Zinc Containing Catalysts, Methods For Preparing The Catalysts, And Compositions Containing The Catalysts

Tin compounds are useful as catalysts for the condensation cure of many polyorganosiloxane compositions, including adhesives, sealants, and low permeability products such as those useful in insulating glass applications, coatings, and silicone elastomer lattices. Organotin compounds for condensation reaction catalysis are those where the oxidation state of the tin is either +4 or +2, i.e., Tin (IV) compounds or Tin (II) compounds. Examples of tin (IV) compounds include stannic salts such as dibutyl tin dilaurate, dimethyl tin dilaurate, di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide, carbomethoxyphenyl tin tris-uberate, dibutyl tin dioctanoate, dibutyl tin diformate, isobutyl tin triceroate, dimethyl tin dibutyrate, dimethyl tin di-neodeconoate, dibutyl tin di-neodeconoate, triethyl tin tartrate, dibutyl tin dibenzoate, butyltintri-2-ethylhexanoate, dioctyl tin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate, dimethyl tin dichloride, a combination thereof, and/or a partial hydrolysis product thereof. Tin (IV) compounds are known in the art and are commercially available, such as Metatin® 740 and Fascat® 4202 from Acima Specialty Chemicals of Switzerland, Europe, which is a business unit of The Dow Chemical Company. Examples of tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, stannous stearate, stannous naphthanate, stannous hexanoate, stannous succinate, stannous caprylate, and a combination thereof.

REACH (Registration, Evaluation, Authorization and Restriction of Chemical) is European Union legislation aimed to help protect human health and the environment and to improve capabilities and competitiveness through the chemical industry. Due to this legislation, tin based catalysts, which are used in many condensation reaction curable polyorganosiloxane products such as sealants and coatings, are to be phased out. Therefore, there is an industry need to replace conventional tin catalysts in condensation reaction curable compositions.

BRIEF SUMMARY OF THE INVENTION

A reaction product of ingredients comprising a Zinc precursor (Zn precursor) and a ligand, and methods for preparation of the reaction product are disclosed. A composition, which is capable of forming a product via condensation reaction, comprises the reaction product.

DETAILED DESCRIPTION OF THE INVENTION

All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all ingredients in a composition total 100% by weight. The Brief Summary of the Invention and the Abstract are hereby incorporated by reference. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.

“Alkyl” means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group. Examples of alkyl groups include Me, Et, Pr, 1-methylethyl, Bu, 1-methylpropyl, 2-methylpropyl, 1,1-dim ethylethyl, 1-methylbutyl, 1-ethylpropyl, pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, and decyl; and as well as other branched saturated monovalent hydrocarbon groups with 6 or more carbon atoms. Alkyl groups have at least one carbon atom. Alternatively, alkyl groups may have 1 to 12 carbon atoms, alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively 1 carbon atom.

“Aralkyl” and “alkaryl” each refer to an alkyl group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyl group. Exemplary aralkyl groups include benzyl, tolyl, xylyl, phenylethyl, phenyl propyl, and phenyl butyl. Aralkyl groups have at least 7 carbon atoms. Monocyclic aralkyl groups may have 7 to 12 carbon atoms, alternatively 7 to 9 carbon atoms, and alternatively 7 to 8 carbon atoms. Polycyclic aralkyl groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

“Alkenyl” means an acyclic, branched, or unbranched unsaturated monovalent hydrocarbon group, where the monovalent hydrocarbon group has a double bond. Alkenyl groups include Vi, allyl, propenyl, and hexenyl. Alkenyl groups have at least 2 carbon atoms. Alternatively, alkenyl groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms.

“Alkynyl” means an acyclic, branched, or unbranched unsaturated monovalent hydrocarbon group, where the monovalent hydrocarbon group has a triple bond. Alkynyl groups include ethynyl and propynyl. Alkynyl groups have at least 2 carbon atoms. Alternatively, alkynyl groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms.

“Aryl” means a hydrocarbon group derived from an arene by removal of a hydrogen atom from a ring carbon atom. Aryl is exemplified by, but not limited to, Ph and naphthyl. Aryl groups have at least 5 carbon atoms. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.

“Carbocycle” and “carbocyclic” refer to a hydrocarbon ring. Carbocycles may be monocyclic or polycyclic, e.g., bicyclic or with more than two rings. Bicyclic carbocycles may be fused, bridged, or spiro polycyclic rings. Carbocycles have at least 3 carbon atoms. Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic carbocycles may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms. Carbocycles may be saturated (e.g., cyclopentane or cyclohexane), partially unsaturated (e.g., cyclopentene or cyclohexene), or fully unsaturated (e.g., cyclopentadiene or cycloheptatriene).

“Cycloalkyl” refers to a saturated hydrocarbon group including a carbocycle. Cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, cyclohexyl, and methylcyclohexyl. Cycloalkyl groups have at least 3 carbon atoms. Monocyclic cycloalkyl groups may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic cycloalkyl groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

“Halogenated hydrocarbon” means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom. Halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyl groups such as trifluoromethyl (CF₃), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl. Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include allyl chloride.

“Heteroatom” means any of the Group 13-17 elements of the IUPAC Periodic Table of the Elements at http://www.iupac.org/fileadmin/user_upload/news/IUPAC_Periodic_Table-1Jun12.pdf, except carbon. “Heteroatom” include, for example, N, O, P, S, Br, Cl, F, and I.

“Heteroatom containing group” means an organic group comprised of a carbon atom and that also includes at least one heteroatom. Heteroatom containing groups may include, for example, one or more of acyl, amide, amine, carboxyl, cyano, epoxy, hydrocarbonoxy, imino, ketone, ketoxime, mercapto, oxime, and/or thiol. For example, when the heteroatom containing group contains one or more halogen atoms, then the heteroatom containing group may be a halogenated hydrocarbon group as defined above. Alternatively, when the heteroatom is oxygen, then the heteroatom containing group may be a hydrocarbonoxy group such as an alkoxy group or an alkylalkoxy group.

“Inorganic heteroatom containing group” means group comprised of at least 1 heteroatom and at least 1 of hydrogen or a different heteroatoms. Heteroatom containing groups may include, for example, one or more of amine, hydroxy, imino, nitro, oxo, sulfonyl, and/or thiol.

“Heteroalkyl” group means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group that also includes at least one heteroatom. “Heteroalkyl” includes haloalkyl groups and alkyl groups in which at least one carbon atom has been replaced with a heteroatom such as N, O, P, or S, e.g., when the heteroatom is O, the heteroalkyl group may be an alkoxy group.

“Heterocycle” and “heterocyclic” each mean a ring group comprised of carbon atoms and one or more heteroatoms in the ring. The heteroatom in the heterocycle may be N, O, P, S, or a combination thereof. Heterocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings. Monocyclic heterocycles may have 3 to 9 member atoms in the ring, alternatively 4 to 7 member atoms, and alternatively 5 to 6 member atoms. Polycyclic heterocycles may have 7 to 17 member atoms, alternatively 7 to 14 member atoms, and alternatively 9 to 10 member atoms. Heterocycles may be saturated or partially unsaturated.

“Heteroaromatic” means a fully unsaturated ring containing group comprised of carbon atoms and one or more heteroatoms in the ring. Monocyclic heteroaromatic groups may have 5 to 9 member atoms, alternatively 6 to 7 member atoms, and alternatively 5 to 6 member atoms. Polycyclic heteroaromatic groups may have 10 to 17 member atoms, alternatively 10 to 14 member atoms, and alternatively 12 to 14 member atoms. Heteroaromatic includes heteroaryl groups such as pyridyl. Heteroaromatic includes heteroaralkyl, i.e., an alkyl group having a pendant and/or terminal heteroaryl group or a heteroaryl group having a pendant alkyl group. Exemplary heteroaralkyl groups include methylpyridyl and dimethylpyridyl.

“Free of” means that the composition contains a non-detectable amount of the ingredient, or the composition contains an amount of the ingredient insufficient to change the cure time measured according to the method in Example 2, as compared to the same composition with the ingredient omitted. For example, the composition described herein may be free of tin catalysts. “Free of tin catalysts” means that the composition contains a non-detectable amount of a tin catalyst capable of catalyzing a condensation reaction with the —OH and —H moieties of the ingredients in the composition, or the composition contains an amount of a tin catalyst insufficient to change the cure time measured according to the method in Example 2, as compared to the same composition with the tin catalyst omitted. The composition may be free of titanium catalysts. “Free of titanium catalysts” means that the composition contains a non-detectable amount of a titanium catalyst capable of catalyzing a condensation reaction with the —OH and —H moieties of the ingredients in the composition, or the composition contains an amount of a titanium catalyst insufficient to change the cure time measured according to the method in Example 2, as compared to the same composition with the titanium catalyst omitted. Alternatively, the composition described herein may be free of metal condensation reaction catalysts (i.e., other than ingredient (A) described herein). “Free of metal condensation reaction catalysts” means that the composition contains a non-detectable amount of a compound of a Group 4, 13, 14, or 15 metal of the IUPAC periodic table dated 1 May 2013 (available at http://www.iupac.org/fileadmin/user_upload/news/IUPAC_Periodic_Table-1May13.pdf), which is capable of catalyzing a condensation reaction, such as compounds of Al, Bi, Sn, Ti, and/or Zr; or an amount of such a metal condensation reaction catalyst insufficient to change the cure time measured according to the method in Example 2 as compared to the same composition with the metal condensation reaction catalyst omitted. For purposes of this definition ‘non-detectable amount’ may be measured, for example, according to the method of ASTM D7151-05 Standard Test Method for Determination of Elements in Insulating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES).

“Non-functional” means that the ingredient, e.g., a polyorganosiloxane, does not have hydrolyzable groups that participate in a condensation reaction.

Abbreviations used herein are defined as follows. The abbreviation “cP” means centiPoise. “DP” means the degree of polymerization of a polymer. “FTIR” means Fourier transform infrared spectroscopy. “GPC” means gel permeation chromatography. “Mn” means number average molecular weight. Mn may be measured using GPC. “Mw” means weight average molecular weight. “NMR” means nuclear magnetic resonance. “Me” means methyl. “Et” means ethyl. “Ph” means phenyl. “Pr” means propyl and includes various structures such as iPr and nPr. “iPr” means isopropyl. “nPr” means normal propyl. “Bu” means butyl and includes various structures including nBu, sec-butyl, tBu, and iBu. “iBu” means isobutyl. “nBu” means normal butyl. “tBu” means tert-butyl.

In one embodiment, a composition comprises:

(A) a catalytically effective amount of the reaction product of the Zn precursor and the ligand, described above, and

(B1) a hydroxy-functional compound having an average, per molecule, of one or more hydroxy (—OH) moieties, and

(B2) a Si—R⁵⁰functional compound having an average, per molecule, of one or more Si—⁵⁰moieties, where ingredient (A) is capable of catalyzing a condensation reaction of the hydroxy moiety on ingredient (B1) and the Si—R⁵⁰moiety on ingredient (B2). The condensation reaction of the —OH and Si—R⁵⁰moieties on ingredients (B1) and (B2) prepares a reaction product.

The composition may optionally further comprise one or more additional ingredients. The one or more additional ingredients are distinct from ingredients (A), (B1), and (B2). Suitable additional ingredients are exemplified by (C) a crosslinker, (D) a drying agent; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a nonreactive binder; (O) an anti-aging additive; (P) a water release agent; (Q) a pigment; (R) a rheological additive; (S) a vehicle (such as a solvent and/or a diluent); (T) a tackifying agent; (U) a corrosion inhibitor; and a combination thereof.

Ingredient (A) comprises a catalytically effective amount of the Zn containing condensation reaction catalyst. The Zn containing condensation reaction catalyst comprises a reaction product of a Zn precursor and a ligand. Without wishing to be bound by theory, it is thought that this reaction product comprises a Zn-ligand complex. The Zn precursor is distinct from a reaction product of the Zn precursor and the ligand. The Zn precursor may be a compound of Zn. The Zn precursor is a compound of Zn having general formula (i): Zn-A_a, where subscript a is 1 to maximum valence of zinc, and each A is independently a displaceable substituent. Each A may be, for example, a monovalent organic group or a monovalent inorganic group, and subscript a has a value ranging from 1 to 2. Alternatively, a=2. Examples of displaceable substituents for A include monovalent hydrocarbon groups, amino groups, silylamide groups, carboxylic ester groups, and hydrocarbonoxy groups. Displaceable substituent means that the group selected for one or more instances of A may be reacted off or otherwise displaced by the ligand.

Examples of monovalent hydrocarbon groups for A include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as phenyl, tolyl, xylyl, mesityl, and naphthyl; and aralkyl such as benzyl or 2-phenylethyl.

Examples of amino groups for A have formula —NA′₂, where each A′ is independently a hydrogen atom or a monovalent hydrocarbon group. Exemplary monovalent hydrocarbon groups for A′ include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as phenyl, tolyl, xylyl, mesityl, and naphthyl; and aralkyl such as benzyl or 2-phenylethyl. Alternatively, each A′ may be a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as methyl or ethyl.

Alternatively, for A in general formula (i) the silylamide group may have general formula —N(SiA′″₃)₂, where each A′″ is independently a monovalent hydrocarbon group. Examples of monovalent hydrocarbon groups for A′″ include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and naphthyl; aralkyl such as benzyl or 2-phenylethyl. Alternatively, each A′″ may be an alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or t-butyl. Alternatively, each A′″ may be an alkyl group, and alternatively each A′″ may be methyl, ethyl, propyl such as iso-propyl or n-propyl, or butyl.

Alternatively, each A in general formula (i) may be a carboxylic ester group. Examples of suitable carboxylic ester groups for A include, but are not limited to ethylhexanoate (such as 2-ethylhexanoate), neodecanoate, octanoate, and stearate.

Examples of monovalent hydrocarbonoxy groups for A may have formula —O-A″, where A″ is a monovalent hydrocarbon group. Examples of monovalent hydrocarbon groups for A″ include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and naphthyl; aralkyl such as benzyl or 2-phenylethyl. Alternatively, each A″ may be an alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or t-butyl. Alternatively, each A″ may be an alkyl group, and alternatively each A″ may be ethyl, propyl such as iso-propyl or n-propyl, or butyl.

Alternatively, each A may be an alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or t-butyl. Alternatively, each A may be selected from the group consisting of ethyl, benzyl, mesityl, phenyl, —NEt₂, cyclooctadiene, ethoxide, iso-propoxide, butoxide, 2-ethylhexanoate, neodecanoate, octanoate, and stearate. Alternatively, each A may be independently selected from a silyl amide group, an alkyl group, and a carboxylic ester group. Alternatively, each A may be a silyl amide group. Alternatively, each A may be a carboxylic ester group.

Organic compounds of Zn suitable for use as precursors are commercially available. For example, dialkyl zinc compounds such as Zn-Et₂and diaryl zinc compounds such as compounds of zinc such as Zn-Ph₂are commercially available from Sigma-Aldrich of St. Louis, Mo., U.S.A. (Aldrich). Zinc(II) bis(trialkylsilyl)amides such as zinc bis(bis(trimethylsilyl)amide) is also commercially available from Aldrich. Diesters of zinc, such as Zn(octanoate)₂, are commercially available from City Chemicals LLC of West Haven, Conn., U.S.A. Zinc 2-ethylhexanoate is commercially available from Strem Chemicals, Inc. of Newburyport, Mass., U.S.A.

The ligand is an organic compound that coordinates with Zn. The organic compound includes neutral and conjugate base forms. Without wishing to be bound by theory, it is thought that the ligand displaces one or more instances of displaceable substituent A in the Zn precursor of general formula (i) above to form the reaction product of ingredient (A).

In one embodiment, the ligand is an amino-functional organic compound comprising 2 or more amino-functional moieties, alternatively 2 to 3 amino-functional moieties, of general formula (ii):

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where subscript x is 1 or 2, and A¹and A²are each independently selected from monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups as defined herein. The monovalent hydrocarbon groups are exemplified by alkyl groups as defined herein. Alternatively, x may be 1. Alternatively x may be 2. Alternatively, A¹and A²may each be alkyl groups of 1 to 6 carbon atoms; alternatively 1 to 4 carbon atoms; and alternatively 1 to 2 carbon atoms.

The ligand may be a triamino-functional compound. For example, the ligand may have formula (iii):

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where x, A¹and A²are as described above and A³is selected from a hydrogen atom and an alkyl group of 1 to 6 carbon atoms; alternatively 1 to 4 carbon atoms; and alternatively 1 to 2 carbon atoms. Examples of ligands of general formula (iii) include N,N,N′,N″,N″-pentamethyldiethylenetriamine or N,N,N′,N′-tetraethyldiethylenetriamine.

Alternatively, the ligand may have general formula (iv):

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where x, A¹, and A²are as described above and group A⁴is a carbocyclic group having at least 3 carbon atoms covalently bonded in a ring, subscript y is at least 1, subscript z is at least 2, and a quantity (y+z) represents valence of A⁴, where the carbocyclic group has a moiety of formula A⁵and the moieties of general formula (ii)

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covalently bonded to carbon atoms in the ring; and each A⁵is independently a hydrogen atom or a hydroxy group. A⁴may be, for example, a cycloalkyl group or an aryl group, as defined herein. Alternatively, A⁴may be an aryl group such as phenyl. Each A⁵is independently a hydrogen atom or a hydroxy group. Alternatively, one A⁵is a hydroxy group and each remaining instance of A⁵is a hydrogen atom. Alternatively, subscript z is 2 to 3; alternatively subscript z is 3. Examples of ligands of general formula (iv): include 2,4,6-tris(dimethylaminomethyl)phenol.

Examples of suitable ligands for use in preparing ingredient (A) include each ligand having a neutral form shown below in Table 1.

Ligand
Structure

N,N,N′,N″,N″- Pentamethyldiethylenetriamine

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N,N,N′,N′- Tetraethyldiethylenetriamine

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2,4,6- Tris(dimethylaminomethyl)phenol

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Various ligands in Table 1 are commercially available. For example, ligands 2,4,6-tris(dimethylaminomethyl)phenol, N,N,N′,N″,N″-pentamethyldiethylenetriamine, and N,N,N′,N′-tetraethyldiethylenetriamine are each commercially available from Aldrich.

In an alternative embodiment, the ligand is an amino-functional organic compound comprising one or more amino-functional moieties of general formula (ii), described above. Alternatively, the ligand may have 1 amino-functional moiety of general formula (ii) per molecule. In this embodiment, the ligand may have general formula (v):

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where subscript x, A¹, and A²are as described above. Each A⁶is independently a monovalent organic group. A⁶may be a monovalent heteroatom containing group or a monovalent hydrocarbon group. Monovalent heteroatom containing groups are exemplified by a monovalent halogenated hydrocarbon group, an amino group of formula:

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where A⁷is hydrogen or A¹, A⁸is hydrogen or A², and subscript aa is 0 to 2; or a hydroxyl functional group of formula

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where subscript bb is 0 to 2; or an amino and hydroxyl functional group of formula

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where subscript cc is 1 or 2, subscript dd is 1 or 2, and A⁹is hydrogen or alkyl. Alternatively, the monovalent hydrocarbon groups are exemplified by alkyl groups as defined herein. Alternatively, x may be 1. Alternatively x may be 2. Alternatively, A¹and A²may each be alkyl groups of 1 to 6 carbon atoms; alternatively 1 to 4 carbon atoms; and alternatively 1 to 2 carbon atoms. Examples of ligands of general formula (v) include ligands L6, L7, L8, L9, L10, and L11 in Table 1-B, below.

Alternatively, A⁶may be the amino group of formula

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and subscript aa may be 0 or 1, A⁷may be hydrogen or alkyl, and A⁸may be hydrogen or alkyl. Alternatively, A⁷may be hydrogen and A⁸may be alkyl. Alternatively, A⁷and A⁸may each be hydrogen. Alternatively, A⁷and A⁸may each be alkyl, such as methyl or ethyl. Examples of ligands with this formula include ligands L8, L9, and L10 in Table 1-B, below.

Alternatively, A⁶may be the hydroxyl functional group of formula

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and subscript bb may be 0 or 1. Examples of ligands with this formula include ligands L6 and L7 in Table 1-B, below.

Alternatively, A⁶may be the amino and hydroxyl functional group of formula

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where subscript cc is 1 or 2, subscript dd is 1 or 2, and A⁹is hydrogen or alkyl. Alternatively, A⁹may be alkyl such as methyl. Examples of ligands with this formula include ligand L11 in Table 1-B, below.

Alternatively, the ligand may have general formula (vi):

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where A¹⁰, A¹¹, A¹², A¹³, A¹⁴, A¹⁵, and A¹⁶are each independently selected from hydrogen and an alkyl group, such as methyl, ethyl, propyl or butyl. Alternatively, A¹⁰, A¹¹, A¹², A¹³, A¹⁴, A¹⁵, and A¹⁶are each hydrogen or methyl. Alternatively, A¹⁰, A¹¹, A¹², A¹³, A¹⁴, A¹⁵, and A¹⁶are each hydrogen. Examples of ligands of general formula (vi) include ligand L12 in Table 1-B.

Examples of suitable ligands for use in preparing ingredient (A) include each ligand having a neutral form shown below in Table 1-B.

TABLE 1-B

Ligand
Structure

L6

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L10

L11

L12

Ingredient (A) may be prepared by a method comprising reacting the ligand and the Zn precursor, described above, thereby forming a catalytically active reaction product. Without wishing to be bound by theory, it is thought that the catalytically active reaction product comprises a Zn-ligand complex. The method may optionally further comprise a step of dissolving either the Zn precursor, or the ligand, or both, in a solvent before combining the Zn precursor and the ligand. Suitable solvents are exemplified by those described below for ingredient (S). Alternatively, the ligand may be dissolved in a solvent in a container, and the solvent may thereafter be removed before adding the Zn precursor to the container with the ligand. The amounts of ligand and Zn precursor are selected such that the mole ratio of ligand to Zn precursor (Ligand:Metal Ratio) may range from 10:1 to 1:1, alternatively 1:1 to 3:1, and alternatively 1:1 to 2:1. Combining the Zn precursor and the ligand may be performed by any convenient means, such as mixing them together in or shaking the container.

Reacting the Zn precursor and ligand may be performed by any convenient means such as allowing the Zn precursor and ligand prepared as described above to react at room temperature (RT) of 25° C. for a period of time, or by heating. Heating may be performed by any convenient means, such as via a heating mantle, heating coil, or placing the container in an oven. The reaction temperature depends on various factors including the reactivities of the specific Zn precursor and ligand selected and the Ligand:Metal Ratio, however, temperature may range from 25° C. to 200° C., alternatively 25° C. to 75° C. Reaction time depends on various factors including the reaction temperature selected, however, reaction time may range from 1 minute to 48 hours, alternatively 45 minutes (min) to 60 min. The ligand and Zn precursor may be combined and heated sequentially. Alternatively, the ligand and Zn precursor may be combined and heated concurrently.

The method of preparing the catalytically active reaction product of ingredient (A) may optionally further comprise adding a solvent after the reaction. Suitable solvents are exemplified by those described below for ingredient (S). Alternatively, the method may optionally further comprise removing a reaction by-product and/or the solvent, if the solvent is present (e.g., used to facilitate combination of the Zn precursor and the ligand before or during heating). By-products include, for example, H-A (where A is as defined above in general formula (i)) or any species resulting from reacting an organic group off the Zn precursor when the ligand reacts with the Zn precursor. By-products may be removed by any convenient means, such as stripping or distillation, with heating or under vacuum, or a combination thereof. The resulting isolated Zn-ligand complex may be used as the catalytically active reaction product of ingredient (A).

Alternatively, the reaction by-products are not removed before using the catalytically active reaction product as ingredient (A). For example, the ligand and Zn precursor may be reacted as described above, with or without solvent removal, and the resulting catalytically active reaction product (comprising the Zn-ligand complex and the reaction by-product and optionally a solvent or diluent) may be used as ingredient (A). Without wishing to be bound by theory, it is thought that a by-product may act as a condensation reaction catalyst in addition to the Zn-ligand complex, or as a co-catalyst or an activator for the Zn-ligand complex. Therefore, the reaction product may catalyze a condensation reaction.

The composition may contain one single catalyst. Alternatively, the composition may comprise two or more catalysts described above as ingredient (A), where the two or more catalysts differ in at least one property such as selection of ligand, selection of precursor, Ligand:Metal Ratio, and definitions for group A in general formula (i). The composition may be free of tin catalysts, alternatively the composition may be free of titanium catalysts, and alternatively the composition may be both free of tin catalysts and free of titanium catalysts. Alternatively, the composition may be free of any Zn compound that would catalyze the condensation reaction of the hydroxy groups on ingredient (B1) other than ingredient (A). Alternatively, the composition may be free of metal condensation reaction catalysts other than ingredient (A). Alternatively, the composition may be free of any ingredient that would catalyze the condensation reaction of the hydroxy groups on ingredient (B1) other than ingredient (A).

Ingredient (A) is present in the composition in a catalytically effective amount. The exact amount depends on various factors including reactivity of ingredient (A), the type and amount of ingredient (B1), and the type and amount of any additional ingredient, if present. However, the amount of ingredient (A) in the composition may range from 1 part per million (ppm) to 10%, alternatively 10 ppm to 5%, alternatively 0.1% to 2%, and alternatively 1 ppm to 1%, based on total weight of all ingredients in the composition.

Ingredient (B1) is a hydroxy-functional compound. Ingredient (B1) has one or more —OH moieties per molecule, alternatively two or more —OH moieties. The hydroxy-functional compound may contain additional functional groups (i.e., one or more functional groups other than OH), such as carboxyl, amino, urea, carbamate, amide, or epoxy. The hydroxy-functional compound may be a diol. Alternatively, the hydroxy-functional compound may be a polyol having an average of more than one OH group per molecule, alternatively 2 or more OH groups per molecule, and alternatively 10 to 1000 OH groups per molecule. Ingredient (B1) may be selected from a polyorganosiloxane such as a polydiorganosiloxane, an organic polymer, or a silicone-organic copolymer (having the one or more hydroxy groups of formula OH covalently bonded to a Si atom and/or carbon atom in the polymer backbone and/or terminus). Alternatively (B1) may be a monohydric alcohol, such as methanol, ethanol, isopropanol, butanol, or n-propanol. Alternatively, ingredient (B1) may be a polyorganosiloxane, or an organic polymer. Alternatively ingredient (B1) may be a polyorganosiloxane. The hydroxy group in ingredient (B1) may be located at terminal, pendant, or both terminal and pendant positions in the polymer. Ingredient (B1) may comprise a linear, branched, cyclic, or resinous structure. Alternatively, ingredient (B1) may comprise a linear, branched or cyclic structure. Alternatively, ingredient (B1) may comprise a linear or branched structure. Alternatively, ingredient (B1) may comprise a linear structure. Alternatively, ingredient (B1) may comprise a linear structure and a resinous structure. Ingredient (B1) may comprise a homopolymer or a copolymer or a combination thereof.

Ingredient (B1) may have the hydroxy groups contained in groups of the formula (ii):

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where each D independently represents an oxygen atom, a divalent organic group, a divalent silicone organic group, or a combination of a divalent hydrocarbon group (what does it mean here about divalent hydrocarbon?) and a divalent siloxane group; each X independently represents a hydroxy group of formula OH; each R independently represents a monovalent hydrocarbon group; subscript c represents 0, 1, 2, or 3; subscript a represents 0, 1, or 2; and subscript b has a value of 0 or greater, with the proviso that the sum of (a+c) is at least 1, such that, on average, at least one X is present in the formula. Alternatively, subscript b may have a value ranging from 0 to 18 (This can be larger than 18. In paper coating, a disilanol gum may be used in formulation).

Alternatively, each D may be independently selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each D may be an oxygen atom. Alternatively, each D may be a divalent hydrocarbon group exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as:

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Alternatively, an instance of D may be an oxygen atom while a different instance of D is a divalent hydrocarbon group. (we can have OH group on the carbon of the divalent hydrocarbon group.) (we can even have OH groups at the terminal of a linear or branch hydrocarbon)

Alternatively, each R in the formula above may be independently selected from alkyl groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, and aralkyl groups of 7 to 20 carbon atoms.

Alternatively, subscript b may be 0.

Ingredient (B1) may comprise the groups described by formula (ii) above in an amount of the base polymer ranging from 0.2 mol % to 10 mol %, alternatively 0.5 mol % to 5 mol %, alternatively 0.5 mol % to 2.0 mol %, alternatively 0.5 mol % to 1.5 mol %, and alternatively 0.6 mol % to 1.2 mol %.

Ingredient (B1) may be a polyorganosiloxane with a linear structure, i.e., a polydiorganosiloxane. When ingredient (B1) is a polydiorganosiloxane, ingredient (B1) may comprise a hydroxy-endblocked polydiorganosiloxane, an hydroxysilylhydrocarbylene-endblocked polydiorganosiloxane, or a combination thereof.

Ingredient (B1) may comprise a polydiorganosiloxane of formula (I):

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where each R¹is independently a hydroxy group, each R²is independently a monovalent organic group, each R³is independently an oxygen atom or a divalent hydrocarbon group, each subscript d is independently 1, 2, or 3, and subscript e is an integer having a value sufficient to provide the polydiorganosiloxane with a viscosity of at least 100 mPa·s at 25° C. and/or a DP of at least 87. DP may be measured by GPC using polystyrene standards calibration. Alternatively, subscript e may have a value ranging from 1 to 200,000.

Suitable organic groups for R²include, but are not limited to, monovalent organic groups such as hydrocarbon groups and halogenated hydrocarbon groups. Examples of monovalent hydrocarbon groups for R²include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and benzyl; and aralkyl such as 2-phenylethyl. Examples of monovalent halogenated hydrocarbon groups for R²include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Examples of other monovalent organic groups for R²include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyl, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl. Alternatively, each R²may be an alkyl group such as methyl.

Ingredient (B1) may comprise an α,ω-difunctional-polydiorganosiloxane when, in formula (I) above, each subscript d is 1 and each R³is an oxygen atom. For example, ingredient (B1) may have formula (II): R¹R²₂SiO—(R²₂SiO)_e′—SiR²₂R¹, where R¹and R²are as described above and subscript e′ is an integer having a value sufficient to give the polydiorganosiloxane of formula (II) the viscosity described above. Alternatively, subscript e′ may have a value ranging from 1 to 200,000, alternatively 50 to 1,000, and alternatively 200 to 700.

Alternatively, in formula (II) described above, each R²may be an alkyl group such as methyl, and subscript e′ may have a value such that the hydroxy functional polydiorganosiloxane has a viscosity of at least 100 mPa·s at 25° C. Alternatively, subscript e′ may have a value ranging from 50 to 700. Exemplary hydroxy-endblocked polydiorganosiloxanes are hydroxy-endblocked polydimethylsiloxanes. Hydroxy-endblocked polydiorganosiloxanes suitable for use as ingredient (B1) may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes.

Alternatively, ingredient (B1) may comprise a hydroxy functional organic polymer. Alternatively, the organic polymer may be a polymer in which at least half the atoms in the polymer backbone are carbon atoms with terminal hydroxy groups. The organic polymer can, for example, be selected from hydrocarbon polymers, polyethers, acrylate polymers, polyols, polyurethanes and polyureas.

Ingredient (B1) may be an organic hydroxy-functional compound. The organic hydroxy-functional compound may be a monohydric alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a polyether polyol, such as dipropylene glycol or a poly(tetraalkyene ether) glycol such as glycerol propoxylate; a polyester polyol; a polyester-amide polyol; a polyacetal polyol; a polycarbonate polyol; a polycaprolactone polyol; a polybutadiene polyol; a poly(propylene oxide)polyol; a poly(propylene oxide/ethylene oxide) copolymer; a polyether polyol; and a polysulfide polyol. Exemplary hydroxy-functional compounds with two OH groups per molecule include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol (1,2-propylene glycol and/or 1,3-propylene glycol), 1,4-butylene glycol, 2,3-butylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, and a combination thereof. Exemplary hydroxy-functional compounds with three OH groups per molecule include glycerol, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, glycerol propoxylate, triglycerol, and a combination thereof.

Other organic polyhydroxy compounds that may be used include, pentaerythritol, mannitol, sorbitol, poly(ethyleneoxy) glycols generally, poly(propyleneoxy) glycols generally, dibutylene glycol, poly(butyleneoxy) glycols, and polycaprolactone. Other polyhydroxy materials of higher molecular weight which may be used are the polymerization products of epoxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and epichlorohydrin. A particularly common high molecular weight polyol is polytetramethylene glycol. A commercial polyol is Desmophen® R-221-75 polyol (equivalent weight 515 g/mol carbon-bonded hydroxy) (Bayer, Pittsburgh, Pa.)

The organic hydroxy-functional compounds have on average at least one carbon-bonded hydroxy group per molecule. Alternatively, the equivalent weight of carbon-bonded hydroxy groups on the organic hydroxy-functional compound may be from 80 to 800, alternatively 100 to 600.

Alternatively, ingredient (B1) may be elastomeric, i.e., have a glass transition temperature (Tg) less than 0° C. When ingredient (B1) is elastomeric, ingredient (B1) may be distinguished, based on the Tg, from semi-crystalline and amorphous polyolefins (e.g., alpha-olefins), commonly referred to as thermoplastic polymers.

Ingredient (B1) may comprise a silylated poly(alpha-olefin), a silylated copolymer of an iso-mono-olefin and a vinyl aromatic monomer, a silylated copolymer of a diene and a vinyl aromatic monomer, a silylated copolymer of an olefin and a diene (e.g., a silylated butyl rubber prepared from polyisobutylene and isoprene, which may optionally be halogenated), or a combination thereof (silylated copolymers), a silylated homopolymer of the iso-mono-olefin, a silylated homopolymer of the vinyl aromatic monomer, a silylated homopolymer of the diene (e.g., silylated polybutadiene or silylated hydrogenated polybutadiene), or a combination thereof (silylated homopolymers) or a combination silylated copolymers and silylated homopolymers. For purposes of this application, silylated copolymers and silylated homopolymers are referred to collectively as ‘silylated polymers’. The silylated polymer may optionally contain one or more halogen groups, particularly bromine groups, covalently bonded to an atom of the silylated polymer.

Examples of suitable mono-iso-olefins include, but are not limited to, isoalkylenes such as isobutylene, isopentylene, isohexylene, and isoheptylene; alternatively isobutylene. Examples of suitable vinyl aromatic monomers include but are not limited to alkylstyrenes such as alpha-methylstyrene, t-butylstyrene, and para-methylstyrene;

alternatively para-methylstyrene. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl; alternatively methyl. Examples of suitable alkenyl groups include, vinyl, allyl, propenyl, butenyl, and hexenyl; alternatively vinyl. The silylated organic polymer may have Mn ranging from 20,000 to 500,000, alternatively 50,000-200,000, alternatively 20,000 to 100,000, alternatively 25,000 to 50,000, and alternatively 28,000 to 35,000; where values of Mn are expressed in grams per mole (g/mol) and were measured by Triple Detection Size Exclusion Chromatography and calculated on the basis of polystyrene molecular weight standards.

Examples of suitable silylated poly(alpha-olefins) are known in the art and are commercially available. Examples include the condensation reaction curable silylated polymers marketed as VESTOPLAST®, which are commercially available from Degussa AG Coatings & Colorants of Marl, Germany, Europe.

Briefly stated, a method for preparing the silylated copolymers involves contacting i) an olefin copolymer having at least 50 mole % of repeat units comprising residuals of an iso-mono-olefin having 4 to 7 carbon atoms and at most 50 mole % of repeat units comprising residuals of a vinyl aromatic monomer; ii) a silane having at least two hydrolyzable groups and at least one olefinically unsaturated hydrocarbon or hydrocarbonoxy group; and iii) a free radical generating agent.

Alternatively, silylated copolymers may be prepared by a method comprising conversion of commercially available hydroxylated polybutadienes (such as those commercially available from Cray Valley SA of Paris, France, under trade names Poly BD and Krasol) by known methods (e.g., reaction with isocyanate functional alkoxysilane, reaction with allyl chloride in presence of Na followed by hydrosilylation).

Alternatively, examples of suitable silyl modified hydrocarbon polymers include silyl modified polyisobutylene, which is available commercially in the form of telechelic polymers. Silyl modified polyisobutylene can, for example, contain curable silyl groups derived from a silyl-substituted alkyl acrylate or methacrylate monomer such as a dialkoxyalkylsilylpropyl methacrylate or trialkoxysilylpropyl methacrylate, which can be reacted with a polyisobutylene prepared by living anionic polymerisation, atom transfer radical polymerization or chain transfer polymerization.

Alternatively, ingredient (B1) may comprise a polyether. One type of polyether is a polyoxyalkylene polymer comprising recurring oxyalkylene units of the formula (—C_tH_2t—O—) where subscript t is an integer with a value ranging from 2 to 4. Polyoxyalkylene polymers typically have terminal hydroxy groups. Alternatively, polymerization may occur via a hydrosilylation type process. Polyoxyalkylenes comprising mostly oxypropylene units may have properties suitable for many sealant uses.

The organic polymer can alternatively be an acrylate polymer, that is an addition polymer of acrylate and/or methacrylate ester monomers, which may comprise at least 50 mole % of the monomer repeat units in the acrylate polymer. Examples of suitable acrylate ester monomers are n-butyl, isobutyl, n-propyl, ethyl, methyl, n-hexyl, n-octyl and 2-ethylhexyl acrylates. Examples of suitable methacrylate ester monomers are n-butyl, isobutyl, methyl, n-hexyl, n-octyl, 2-ethylhexyl and lauryl methacrylates. For some applications, the acrylate polymer may have a Tg below ambient temperature; and acrylate polymers may form lower Tg polymers than methacrylate polymers. An exemplary acrylate polymer is polybutyl acrylate. The acrylate polymer may contain lesser amounts of other monomers such as styrene, acrylonitrile or acrylamide. The acrylate polymer can be prepared by various methods such as conventional radical polymerization, or living radical polymerization such as atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, or anionic polymerization including living anionic polymerization. The curable silyl groups can, for example, be derived from a silyl-substituted alkyl acrylate or methacrylate monomer. Hydrolysable silyl groups such as dialkoxyalkylsilyl or trialkoxysilyl groups can, for example, be derived from a dialkoxyalkylsilylpropyl methacrylate or trialkoxysilylpropyl methacrylate. When the acrylate polymer has been prepared by a polymerization process which forms reactive terminal groups, such as atom transfer radical polymerization, chain transfer polymerization, or living anionic polymerization, it can readily be reacted with the silyl-substituted alkyl acrylate or methacrylate monomer to form terminal hydrolyzable silyl groups.

Silyl modified polyurethanes or polyureas can, for example, be prepared by the reaction of polyurethanes or polyureas having terminal ethylenically unsaturated groups with a silyl monomer containing hydrolyzable groups and a Si—H group, for example a dialkoxyalkylsilicon hydride or trialkoxysilicon hydride.

Alternatively, ingredient (B1) may have a silicone-organic block copolymer backbone, which comprises at least one block of polyorganosiloxane groups and at least one block of an organic polymer chain. The polyorganosiloxane groups may comprise groups of formula —(R⁴_fSiO_(4-f/2)—, in which each R⁴is independently an organic group such as a hydrocarbon group having from 1 to 18 carbon atoms, a halogenated hydrocarbon group having from 1 to 18 carbon atoms such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl, a hydrocarbonoxy group having up to 18 carbon atoms, or another organic group exemplified by an oxygen atom containing group such as (meth)acrylic or carboxyl; a nitrogen atom containing group such as amino-functional groups, amido-functional groups, and cyano-functional groups; a sulfur atom containing group such as mercapto groups; and subscript f has, on average, a value ranging from 1 to 3, alternatively 1.8 to 2.2.

Alternatively, each R⁴may be a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group; and subscript f may be 0, 1 or 2. Examples of groups suitable for R⁴include methyl, ethyl, propyl, butyl, vinyl, cyclohexyl, phenyl, tolyl group, a propyl group substituted with chlorine or fluorine such as 3,3,3-trifluoropropyl, chlorophenyl, beta-(perfluorobutyl)ethyl or chlorocyclohexyl group.

The organic blocks in the polymer backbone may comprise, for example, polystyrene and/or substituted polystyrenes such as poly(α-methylstyrene), poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl-α-methylstyrene). Other organic groups, which may be incorporated in the polymer backbone, may include acetylene terminated oligophenylenes, vinylbenzyl terminated aromatic polysulphones oligomers, aromatic polyesters, aromatic polyester based monomers, polyalkylenes, polyurethanes, aliphatic polyesters, aliphatic polyamides and aromatic polyamides.

Alternatively, the organic polymer blocks in a siloxane organic block copolymer for ingredient (B1) may be polyoxyalkylene based blocks comprising recurring oxyalkylene units, illustrated by the average formula (—C_gH_2g—O—)_hwhere subscript g is an integer with a value ranging from 2 to 4 and subscript h is an integer of at least four. The number average molecular weight (Mn) of each polyoxyalkylene polymer block may range from 300 to 10,000. Moreover, the oxyalkylene units are not necessarily identical throughout the polyoxyalkylene block, but can differ from unit to unit. A polyoxyalkylene block, for example, can comprise oxyethylene units (—C₂H₄—O—), oxypropylene units (—C₃H₆—O—) or oxybutylene units (—C₄H₈—O—), or combinations thereof. Alternatively, the polyoxyalkylene polymeric backbone may consist essentially of oxyethylene units and/or oxypropylene units. Other polyoxyalkylene blocks may include for example, units of the structure: -[—R⁵—O—(—R⁶—O—)_i-Pn-CR⁷₂-Pn-O—(—R⁶—O—)_i—R⁵]—, in which Pn is a 1,4-phenylene group, each R⁵is the same or different and is a divalent hydrocarbon group having 2 to 8 carbon atoms, each R⁶is the same or different and is an ethylene group or propylene group, each R⁷is the same or different and is a hydrogen atom or methyl group and each of the subscripts i and j each represent a positive integer having a value ranging from 3 to 30.

Alternatively, ingredient (B1) may be a carbinol functional polyorganosiloxane. Exemplary carbinol functional polyorganosiloxanes may have unit formula [III]. Unit formula [III] is: (R⁴¹₃SiO_1/2)_e(R⁴²₂SiO_2/2)_f(R⁴³SiO_3/2)_g(SiO_4/2)_h. In unit formula [III], each R⁴¹is independently a hydrogen atom, a monovalent hydrocarbon group such as an alkyl group of 1 to 8 carbon atoms or an aryl group; or a carbinol group; each R⁴²is independently a hydrogen atom, a monovalent hydrocarbon group such as an alkyl group of 1 to 8 carbon atoms or an aryl group, or a carbinol group; and R⁴³is a monovalent hydrocarbon group such as an alkyl group of 1 to 8 carbon atoms or an aryl group. In unit formula [III], subscript e≧0, f≧0, g≧0, h≧0, and a quantity 0≦(e+f+g+h)≦1. Alternatively, subscript e<0.5, f≧0, g>0, h<0.5, a quantity (g+h)>0, and the quantity (e+f+g+h)=1.

As described herein, “carbinol group” is defined as any group containing at least one carbon-bonded hydroxy (COH) group. Thus the carbinol groups may contain more than one COH group such as, for example,

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The carbon in the carbon-bonded hydroxy group may be a carbon atom in a hydrocarbon group such as alkyl or aryl or in a halogenated hydrocarbon group, such as chlorophenyl, bromophenyl, or fluorophenyl; as described below. Alternatively, the carbinol group may have formula R⁴⁴OH where R⁴⁴is a divalent hydrocarbon group having at least 3 carbon atoms or divalent hydrocarbonoxy group having at least 3 carbon atoms. The group R⁴⁴is illustrated by alkylene groups selected from —(CH₂)_x—, —CH₂CH(CH₃)—, —CH₂CH(CH₃)CH₂—, —CH₂CH₂CH(CH₂CH₃)CH₂CH₂CH₂—, and —OCH(CH₃)(CH₂)_x— where subscript x is 1 to 10. An aryl-containing carbinol group having at least 6 carbon atoms is illustrated by groups having the formula R⁴⁵OH wherein R⁴⁵is an arylene group selected from —(CH₂)_yC₆H₄—, and —CH₂CH(CH₃)(CH₂)_yC₆H₄— where subscript y is 0 to 10, and —(CH₂)_xC₆H₄(CH₂)_x— where subscript x is as defined above.

The carbinol-functional polyorganosiloxane may be a carbinol-functional silicone resin. Suitable carbinol-functional silicone resins are exemplified by