that imparts color and / or other opacity and / or other visual effect to the composition. A dye can have any suitable shape, such as discrete particles, dispersions, solutions, and / or scales. A single dye or combination of two or more dyes can be used in a composition.
[0129] Examples of dyes include pigments, dyes and inks, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A dye may include, for example, a finely divided solid powder that is insoluble, but wettable under the conditions of use. A dye can be organic or inorganic and can be either agglomerated or non-agglomerated. Dyes can be incorporated into a composition using a grinding vehicle, such as an acrylic grinding vehicle. Examples of pigments and / or pigmented compositions include crude carbazole dioxazin pigment, azo, monoazo, diazo, naphthol AS pigments, saline type (scales), benzimidazolone, isoindolinone, isoindoline, polycyclic phthalocyanine, quinacridone, perylene, perinone, pyrrolidone, pyrrolidone, pyrrolidone, pyrrolidone, pyrrolidone, pyrrolidone. thioindigo, anthraquinone, indantrone, anthrapyrimidine, flavantrone, pyrantrone, antantrone, dioxazine, triarylcarbonium, quinophthalone, pyrrole pyrrole red (DPPNBO red), titanium dioxide, carbon black, and combinations of any of the aforementioned. Examples of dyes include those based on solvent and / or aqueous, such as phthalal green or phthalate blue, iron oxide, bismuth vanadate, anthraquinone, perylene, and quinacridone. Examples of inks include pigments dispersed in water-based or water-miscible carriers, such as AQUA-CHEM 896 sold by Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTES from Accurate Dispersions division Eastman Chemical, Inc.
[0130] As noted above, a dye can be in the form of a dispersion that includes, for example, a nanoparticulate dispersion. Nanoparticulate dispersions can include one or more dispersed nanoparticulate dyes and / or coloring particles that produce a visible color and / or opacity and / or desired visual effect. Nanoparticulate dispersions can include dyes, such as pigments or dyes with a particle size less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by grinding organic or inorganic pigments with grinding media having a particle size less than 0.5 mm. Examples of nanoparticulate dispersions and methods for their manufacture are described in U.S. Patent No. 6,875,800. Nanoparticulate dispersions can also be produced by crystallization, precipitation, gas-phase condensation, and / or chemical friction (ie, partial dissolution). To minimize the re-agglomeration of nanoparticles in the coating, a dispersion of nanoparticles coated with resin can be used. As used herein, a "dispersion of resin coated nanoparticles" refers to a continuous phase in which composite "discrete microparticles" are dispersed that comprise a nanoparticle and a resin coating on the nanoparticle. Examples of dispersions containing resin coated nanoparticles and methods for their preparation are described in U.S. Patent No. 7,438,972.
[0131] Examples of special effect compositions that can be used in the compositions provided by the present invention include pigments and / or compositions that produce one or more effects on appearance, such as reflectance, pearl (pearly luster), metallic luster, phosphorescence, fluorescence , photochromism, photosensitivity, thermochromism, goniochromism, and / or color change. Additional special-effect compositions can provide other noticeable properties, such as opacity and texture. In certain embodiments, special effect compositions can produce a color change, so that the color of a composition changes when the coating is viewed from different angles. Examples of color compositions are described in U.S. Patent No. 6,894,086. Compositions with special color effects may include transparent coated mica and / or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating and / or any composition in which interference results from an index differential of refraction in the material and not due to a difference in the refractive index between the material surface and the air. In general, a dye can comprise from 1% by weight to 65% by weight of a composition, from 2% by weight to 50% by weight, such as 3% by weight to 40% by weight, or 5% by weight. weight to 35% by weight, with the weight percentage based on the total dry weight of the composition.
[0132] Thixotropes, for example, silica, can be used in an amount of 0.1% by weight to 5% by weight, based on the total dry weight of the composition.
[0133] Accelerants can be present in an amount of 0.1 to 5% by weight, based on the total weight of the composition. Examples of suitable accelerants include 1,4-diaza-bicyclo [2.2.2] octane (DABCO®, Air Products, Chemical Additives Division) and DMP-30® (an accelerant composition including 2,4,6-tris (dimethylaminomethyl) phenol ).
[0134] Adhesion promoters can be present in an amount of 0.1% by weight to 15% by weight of a composition, based on the total dry weight of the composition. Examples of adhesion promoters include phenolics, such as METHYLON® phenolic resin from Occidental Chemicals, and organosilanes, such as epoxy, mercapto or silanes with amino functionality, such as SILQUEST® A-187 and SILQUEST® A-1100 from Momentive Performance Materials.
[0135] Masking agents, such as pine fragrance or other fragrances, which can be useful to mask any low level odor in the composition, can be present in an amount of 0.1% by weight to 1% by weight, based on total dry weight of the composition.
[0136] In certain embodiments, the compositions provided by the present invention may comprise a plasticizer that can facilitate the use of prepolymers with a higher glass transition temperature, Tg, than would be commonly useful in an aerospace sealant. For example, the use of a plasticizer can effectively reduce the Tg of a composition, and thus increase the low temperature flexibility of the cured polymerizable composition beyond what would be expected based on the Tg of the individual prepolymers. Suitable plasticizers in certain embodiments of the compositions include, for example, phthalate esters, chlorinated paraffins, and hydrogenated terphenyls. A plasticizer or combination of plasticizers can comprise from 1% by weight to 40% by weight of a composition, or from 1% by weight to 10% by weight of a composition. In certain embodiments, a composition may comprise one or more organic solvents, such as isopropyl alcohol, in an amount, for example, from 0% by weight to 15% by weight, from 0% by weight to 10% by weight, or 0 wt% to 5 wt%, based on the non-dry weight of the composition.
[0137] In certain embodiments, the compositions provided by the present invention are substantially free or, in some cases, completely free of any solvent, such as an organic solvent or an aqueous solvent, i.e., water. Otherwise, in certain embodiments, the compositions provided by the present invention are substantially 100% solid.
[0138] In certain embodiments, compositions, such as sealing compositions, can be provided as multipack compositions, such as double pack compositions, wherein one of the packs comprises one or more prepolymers provided by the present invention and a second pack comprises one or more amine curing agents for the one or more prepolymers. Additives and / or other materials can be added to any of the packages, as desired or necessary. The two packages can be combined and mixed before use. In certain embodiments, the pot life of the one or more mixed prepolymer and curing agent is at least 30 minutes, at least one hour, at least two hours, and in certain embodiments, more of two hours, and the shelf life after mixing refers to the period of time that the mixed composition remains suitable for use as a sealant after mixing.
[0139] The compositions provided by the present invention can be applied to any of a variety of substrates. Examples of substrates to which the compositions can be applied include metals, such as titanium, stainless acid, and aluminum, which can be anodized, primed, coated with organic or coated with chromate; epoxy; urethane; graphite; fiberglass composite; KEVLAR®; acrylics; and polycarbonates.
[0140] The compositions provided by the present invention can be applied directly to the surface of a substrate or over an sublayer through any coating process known in the art.
[0141] In certain embodiments, the compositions provided by the present invention are resistant to fuel. As used herein, the term "fuel resistant" means that a composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that exhibits a maximum volumetric percentage swelling of at most 20%, in other cases maximum 10% after immersion for 140 days at 140 ° F (60 ° C) and ambient pressure in Jet Reference Fluid (JRF) Type 1 according to methods similar to those described in ASTM D792 (American Society for Testing and Materials ) or AMS 3269 (Aerospace Material Specification. Jet Reference Fluid JRF Type I, used to determine fuel resistance, and which has the following composition: toluene: 28 ± 1% by volume; cyclohexane (technical): 34 ± 1% in volume; isooctane: 38 ± 1% by volume; and tertiary dibutyl disulfide: 1 ± 0.005% by volume (see AMS 2629, issued on July 1, 1989, §3.1.1 etc., from the SAE (Society of Automotive Engineers)).
[0142] In certain embodiments, the compositions provide a cured product, such as a sealant, exhibiting an elongation of at least 100% and a tensile strength of at least 400 psi when measured according to the procedure described in AMS 3279 §3.3 .17.1, test procedure AS5127 / 1, §7.7. [0143] In certain embodiments, the compositions provide a cured product, such as a sealant, exhibiting an overlapping shear strength greater than 200 psi and in some cases at least 400 psi, when measured according to the procedure described in SAE AS5127 / 1 paragraph 7.8.
[0144] In certain embodiments, a cured sealant comprising a composition provided by the present invention meets or exceeds the requirements for aerospace sealants set out in AMS 3277.
[0145] In addition, methods are provided for sealing an opening using a composition provided by the present invention. Such methods comprise, for example, applying a composition provided by the present invention to a surface to seal an opening, and to cure the composition. In certain embodiments, a composition can be cured under environmental conditions, with such conditions referring to a temperature of 20 ° C to 25 ° and atmospheric humidity. In certain embodiments, a composition can be cured under conditions ranging from a temperature of 0 ° C to 100 ° C and 0% relative humidity to 100% relative humidity. In certain embodiments, a composition can be cured at a higher temperature, such as at least 30 ° C, at least 40 ° C and, in certain embodiments, at least 50 ° C. In certain embodiments, a composition can be cured at room temperature, for example, 25 ° C. In certain embodiments, a composition can be cured by exposure to actinic radiation, such as ultraviolet radiation. As will also be appreciated, the methods can be used to seal openings in aerospace vehicles.
Examples [0146] The embodiments provided by the present invention are also illustrated by reference to the following examples, which describe the synthesis, properties, and uses of polyether polyols and their prepolymers, polyform polyols and their prepolymers, and compositions of any previously mentioned. It will be apparent to those skilled in the art that many modifications, both in relation to materials and methods, can be practiced without departing from the scope of the invention.
Example 1 Polyformal Polyol [0147] Thiodiglycol (1.833 g), paraformaldehyde (95% purity) (360 g), AMBERLYST ™ 15 (319 g, from the Dow Chemical Company) and toluene (1,000 mL) were loaded into a round bottom flask of 4 mouths of 5 liters. The flask was equipped with a heating blanket, a thermocouple, temperature controller, and Dean-Stark adapter equipped with a reflux condenser, a funnel with a tap and an inlet for positive nitrogen pressure. The reagents were stirred under nitrogen, heated to 118 ° C and maintained at 118 ° C for 7 hours. During this period, the collected water was periodically removed from the Dean Stark adapter. The reaction mixture was then cooled to room temperature and filtered in a deep fried Buchner funnel (600 ml volume) with a 9.0 cm diameter Whatman GF / A paper filter over the frit. The flask and filter cake were washed with 500 ml of toluene. A filtrate was obtained. The filtrate was then vacuum dried using a 2 liter round bottom flask (rotary evaporator, 7 torr final vacuum, 90 ° C water bath) to provide a viscous yellow polymer (1,456 g). The resulting polyformal thiodiglycol polyol had a hydroxyl index of 34.5 and a viscosity of 92 poises.
Example 2 H12-MDI-terminated polyiform-isocyanate prepolymer [0148] The polyiform polyol thiodiglycol of Example 1 (450 g) was loaded into a 4-mouth round-bottomed flask with a capacity of 1,000 ml. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive pressure of nitrogen and a mechanical stirrer (paddle and bearing in PTFE). The polyform polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of DESMODUR® W (H12MDI) (99.5 g) and a 0.01% solution of dissolved dibutyltin dilaurate in methyl ethyl ketone (5.50 g). The reaction mixture was kept at 76.6 ° C for 7 h and then cooled to room temperature. A 1% benzyl chloride solution dissolved in methyl ethyl ketone (5.50 g) was then added to the reaction mixture. The resulting polyformal thiodiglycol prepolymer-isocyanate had an isocyanate content of 3.73% and a viscosity of 356 poises.
Example 3 HDI-Uretidione-terminated polyiform-isocyanate prepolymer [0149] The polyiformal polyol thiodiglycol of Example 1 (101 g) was loaded into a 500 ml 4-mouth round-bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure and a mechanical stirrer (PTFE paddle and bearing). The polyform polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of DESMODUR® XP2730 (aliphatic HDI-uretidione polyisocyanate) (33.4 g) and a 0.01% solution dibutyltin dilaurate dissolved in methyl ethyl ketone (1.4 g). The reaction mixture was kept at 76.6 ° C for 7 h and then cooled to room temperature. A 1% benzyl chloride solution dissolved in methyl ethyl ketone (1.4 g) was then added to the reaction mixture. The resulting prepolymer had an isocyanate content of 3.41% and a viscosity of 695 poises.
Example 4 HDI-Uretidione-terminated polyiform-isocyanate prepolymer [0150] The polyiform polyol thiodiglycol of Example 1 (400 g) was loaded into a 1000 ml 4-neck round bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure and a mechanical stirrer (PTFE paddle and bearing). The polyform polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of DESMODUR® N-3400 (137 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (5.50 g). The reaction mixture was kept at 76.6 ° C for 7 h and then cooled to room temperature. A 1% solution of benzyl chloride dissolved in methyl ethyl ketone (5.5 g) was then added to the reaction mixture. The resulting polyformal thiodiglycol prepolymer-isocyanate had an isocyanate content of 3.31% and a viscosity of 697 poises.
Example 5 HDI-Uretidione-terminated polyiform-isocyanate prepolymer [0151] The polyiform polyol thiodiglycol of Example 1 (504 g) was loaded into a 1000 ml 4-neck round bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure and a mechanical stirrer (PTFE paddle and bearing). The polyform polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of DESMODUR® N-3400 (521 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (10.3 g). The reaction mixture was kept at 76.6 ° C for 7 h and then cooled to room temperature. A 1% solution of benzyl chloride dissolved in methyl ethyl ketone (10.4 g) was then added to the reaction mixture. The resulting polyformal thiodiglycol prepolymer-isocyanate had an isocyanate content of 8.94% and a viscosity of 46 poises.
Example 6 Isoforone-terminated polyform-isocyanate prepolymer [0152] The polyiform polyol thiodiglycol of Example 1 (325 g) was loaded into a 500 ml 4-mouth round-bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure and a mechanical stirrer (PTFE paddle and bearing). The polyformal polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of DESMODUR® N-3400 (62.5 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (4 g). The reaction mixture was kept at 76.6 ° C for 7 h and then cooled to room temperature. A 1% benzyl chloride solution dissolved in methyl ethyl ketone (4 g) was then added to the reaction mixture. The resulting polyformal thiodiglycol prepolymer-isocyanate had an isocyanate content of 3.51% and a viscosity of 229 poises.
Example 7 H12-MDI-terminated polythio-isocyanate prepolymer [0153] A thiol-terminated polythio-ether was prepared according to Example 1 of U.S. Patent No. 6,172,179. In a 2 liter flask, 524.8g (3.32 mol) of diethylene glycol divinyl ether (DEG-DVE) and 706.7 g (3.87 mol) of dimercaptodioxaoctane (DMDO) were mixed with 19.7 g (0 , 08 mol) trialylcyanurate (TAC) and heated to 77 ° C. To the reaction mixture, 4.6 g (0.024 mol) of a free radical azobisnitrile catalyst (VAZO®67, 2,2'-azobis (2-methylbutyronitrile) were added. The reaction proceeded substantially until completion after 2 hours to give 1.250g (0.39 mol, 100% yield) of a thiol-terminated polythioether liquid resin having a Tg of -68 ° C and a viscosity of 65 poises. The resin had a slightly yellowish color and low odor. [0154] A 4-liter, 1-bore, round-bottom flask was equipped with a blanket, thermocouple, temperature controller, nitrogen line, mechanical stirrer and funnel with tap, the flask was loaded with a prepared polythether with a thiol termination (652.30 g) prepared according to Example 1 of US patent No. 6,172,179 (see previous paragraph) The flask was heated to 71 ° C under nitrogen and stirred at 300 rpm A mixture of 4-hydroxybutyl vinyl ether (47.40 g) and Vazo-67 (1.19 g) was added to the flask in 1 hour via a tap funnel. the reaction was maintained at 71 ° C for 41 hours, during which time the reaction was completed. After that, the reaction apparatus was then equipped with a vacuum line and the product heated to 94 ° C. Heating continued for 1.3 hours under vacuum. After vacuum treatment, a pale yellow viscous polythio polyether (678.80 g) was obtained. The polythioether polyol had a hydroxyl index of 31.8 and a viscosity of 77 poises.
[0155] The polythioether polyol (300.03 g) was then loaded into a 500 ml 4-neck round bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, and inlet to provide positive nitrogen pressure, and a mechanical stirrer (PTFE paddle and bearing). The polythioether polyol was stirred at 200 rpm and heated to 76.6 ° C (170 ° C), followed by the addition of DESMODUR W (Hi2MDI) (82.90 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (3.90 g). The reaction mixture was kept at 76.6 ° C for 7h and then cooled to room temperature. A 1% solution of benzyl chloride dissolved in methyl ethyl ketone (3.80g) was then added to the reaction mixture. The H12MDI terminated polythether prepolymer had an isocyanate content of 4.47% and a viscosity of 282 poises.
Comparative Example 8 H12MDI-terminated poly (tetrahydrofuran) prepolymer [0156] TERATHANE® T-2000 (poly (tetrahydrofuran)) (400g) was loaded into a 1,000 ml 3-neck round bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure and a mechanical stirrer (shovel and PTFE bearing). TERATHANE® T-2000 was heated to 76.6 ° C (170 ° F) and stirred. DESMODUR® W (H12MDI) (137.2 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (3.3 g) were added to the flask. The mixture was reacted at 76.6 ° C (170 ° F) for 6 h, when then a 1% solution of benzyl chloride dissolved in methyl ethyl ketone (3.3 g) was added. The resulting poly (tetrahydrofuran) -isocyanate prepolymer had an isocyanate content of 4.67% and a viscosity of 479 poises.
Comparative Example 9 H22MDI terminated polybutadiene prepolymer
[0157] KRASOL® LBH-2000 (polybutadiene with hydroxyl termination) (200g) and KRASOL® HLBH-P 2000 (polyolefin with hydrogenated hydroxyl termination) (200g) were loaded into a 1,000 ml 3-neck round bottom flask. The flask was equipped with a blanket, thermocouple, temperature controller, an inlet to provide positive nitrogen pressure, and a mechanical stirrer (PTFE paddle and bearing). The mixture was heated to 76.6 ° C (170 ° F) and stirred. DESMODUR® W (H12MDI) (137.4 g) and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (5.4 g) were added to the flask. The mixture was reacted at 76.6 ° C (170 ° F) for 6 h, when then a 1% solution of benzyl chloride dissolved in methyl ethyl ketone (5.4 g) was added to the reaction mixture. The resulting polybutadiene-isocyanate prepolymer had an isocyanate content of 5.34% and a viscosity of 892 poises.
Example 10 Cured composition of H12-MDI terminated polyform prepolymer
[0158] A 12 x 12 square inch polyethylene sheet was placed on a 12x12x12 cubic inch flat stainless steel plate. Four 12x1x0.125 cubic inch spacers were placed over the edges of the polyethylene sheet. The polyform-isocyanate prepolymer of Example 2 (90g), pelargonic acid (1.1g) and ETHACURE® 300 (8.15g, Albernale Corporation) were added to the plastic container. The materials were first mixed manually, and then for 60 seconds at 2,300 rpm in a mixer (DAC 600 FVZ).
[0159] The mixed composition was poured evenly over the polyethylene sheet between the spacers. A second 12x12 square inch polyethylene sheet was placed over the top of the composition so that the second polyethylene sheet was separated from the first polyethylene sheet by the 0.124 inch spacers. A second 12x12x0.125 cubic inch thick stainless steel plate was placed on top of the second polyethylene sheet. The composition, interspersed between the two polyethylene sheets, was cured at room temperature for 48 hours, followed by 24 hours at 140 ° F. Finally, the polyethylene sheets were removed to provide a cured polymer sheet 0.125 inches thick.
[0160] The hardness, tensile and elongation resistance, tear resistance, volumetric swelling and water resistance of the polymer sheet are shown in Table 1. The hardness of the cured polymer was measured according to ASTM D2240; tensile strength and elongation were measured according to ASTM D412; and tear strength was measured according to ASTM D624 Matrix C. Weight loss was measured according to SAE AS5127 / 1B §7.4, and volumetric swelling was measured according to SAE AS 5127 / 1B §7.5.
Example 11 Cured polyiform prepolymer composition with HDI-uretidione termination [0161] A cured polymer sheet was prepared as described in Example 10 for a composition containing the polyiform-isocyanate prepolymer (with HDI-uretidione termination) Example 3 (50g), pelargonic acid (0.55 g) and ETHACURE® 300 (4.13 g). The properties of the cured sealant are shown in Table 1.
Example 12 Cured polyiform prepolymer composition with HDI-uretidione termination [0162] A cured polymer sheet was prepared as described in Example 10 for a composition containing the polyiform-isocyanate prepolymer (with HDI-uretidione termination) Example 4 (50g), pelargonic acid (0.55 g) and ETHACURE® 300 (4.02 g). The properties of the cured sealant are shown in Table 1.
Example 13 Cured composition of HDI / IPDI-uretidione-terminated polyform prepolymer [0163] A cured polymer sheet was prepared as described in Example 10 for a composition containing HDI-uretidione-terminated polyformal-isocyanate prepolymer. Example 5 (12g), of the IPDI-terminated polyformal isocyanate prepolymer of Example 6 (48g), pelargonic acid (0.72 g) and ETHACURE® 300 (6, 69 g). The properties of the cured sealant are shown in Table 1. Comparative Example 14 Cured composition of poly (tetrahydrofuran) with H12MDI termination
[0164] A cured polymer sheet was prepared as described in Example 10 for a composition containing the poly (tetrahydrofuran) prepolymer with H12MDI ending in Comparative Example 8 (50g), pelargonic acid (0.6 g) and ETHACURE® 300 (5.67 g). The properties of the cured sealant are shown in Table 1.
Comparative Example 15 Cured composition of hydrogenated hydroxyl terminated polyolefin prepolymer / hydroxyl terminated polybutadiene [0165] A cured polymer sheet was prepared as described in Example 10 for a composition containing the hydrogenated hydroxyl terminated polyolefin prepolymer / H12MDI-terminated hydroxyl-terminated polybutadiene of Comparative Example 9 (50 g), pelargonic acid (0.6 g) and ETHACURE® 300 (6.48 g). The properties of the cured sealant are shown in Table 1.
Example 16 Cured compositions of H12MDI terminated polythiopolymer prepolymer and H12MDI terminated polyform prepolymer
[0166] Cured polymer sheets were prepared as described in Example 10 for compositions containing H12MDI-terminated polymorph-isocyanate prepolymer from Example 2 (32g), the H12MDI-terminated polyether ether prepolymer from Example 7 (18g ), pelargonic acid (0.6 g) and ETHACURE® 300 (4.85 g). The properties of the cured sealant are shown in Table 1.
Example 17 Cured compositions prepared using polyform-isocyanate prepolymers, polythio-isocyanate prepolymer and amine curing agents [0167] AK cured compositions were prepared according to Example 10. AK compositions contained the components shown in Table 2, with the properties of the cured compositions shown in Tables 3-6. In Table 2, the isocyanate content refers to the percentage isocyanate of the prepolymer and the weight of the isocyanate prepolymer refers to the weight in grams of the reacted isocyanate prepolymer to provide the composition. N3400 refers to DESMODUR® N3400 and H12MDI refers to DESMODUR®W. To form the polyform-isocyanate prepolymers, a polyform thiodiglycol prepared according to Example 1 was reacted with DESMODUR® N3400 or DESMODUR® W as described in Example 2. To form the polythio-isocyanate prepolymers, a polythioether polyol prepared as described in Example 7, was reacted with DESMODUR®W, as described in Example 7.
Table 1 · Tested after immersing a sample in type I aviation fuel (Jet Reference Fuel) for 7 days at 140 ° F. ** Tested after immersing the sample in water for 7 days at 200 ° F. * Tested after immersing the sample in Jet Reference Fuel Type I for 7 days at 140 ° F. ** Tested after immersing the sample in water for 7 days at 200 ° F. 1 Tensile strength (psi) / elongation (%) § Volumetric swelling (%) / Weight loss (%) Table 4 * Tested after immersing the sample in jet fuel (Type I) for 7 days at 140 ° F . ** Tested after immersing the sample in water for 7 days at 200 ° F. * Tested after immersing the sample in Jet Reference Fuel Type I for 7 days at 140 ° F. ** Tested after immersing the sample in water for 7 days at 200 ° F.
Table 6 * Tested after immersing the sample in jet fuel (Type I) for 7 days at 140 ° F. ** Tested after immersing the sample in water for 7 days at 200 ° F.
[0168] Finally, it should be understood that there are alternative ways to implement the embodiments described here. Consequently, the embodiments of the present invention are to be considered as illustrative and not restrictive. In addition, the claims are not restricted to the details shown here, being granted the full scope and its equivalents.

权利要求:
Claims (11)
[1]
1. Polyurea composition, characterized by the fact that it comprises: - a polyform-isocyanate prepolymer comprising the reaction products of reagents comprising a polyform polyol and a first diisocyanate; - a polythio-isocyanate prepolymer comprising reaction products of reagents comprising a polythioether polyol and a second diisocyanate; and - a curing agent comprising an amine, the polyform polyol comprising a polyform polyol selected from a polyform polyol of Formula (4), a polyform polyol of Formula (5), and a combination thereof: where: each w is independently selected from an integer from 1 to 50; z is an integer from 3 to 6; each R is independently C2-6 alkanediyl; each R4 is independently selected from hydrogen, C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl , and substituted C6-12 aryl; and E represents the nucleus of a parental z-valent polyol E (OH) z and the polythioether polyol comprising a polythioether polyol of Formula (12); -R1- [-S- (CH2) 2-O- [-R2-O-] m- (CH2) 2-S-R1-] n (12) where: each R1 is independently selected from C2-6 alkanediyl, C6-8 cycloalkanodiyl, C6-1o alkanocycloalkanodiyl, - [(- CH2-) p- X-] q - (- CH2-) r- and - [(- CH2-) pX-] q - (- CH2-) r -, where at least one -CH2- group is replaced with a methyl group; 2 each R is independently selected from C2-6 alkanediyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkanediyl, - [(- CH2-) p-X-] q - (- CH2-) r-; each X is selected from -O-, -S- and -NR10-, where R10 is selected from hydrogen and methyl; each m is independently selected from a rational number from 0 to 10; each n is independently selected from an integer from 1 to 60; each p is independently selected from an integer from 2 to 6; each q is independently selected from an integer from 0 to 5; and each r is independently selected from an integer from 2 to 10.
[2]
2. Composition according to claim 1, characterized by the fact that the molar ratio of the first diisocyanate to the polyform polyol is greater than 2 to 1; or the polyform polyol being selected: (i) from the reaction products of reagents comprising a sulfur-containing diol; and a reagent selected from an aldehyde, a ketone, and a combination thereof; (ii) reagent reaction products comprising a sulfur-containing diol; a polyol containing at least three hydroxyl groups per diol molecule; and a reagent selected from an aldehyde, a ketone, and a combination thereof; and (iii) a combination of (i) and (ii).
[3]
3. Composition according to claim 1, characterized in that the polyform polyol comprises a polyform polyol of Formula (4), with each R3 being ethane-1,2-diyl and each R4 being hydrogen.
[4]
4. Composition according to claim 1, characterized in that the amine is selected from diethyltoluenediamine, dimethyltiotoluenediamine and a combination thereof.
[5]
5. Composition according to claim 1, characterized by the fact that it comprises a polythio-isocyanate prepolymer comprising the reaction products of reagents comprising a polythioether polyol and a second diisocyanate, with the polyether polyether comprising a selected polyether polyether of: a polyethylene polyol of Formula (13), a polyethylene polyol of Formula (14), or a combination thereof: R4- [R3] yA- [R3] y-R4 (13) B- (A) - [R3 ] y-R4) z (14) where: each A independently has the structure of Formula (12): -R1- [-S- (CH2) 2-O- [-R2-O-] m- (CH2) 2 -S-R1-] n (12) where: each R1 is independently selected from C2-6 alkanodiyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkanediyl, - [(- CH2-) p- X-] q - (- CH2 -) r- and - [(- CH2-) pX-] q - (- CH2-) r-, where at least one -CH2- group is replaced with a methyl group; 2 each R is independently selected from C2-6 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkanediyl, and - [(- CH2-) p-X-] q - (- CH2-) r-; each X is selected from -O-, -S- and -NR10-, where R10 is selected from hydrogen and methyl; each m is independently selected from a rational number from 0 to 10; each n is independently selected from an integer from 1 to 60; each p is independently selected from an integer from 2 to 6; each q is independently selected from an integer from 0 to 5; each r is independently selected from an integer from 2 to 10; each y is independently selected from 0 and 1; each R is a single bond where y is 0; or each R is 2 independently -S- (CH2) 2 - [- O-R -] m-O-, where y is 1; each R4 is independently -S- (CH2) 2 + s-O-R5, where y is 0; or each R4 is independently - (CH2) 2-S-R5, where y is 1; each m is independently selected from a rational number from 0 to 10; each s is independently selected from an integer from 0 to 10; and each R5 is independently - (CH2) t-OH, where each t is independently selected from an integer from 1 to 6; z is independently selected from an integer from 3 to 6; and B is a z-valent residue of a polyfunctionalizing agent B (R) z, where each R is a moiety that is reactive with a -SH terminal group or -CH = CH2 terminal group.
[6]
6. Composition according to claim 1, characterized by the fact that the polyether polyol comprises the reaction products of a thiol terminated polyether and a vinyl ether with hydroxy functionality.
[7]
7. Composition, according to claim 6, characterized by the fact that the thiol-terminated polythether comprises the reaction products of one or more compounds of Formula (15); one or more compounds of Formula (16); and one or more polyfunctionalizing agents: HS-R1-SH CH2 = CH-O- [-R2-O-] m-CH = CH2 (15) (16) where: each R1 is independently selected from alkanediyl C2-6, cycloalkanediyl C6 -8, C6-10 alkanocycloalkanodiyl, - [(- CH2-) pX-] q - (- CH2-) r-, and - [(- CH2-) pX-] q (-CH2-) r-, where at at least one -CH2- group is replaced with a methyl group; 2 each R is independently selected from C2-6 alkanodiyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkanodiyl, - [(- CH2-) pX-] q - (- CH2-) r-, and - [(- CH2-) pX-] q (-CH2-) r-; each X is selected from -O-, -S- and -NR10-, where R10 is selected from hydrogen and methyl; each m is independently selected from a rational number from 0 to 10; each p is independently selected from an integer from 2 to 6; each q is independently selected from an integer from 0 to 5; and each r is independently selected from an integer from 2 to 10.
[8]
8. Composition according to claim 6, characterized in that the first diisocyanate and the second diisocyanate comprise an aliphatic diisocyanate.
[9]
9. Composition according to claim 6, characterized in that it comprises from 15% by weight to 55% by weight of the polyiform isocyanate prepolymer and from 45% by weight to 85% by weight of the prepolymer of polythio-isocyanate, where the weight percentage is based on the total weight of the polyiform-isocyanate prepolymer and the polythio-isocyanate prepolymer in the composition.
[10]
10. Composition according to claim 6, characterized by the fact that the molar ratio of the second diisocyanate to the polyether polyol is greater than 2 to 1.
[11]
11. Opening sealed with sealant, characterized by the fact that it comprises the composition, as defined in any one of claims 1 to 10.

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

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-01-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/03/2012, 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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US13/051,002|US8507617B2|2011-03-18|2011-03-18|Polyurea compositions and methods of use|

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US13/051,002|2011-03-18|

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PCT/US2012/029447|WO2012141841A1|2011-03-18|2012-03-16|Polyurea compositions and methods of use|

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