WO2015020689A1

WO2015020689A1 - Catalysts, compositions containing the catalysts, and methods for the preparation thereof

Info

Publication number: WO2015020689A1
Application number: PCT/US2014/013718
Authority: WO
Inventors: Pierre Leger; David Pierre; Avril Surgenor; Ming-Shin Tzou
Original assignee: Dow Corning Corporation
Priority date: 2013-08-06
Filing date: 2014-01-30
Publication date: 2015-02-12

Abstract

A catalyst includes a reaction product of a metal precursor and a ligand. The catalyst may be used to react polyurethane compositions, polyester compositions, and condensation reactable polyorganosiloxane compositions.

Description

CATALYSTS, COMPOSITIONS CONTAINING THE CATALYSTS, AND METHODS FOR

THE PREPARATION THEREOF

[0001 ] Organotin compounds, such as dibutyl tin dilaurate and dibutyl tin diacetate, have been used as catalysts for various chemical reactions. 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, certain organotin catalysts, which are used in many products such as sealants and coatings, are to be phased out.

Therefore, there is an industry need to replace conventional tin catalysts in reactive compositions.

BRIEF SUMMARY OF THE INVENTION

[0002] A catalyst comprises a reaction product of ingredients comprising

(i) a metal precursor of general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent, and subscript a has a value from 1 to maximum valence of the metal selected for M; and

(ii) a ligand that differs from the displaceable substituent selected for A. The catalyst is useful for catalyzing chemical reactions such as urethane formation and ester formation, as well as other condensation reactions.

DETAILED DESCRIPTION OF THE INVENTION

[0003] The Brief Summary of the Invention and the Abstract are hereby incorporated by reference into the specification. All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all ingredients in a composition total 100% by weight. The articles 'a', 'an', and 'the' each refer to one or more, unless otherwise indicated by the context of specification. The abbreviation 'DBTDL' means dibutyl tin dilaurate, 'g' means grams, 'μ' means micrometers, 'μί' means microliters, 'h' means hours, 'min' means minutes, and 's' means seconds. The abbreviation 'Me' means methyl, 'Et' means ethyl, 'Pr' means propyl and includes n-propyl and iso-propyl, 'Bu' means butyl and includes n- butyl, tert-butyl, isobutyl, and sec-butyl; 'Ph' means phenyl and 'Vi' means vinyl. 'I R' means infra-red, 'GPC means gel permeation chromatography, and 'DSC means differential scanning calorimetry.

[0004] "Alkyl" means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group. Alkyl is exemplified by, but not limited to, Me, Et, Pr, Bu, pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups of 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.

[0005] "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.

[0006] "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 may 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.

[0007] "Aryl" means a cyclic, fully unsaturated, hydrocarbon group. Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 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.

[0008] "Aralkyi" means an alkyl group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyl group. Exemplary aralkyi groups include tolyl, xylyl, benzyl, phenylethyl, phenyl propyl, and phenyl butyl. Aralkyi groups have at least 4 carbon atoms. Monocyclic aralkyi groups may have 4 to 12 carbon atoms, alternatively 4 to 9 carbon atoms, and alternatively 4 to 7 carbon atoms. Polycyclic aralkyi groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

[0009] "Carbocycle" and "carbocyclic" each mean a hydrocarbon ring. Carbocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings. 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 or partially unsaturated.

[0010] "Cycloalkyl" means a saturated hydrocarbon group including a saturated 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 cycloalkyi groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

[0011 ] "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 cycloalkyi groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4- difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyi groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include allyl chloride.

[0012] "Heteroatom" means any of the Group 13-17 elements of the lUPAC Convention, see the lUPAC Periodic Table of the Elements at dated 1 June 2012, which may be found at http://www.iupac.org/fileadmin/user_upload/news/IUPAC_Periodic_Table-1 Jun12.pdf, except carbon. "Heteroatom" includes, for example, N, O, P, S, Br, CI, F, and I.

[0013] "Heterocycle" and "heterocyclic" each mean a ring structure 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.

[0014] "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 and thiophenyl. 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. [0015] Urethane linkages are produced by reacting an isocyanate-functional compound containing one or more isocyanate groups per molecule and a hydroxy-functional compound containing one or more hydroxy groups per molecule in the presence of a urethane catalyst. The isocyanate functional compound may have formula: R-(N=C=0)_m, where R is an organic group and subscript m is an integer representing the number of isocyanate groups per molecule, and m≥ 1 , alternatively m≥ 2. The hydroxy-functional compound may have formula: R'-(OH)_n, where R' is an organic group, subscript n represents the number of hydroxy groups per molecule, and n≥1 , alternatively n≥ 2.

[0016] In one embodiment, the reactive component (X) is capable of producing a urethane, and the reactive component (X) comprises ingredient (B) an isocyanate- functional compound having an average, per molecule, of one or more isocyanate groups, and (C) hydroxy-functional compound having an average, per molecule, of one or more hydroxy groups capable of reacting with the isocyanate groups of ingredient (B). A urethane composition comprises:

(A) the catalyst, and

(B) the isocyanate-functional compound having an average, per molecule, of one or more isocyanate groups, and

(C) the hydroxy-functional compound having an average, per molecule, of one or more hydroxy groups capable of reacting with the isocyanate groups of ingredient (B). Without wishing to be bound by theory, it is thought that ingredient (A) is characterizable as being effective for catalyzing the reaction of ingredients (B) and (C) to form a urethane bond.

[0017] Ester linkages may be produced by reacting an acid-functional compound containing one or more carboxylic acid functional groups per molecule and a hydroxy- functional compound containing one or more hydroxy groups per molecule in the presence of a catalyst. Alternatively, ester linkages may be produced by reacting an ester-functional compound containing one or more ester-functional groups per molecule is reacted with a hydrocarbonoxide-functional compound or a hydroxy-functional compound as described above. The acid-functional or ester-functional compound may have formula: R(C(=0)- OR")p, where R is an organic group, each R" is independently a hydrogen atom (H) (i.e., the carboxylic acid-functional compound) or a monovalent hydrocarbon group (i.e., the ester-functional compound), and subscript p is an integer representing the number of functional groups per molecule, and p≥ 1 , alternatively p≥ 2. The hydroxy-functional compound may be the same as or different from the hydroxy-functional compound described above for ingredient (C), and it may have formula: R'-(OH)_n, where R' is an organic group, subscript n represents the number of hydroxy groups per molecule, and n ≥1 , alternatively n≥ 2. Alternatively, the hvdrnnarbonoxide or hydroxy-functional compound may have formula R'(OR"')_m, where R' is as described above, subscript m represents the number of functional groups per molecule, and R'" is H or a monovalent hydrocarbon group, such as an alkyl group, and m≥ 1 , alternatively m≥ 2.

[0018] In an alternative embodiment, the reactive component (X) is capable of producing an ester, and the reactive component (X) comprises ingredient (Β') a compound of formula R(C(=0)-OR")p, where R is an organic group, each R" is independently a hydrogen atom (H) or a monovalent hydrocarbon group, and subscript p is an integer representing the number of functional groups per molecule, and p≥ 1 , alternatively p≥ 2; and

(C) A compound of formula R'(OR"')_m, where R' is an organic group, each R'" is independently a hydrogen atom or a monovalent hydrocarbon group, subscript m is an integer representing the number of functional groups per molecule, and m≥ 1 , alternatively m≥ 2. Ingredients (Β') and (C) form an ester. The composition may undergo

transesterification, for example, when ingredient (C) is selected such that R' is an organic group of formula R-C(=0)-, where R is as described above for ingredient (Β').

[0019] An ester composition comprises:

(A) the catalyst, and

(Β') the compound of formula R(C(=0)-OR")p, where R is an organic group, each R" is independently a hydrogen atom (H) or a monovalent hydrocarbon group, and subscript p is an integer representing the number of functional groups per molecule, and p≥ 1 , alternatively p≥ 2; and

(C) the compound of formula R'(OR"')_m, where R' is an organic group, each R'" is independently a hydrogen atom or a monovalent hydrocarbon group, subscript m is an integer representing the number of functional groups per molecule, and m≥ 1 , alternatively m≥2. Ingredients (Β') and (C) form an ester. . Without wishing to be bound by theory, it is thought that ingredient (A) is characterizable as being effective for catalyzing the reaction of ingredients (Β') and (C) to form an ester bond.

[0020] In an alternative embodiment, the reactive component (X) is capable of producing a siloxane product via a condensation reaction, and the reactive component (X) comprises ingredient (B") a silicon containing base polymer having an average, per molecule, of one or more hydrolyzable substituents, and optionally (C") a crosslinker.

[0021] A siloxane composition comprises

(A) the catalyst,

(B") the silicon containing base polymer having an average, per molecule, of one or more hydrolyzable substituents, and

optionally (C") a crosslinker and/or (L") a chain lengthener. [0022] Ingredient (A) is added to the composition in a catalytic quantity, i.e., an amount sufficient to catalyze a chemical reaction of ingredient (X) the reactive component.

Ingredient (A) is a catalyst, which comprises a reaction product of a metal precursor and a ligand. Without wishing to be bound by theory, it is thought that this reaction product comprises a metal-ligand complex (M-ligand complex). The metal precursor is distinct from a reaction product of the metal precursor and the ligand. The metal precursor has general formula (i): M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu,

Fe, Hf, Ti, Zn, and Zr, each A is independently a displaceable substituent. Each A may be a halogen atom or a monovalent organic group, and subscript a has a value from 1 to maximum valence of the metal selected for M. Alternatively, each A may be independently an organic group. Alternatively subscript a is 1 to 3. Examples of monovalent organic groups for A include monovalent hydrocarbon groups, amino groups, silazane groups, carboxylic ester groups, and hydrocarbonoxy groups. Each instance of A may be the same or different.

[0023] 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.

[0024] 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.

[0025] Alternatively, each A in general formula (i) may be a silazane group.

[0026] 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. [0027] 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.

[0028] Alternatively, each A may be may be selected from the group consisting of alkoxy and carboxylic acid ester. Alternatively, each A may be selected from the group consisting of ethoxy, propoxy, and ethylhexanoate.

[0029] Compounds of M suitable for use as metal precursors for use herein are commercially available, see Table 1 below. Alternatively, the metal precursor may be selected from Bismuth(lll) 2-ethylhexanoate, Iron(lll) 2-ethylhexanoate, and Zinc(ll) 2- ethylhexanoate. Alternatively, the metal precursor may be selected from Titanium(IV) ethoxide and Zirconium(IV) isopropoxide.

Table 1 - Metal Precursors

Chemical Name Vendor

Hafnium (IV) t-butoxide Strem

Hafnium (IV) ethoxide Strem

Hafnium (IV) n-butoxide Aldrich

TITANI UM ISOPROPOXI DE Gelest

TITANIUM DI-n-BUTOXIDE BIS(2,4-PENTANEDIONATE) Gelest

TITANIUM n-BUTOXI DE Gelest

TITANIUM 2-ETHYLHEXOXIDE Gelest

TITANIUM DI ISOPROPOXIDE BIS(2,4-PENTANEDIONATE), 75% in Gelest isopropanol

TITANIUM TETRAKIS(DIMETHYLAMI DE), 99+% Gelest

TITANIUM t-BUTOXIDE Gelest

Titanium(IV) 2-ethylhexoxide Strem

TITANI UM ETHOXIDE, 99% Gelest

Titanium(IV) butoxide Fluka

TETRAKIS(TRIMETHYLSILOXY)TITANIUM Gelest

Titanium(IV) ethoxide (99.99%-Ti) PURATREM Strem

Titanium(IV) tert-butoxide Aldrich

Trichlorotris(tetrahydrofuran)titanium(lll), min. 97% Strem

Tetrakis(diethylamino)titanium(IV), 99% Strem

Titanium(IV) isopropoxide Aldrich

TITANIUM DIISOPROPOXIDE BIS(ETHYLACETOACETATE), 95% Gelest

Titanium(IV) isopropoxide, 98+% Acros

Zinc 2-ethylhexanoate, -80% in mineral spirits (17-19% Zn) Strem

ZINC 2-ETHYLHEXANOATE Gelest

Zinc Octoate City

Chemical

Zinc chloride, ultradry (H20, oxide, OH < 100ppm) (99.99%-Zn) PURATREM Strem

Diethylzinc, min. 95% (10 wt% in hexane) (Sure/Seal™ Bottle) Strem

ZIRCONIUM DIISOPROPOXIDE BIS(2,2,6,6-TETRAMETHYL-3,5- Gelest

HEPTANEDIONATE), tech-90

ZIRCONIUM ISOPROPOXIDE, 70-75% in heptane Gelest

Zirconium(IV) ethoxide Aldrich

ZIRCONI UM n-BUTOXIDE, 80% in n-butanol Gelest

ZIRCONIUM DI-n-BUTOXIDE BIS(2,4-PENTANEDIONATE), 25% in n- Gelest Chemical Name Vendor butanol/toluene

ZIRCONIUM TETRAKIS(DIMETHYLAMIDE) Gelest

Zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate) Aldrich

ZIRCONIUM 2-ETHYLHEXANOATE, 90% Gelest

Zirconium(IV) acetylacetonate Aldrich

ZIRCONIUM n-PROPOXIDE, 70% in n-propanol Gelest

Tetrabenzylzirconium, min. 95% Strem

Tetrakis (dimethylamino) Zirconium (TDMAZ) Strem

[0030] In the table above, "Aldrich" refers to Sigma Aldrich, Inc. of St. Louis, Missouri, USA; "Alfa Aesar" refers to Alfa Aesar of Ward Hill, Massachusetts, USA; "Gelest" refers to Gelest Inc., of Morrisville, Pennsylvania, U.S.A.; and "Strem" refers to Strem Chemicals Inc. of Newburyport, Massachusetts, U.S.A.

[0031] The ligand is an organic compound that, without wishing to be bound by theory, is thought to coordinate with M. The ligand differs from the displaceable substituent selected for A. 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 M precursor of general formula (i) above to form the reaction product.

[0032] The ligand may have general formula (ii):

[0033] In general formula (ii), D is a divalent hydrocarbon group of formula (CR⁸2)x, where subscript x is 0, 1 or 2 and each R⁸ is independently H, an alkyl group, or a haloalkyl group. Alternatively, D is a divalent hydrocarbon group and x is 1. Alternatively, D is a covalent bond (between the carbon atom in the ring and the carbon atom in the carbonyl group i.e., when x = 0). The alkyl group and/or the haloalkyl group for R⁸ may have 1 to 6 carbon atoms; alternatively 1 to 4 carbon atoms. Alternatively, each R⁸ is H.

[0034] In general formula (ii), R⁵, R⁶, and R⁷ are each independently selected from a monovalent organic group, a heteroatom, and H. Alternatively, the heteroatom for R⁵, R⁶, and R⁷ may be a halogen atom; alternatively, Br, CI, or F. The monovalent organic group for R⁵, R⁶, and R⁷ may be a hydrocarbon nm n such as alkyl group or an alkenyl group; or a heteroatom containing group such as alkoxy. The alkyl group and/or the alkoxy group for R⁵, R⁶, and R⁷ may have 1 to 6 carbon atoms; alternatively 1 to 4 carbon atoms.

Alternatively, R^, R6, and R⁷ are each independently selected from H and alkyl.

Alternatively, R⁵, R⁶, and R⁷ are each H. Examples of ligands of general formula (ii) include 2-thiopheneacetic acid. When the ligand has general formula (ii), the metal precursor may be any metal precursor described above; alternatively, M in the metal precursor may be selected from Fe, Ti, and Zr; and alternatively M may be Zr.

[0035] Alternatively, the ligand may have general formula (iii):

[0036] In general formula (iii), Q is selected from O and S, alternatively O. R^{1 5} is selected from a monovalent organic group and H. Alternatively, R^{1 5} is H or alkyl.

Alternatively, R¹ ^ is H. Each R¹ ^ is independently selected from a monovalent organic group, H, and a halogen. Alternatively, each R^{1 6} is independently selected from H, alkyl, and haloalkyl. Alternatively, each R¹ ^ j_s H. In general formula (iii), R^{1 7}, R¹ ^ R19_j and R²⁰ are each independently selected from H, a monovalent organic group, and a halogen. Alternatively, each R^{1 7}, R¹ ^ R19_{j anc}| R20 j_s independently selected from H, a hydrocarbon group such as alkyl, or a heteroatom containing group such as alkoxy or haloalkyl; where the alkyl groups may have 1 to 12 carbon atoms, the alkoxy groups may have 1 to 12 carbon atoms, and haloalkyl groups may have 1 to 12 carbon atoms.

Alternatively, R^{1 7}, R¹ ^ and R¹ ^ are each H. Alternatively, R¹ ^ and R²^ may combine to form a fused ring structure with the pyridyl group shown. The ring structure may be an aryl group or an aralkyl group which is fused to the pyridyl group shown. Examples of ligands of general formula (iii) include 8-hydroxyquinoline. When the ligand has general formula (iii), M in the metal precursor may be selected from Bi and Fe; alternatively M may be Bi; and alternatively M may be Fe.

[0037] Alternatively, the ligand may have general formula (iv):

[0038] In general formula (iv), R¹ and R² are each independently selected from H, and a monovalent organic group. The monovalent organic group may be a hydrocarbon group or a heteroatom containing group. Alternatively, R¹ and R² are each independently selected from H, hydrocarbon groups such as alkyl, and heteroatom containing groups such as alkoxy or haloalkyi groups. The alkyl groups may have 1 to 6 carbon atoms; the haloalkyi groups may have 1 to 6 carbon atoms; and the alkoxy groups may have 1 to 6 carbon atoms. R³ and R⁴ are each independently a monovalent organic group. The monovalent organic group may be a hydrocarbon group or a heteroatom containing group.

Alternatively, R³ and R⁴ are each independently selected from alkyl groups, haloalkyi groups, and alkoxy groups or groups of formula -CR²¹2-C(=0)OR²², where R²¹ is alkyl or haloalkyi; and where R²² is alkyl or haloalkyi; such as alkyl groups of 1 to 12 carbon atoms, alkoxy groups of 1 to 12 carbon atoms, and haloalkyi groups of 1 to 12 carbon atoms. The alkyl groups for R³ , R⁴, R²¹ , and R²² may have 1 to 12 carbon atoms, the alkoxy groups for R³ , R⁴, R²¹ , and R²² may have 1 to 12 carbon atoms, and the haloalkyi groups for R³ , R⁴, R²¹ , and R²² may have 1 to 12 carbon atoms. Alternatively, R¹ and

R² may both be H. Alternatively, R³ is alkyl or haloalkyi or alkylacetate. Alternatively, R⁴ is alkyl or alkoxy; alternatively alkyl; and alternatively alkoxy. Examples of ligands of general formula (iv) include 3,5-heptanedione, ethylacetylacetonate, ethyl-3-oxopentanoate and n-octylchloroacetoacetate, and ethyl-4-chloroacetoacetate.

[0039] In one embodiment, when the ligand has general formula (iv), M in the metal precursor may be selected from Fe and Zn; alternatively M may be Fe; and alternatively M may be Zn.

[0040] Alternatively, when the ligand has general formula (iv), where R¹ and R² are each independently selected from H and a monovalent organic group, and R³ and R⁴ are each independently a monovalent organic group, but with the proviso that at least one of R³ and R⁴ has formula -CR²¹2-C(=0)OR²², where R²¹ is alkyl or haloalkyi; and where R²² is alkyl or haloalkyi; then M in the metal precursor may be selected from Bi, Cu, Fe, Hf, Ti, Zn, and Zr.

[0041] Alternatively, when the ligand has general formula (iv), where R¹ and R² are each independently selected from H and a monovalent organic group, R³ is alkyl of 1 or 2 carbon atoms and R⁴ is alkoxy of 1 or 2 carbon atoms, with the proviso that when R³ has 2 carbon atoms then R⁴ has 1 carbon atom and when R⁴ has 2 carbon atoms then R³ has 1 carbon atom, then M in the metal precursor may be Ti. [0042] Alternatively, the ligand may have general formula

[0043] In general formula (v), each R⁹ and each R^{1 0} is independently selected from H and a monovalent organic group. Alternatively, each R⁹ and each R^{1 0} is independently selected from H and a monovalent organic group selected from hydrocarbon groups such as alkyi or alkenyl, and heteroatom containing groups such as haloalkyi. Alternatively, each R⁹ is alkyi or haloalkyi; such as alkyi groups of 1 to 12 carbon atoms, alkoxy groups of 1 to 12 carbon atoms, and haloalkyi groups of 1 to 12 carbon atoms. Alternatively, each R^{1 0} is alkyi or haloalkyi; such as alkyi groups of 1 to 12 carbon atoms, alkoxy groups of 1 to 12 carbon atoms, and haloalkyi groups of 1 to 12 carbon atoms. Alternatively, each R⁹ and each R¹0 is H.

[0044] In general formula (v), each R^{1 1} , each R^{1 2}, and each R^{1 3} is independently selected from H, halogen, and a monovalent organic group. Alternatively, each R^{1 1} , each

R^{1 2}, and each R^{1 3} is independently selected from H and a monovalent organic group selected from hydrocarbon groups such as alkyi and alkenyl, and heteroatom containing groups such as alkoxy or haloalkyi. Alternatively, each R^{1 1} , each R^{1 2}, and each R^{1 3} is independently selected from H, alkyi, alkoxy or haloalkyi; where the alkyi groups may have 1 to 12 carbon atoms, the alkoxy groups may have 1 to 12 carbon atoms, and haloalkyi groups may have 1 to 12 carbon atoms. Alternatively, each R^{1 1} , each R^{1 2}, and each R^{1 3} is H. Examples of ligands of this formula include N,N'-dimethyl-1 ,3-propanediamine. When the ligand has general formula (v), then M in the metal precursor may be selected from Bi, Cu, Fe, Hf, Ti, Zn, and Zr.

[0045] Alternatively, the ligand may have general formula (vii) :

. In this formula, each dotted line represents that the bond may be a single bond or a double bond. Subscript aa is 0 or 1 , depending on whether the bond from the carbon atom to the oxygen atom is a single bond or a double bond. Subscript bb is 0 or 1 . Subscript ee is 1 or 2.

[0046] In general formula (vii), R³² and R³³ are each independently a monovalent organic group. The monovalent organic group for R³² and R³³ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from alkyl, aryl, or aralkyi groups. Alternatively, the monovalent hydrocarbon group may be selected from methyl, ethyl , isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl. Alternatively, the monovalent organic group for R³² and/or R³³ may be a heteroatom containing group. The heteroatom containing group may be a halogenated alkyl group, an alkoxy group, or an organosilane group. Alternatively, R³² and/or R³³ may be a halogenated alkyl group such as CF3 or CH2CF3. Alternatively, R³² and/or R³³ may be an alkoxy group, such as OMe,

OEt, OPr, or OBu.

[0047] In general formula (vii), each R³⁰ and each R³¹ are each independently selected from H, a monovalent organic group and an inorganic group. Alternatively, each R³⁰ and each R³¹ may be H. Alternatively, the monovalent organic group for R³^ and/or R³¹ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from alkyl, aryl, or aralkyi groups. Alternatively, the monovalent hydrocarbon group may be selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl.

Alternatively, the monovalent organic group for R³⁰ and/or R³¹ may be a heteroatom containing group. The heteroatom containing group may be an alkylamine group, an alcoholic group, an alkoxy group, an ether group, an organosilane group, an organothiol group, or a thioether group. Alternatively, one or more R³⁰ and/or R³¹ may independently be an alkylamine group, such as -CH2CH2-NH2, -CH2CH2NHCH3, or ΟΗ₂ΟΗ₂-

N(CH2CH3)2. Alternatively, one or more R³^ and/or R³¹ may be independently selected from an alcoholic, an alkoxy, or an ether group, such as -CH2CH2OH, -CH2CH2CH2OH, -

CH2CH2OCH3, CH2CH2CH2OCH2CH3. Alternatively, one or more R³⁰ and/or R³¹ may be independently an organosilane group, such as CH2CH2CH2-Si(Me)3 or -CH2CH2CH2-

Si(Et)3- Alternatively, one or more R³^ and/or R³¹ may be independently selected from organothiol and thioether groups, such as -CH2CH2-SH, -CH2CH2-S-CH3, -CH2CH2-S- CH₂CH₃.

[0048] Alternatively, at least one of R³^ and/or R³¹ is an organosilane. R³^ and/or R³¹ may be an organosilane group of formula -R³⁵ _ccSi(R³⁶), where subscript cc is 0 or 1 , R³⁵ is a divalent hydrocarbon group, and each R³⁶ is independently H or a monovalent hydrocarbon group. R³⁵ is exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such

exemplified by alkyl groups such as Me, Et, Pr, and Bu; alternatively Me or Et.

Alternatively, R³⁰ may be -Si(Me)₃, CH₂CH₂CH2-Si(Me)3 or -CH₂CH₂CH2-Si(Et)3.

[0049] Each R³⁴ is independently selected from H and a monovalent organic group.

Alternatively, R³⁴ may be H. The monovalent organic group may be a hydrocarbon group or a heteroatom containing group. Alternatively, each R³⁴ is independently selected from H, hydrocarbon groups such as alkyl, and heteroatom containing groups such as alkoxy or haloalkyl groups. Alternatively, the monovalent organic group for R³⁴ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from an alkyl, aryl, or aralkyl group. Alternatively, the monovalent hydrocarbon group may be independently selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl. Alternatively, the monovalent organic group for R³⁴ may be a heteroatom containing group such as an ester group. Alternatively, the inorganic group for R³⁴ may be a nitrite or nitrile group. Alternatively, one or more R³⁴ may be selected from nitrite, nitrile, and ester groups. Alternatively, R³¹ and R³² can combine to form a ring moiety.

Alternatively, R³^ and R³³ can combine to form a ring moiety. Alternatively, R³² and R³⁴ can combine to form a ring moiety. Alternatively, R³³ and R³⁴ can combine to form a ring moiety.

[0050] Examples of ligands of general formula (vii) include isomers of formula

, and their corresponding enolate isomers, which include one or more of the isomers having general formulae

where R³⁰, R³¹ , R³², R³³, R³⁴, subscript aa, subscript bb, and subscript ee are as described above. Alternatively, the ligand of formula (vii) may be an enolate isomer.

Alternatively, either subscript aa or subscript bb, or both is 1 , and at least one of R³⁰ and

R³¹ is an organosilane group. The ligand of general formula (vii) may be 3,5- heptanedione, ethylacetylacetonate, ethyl-3-oxopentanoate, n-octylchloroacetoacetate, and ethyl-4-chloroacetoacetate, trimethylsilyloxy-3-penten-2-one, ereof

[0051] Alternatively, the ligand may have general formula (vii):

[0052] In general formula (vii), R³² and R³³ are each independently a monovalent organic group. The monovalent organic group for R³² and R³³ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from alkyl, aryl, or aralkyl groups. Alternatively, the monovalent hydrocarbon group may be selected from methyl, ethyl , isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl. Alternatively, the monovalent organic group for R³² and/or R³³ may be a heteroatom containing group. The heteroatom containing group may be a halogenated alkyl group, an alkoxy group, or an organosilane group. Alternatively, R³² and/or R³³ may be a halogenated alkyl group such as CF3 or CH2CF3. Alternatively, R³² and/or R³³ may be an alkoxy group, such as OMe,

OEt, OPr, or OBu.

[0053] In general formula (vii), each R³⁰ and each R³¹ are each independently selected from H, a monovalent organic group and an inorganic group. Alternatively, each R³⁰ and each R³¹ may be H. Alternatively, the monovalent organic group for R³^ and/or R³¹ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from alkyl, aryl, or aralkyi groups. Alternatively, the monovalent hydrocarbon group may be selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl.

Alternatively, the monovalent organic group for R³⁰ and/or R³¹ may be a heteroatom containing group. The heteroatom containing group may be an alkylamine group, an alcoholic group, an alkoxy group, an ether group, an organosilane group, an organothiol group, or a thioether group. Alternatively, one or more R³⁰ and/or R³¹ may independently be an alkylamine group, such as -CH₂CH₂-NH₂, -CH₂CH₂NHCH₃, or CH₂CH₂-

N(CH₂CH3)₂. Alternatively, one or more R³^ and/or R³¹ may be independently selected from an alcoholic, an alkoxy, or an ether group, such as -CH₂CH₂OH, -CH₂CH₂CH₂OH, -

CH₂CH₂OCH₃, CH₂CH₂CH₂OCH₂CH₃. Alternatively, one or more R³⁰ and/or R³¹ may be independently an organosilane group, such as CH₂CH₂CH₂-Si(Me)3 or -CH₂CH₂CH₂-

Si(Et)3- Alternatively, one or more R³^ and/or R³¹ may be independently selected from organothiol and thioether groups, such as -CH₂CH₂-SH, -CH₂CH₂-S-CH₃, -CH₂CH₂-S- CH₂CH₃.

[0054] Alternatively, at least one of R³^ and/or R³¹ is an organosilane. R³^ and/or R³¹ may be an organosilane group of formula -R³⁵ _ccSi(R³⁶), where subscript cc is 0 or 1 , R³⁵ is a divalent hydrocarbon group, and each R³⁶ is independently H or a monovalent hydrocarbon group. R³⁵ is exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such

exemplified by alkyl groups such as Me, Et, Pr, and Bu; alternatively Me or Et.

Alternatively, R³⁰ may be -Si(Me)₃, CH₂CH₂CH₂-Si(Me)₃ or -CH₂CH₂CH₂-Si(Et)₃.

[0055] Each R³⁴ is independently selected from H and a monovalent organic group.

Alternatively, R³⁴ may be H. The monovalent organic group may be a hydrocarbon group or a heteroatom containing group. Alternatively, each R³⁴ is independently selected from H, hydrocarbon groups such as alkyl, and heteroatom containing groups such as alkoxy or haloalkyl groups. Alternatively, the monovalent organic group for R³⁴ may be a monovalent hydrocarbon group. The monovalent hydrocarbon group may be selected from an alkyl, aryl, or aralkyi group. Alternatively, the monovalent hydrocarbon group may be independently selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, phenyl, or benzyl. Alternatively, the monovalent organic group for R³⁴ may be a heteroatom containing group such as an ester group. Alternatively, the inorganic group for R³⁴ may be a nitrite or nitrile group. Alternatively, one or more R³⁴ may be selected from nitrite, nitrile, and ester groups. Alternatively, R³¹ and R³² can combine to form a ring moiety.

Alternatively, when R³⁰ is an organosilane group, the ligand may be trimethylsilyloxy-3- penten-2-one.

[0056] Examples of suitable ligands for use in preparing ingredient (A) include the ligands listed below in Table 2. The neutral forms of the ligands are shown below in Table 2.

Ligand Structure

trimethylsilyloxy-3- penten-2-one

0 ethyl-4- O 0

chloroacetoacetate

[0057] Various ligands in Table 2 are commercially available. For example, 3,5- heptandione, 8-hydroxyquinoline, 2-thiopheneacetic acid, ethylacetylacetonate, and ethyl 3-oxopentanoate are available from Sigma-Aldrich of St. Louis, Missouri, USA. N- octylchloroacetoacetate is available from Acros Organics, a part of Fisher Scientific USA of Pittsburgh, Pennsylvania, U.S.A.

[0058] Ingredient (A) may be prepared by a method comprising combining the ligand and the M precursor, described above, thereby forming a catalytically active condensation catalyst comprising the M-ligand complex. The method may optionally further comprise a step of dissolving either the M precursor, or the ligand, or both, in a solvent before combining the M precursor and the ligand. Suitable solvents are exemplified by those described below for ingredient (F) and/or (S"). Alternatively, the ligand may be dissolved in a solvent in a container, and the solvent may thereafter be removed before adding the M precursor to the container with the ligand. The amounts of ligand and M precursor are selected such that the mole ratio of ligand to M precursor (Ligand:Metal Ratio) may range from 10:1 to 1 :1 , alternatively 6:1 to 1 :1 , alternatively 3:1 to 1 :1 , and alternatively 2:1 to 1 :1 . Combining the M precursor and the ligand may be performed by any convenient means, such as mixing them together in a container or shaking the container.

[0059] Combining the M precursor and ligand may be performed by any convenient means such as allowing the M 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 M precursor and ligand selected and the Ligand:Metal Ratio, however, temperature may range from 25 °C to 200 ^<€, 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 M precursor may be combined and heated sequentially.

Alternatively, the ligand and M precursor may be combined and heated concurrently.

[0060] The method of preparing the catalytically active condensation catalyst of ingredient (A) may optionally further comprise adding a solvent after the combining of the M precursor and the ligand. Suitable solvents are exemplified by those described below for ingredient (F) and/or (S"). Alternatively, the method may optionally further comprise removing all or a portion of, unreacted M precursor, unreacted ligand, a reaction by-product and/or the solvent, if the solvent is present (e.g., used to facilitate combination of the M precursor and the ligand before or during combining and/or 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 M precursor when the ligand reacts with the M precursor. Unreacted reactants (M precursor and/or ligand) and 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 M-ligand complex may be used as the catalytically active condensation catalyst of ingredient (A).

[0061] Alternatively, the reaction by-products and/or unreacted reactants are not removed before using the catalytically active condensation catalyst as ingredient (A). For example, the ligand and M precursor may be combined as described above, with or without solvent removal, and the resulting catalytically active catalyst (comprising the M-ligand complex and the reaction by-product and optionally a solvent or diluent and optionally one or more unreacted reactants) may be used as ingredient (A). Without wishing to be bound by theory, it is thought that a by-product may act as a reaction catalyst in addition to the M- ligand complex, or as a co-catalyst or an activator for the M-ligand complex. Therefore, the mixture of one or more of the reactants and/or by-products forming ingredient (A) may catalyze a reaction of the isocyanate groups and hydroxy groups of ingredients (B) and (C) and/or ingredient (A) may catalyze a reaction of the ester and hydroxy groups of ingredients (Β') and (C), and/or ingredient (A) may catalyze a reaction of the hydrolyzable moieties of ingredient (B").

[0062] 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 any M compound that would catalyze the reaction of (X) the reactive component, other than ingredient (A). Alternatively, the composition may be free of metal catalysts other than ingredient (A). [0063] 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 (X), 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 0.1 % to 7%, and alternatively 0.5% to 6.5%, based on total weight of all ingredients in the composition.

Reactive Component

[0064] The reactive component (X) comprises one or more ingredients with functional groups capable of being catalyzed by Ingredient (A). The reactive component may be (X1 ) a urethane component comprising (B) an isocyanate-functional compound and (C) a hydroxy-functional compound.

[0065] Ingredient (B) in the urethane composition described above is an isocyanate- functional compound. The isocyanate-functional compound has an average of one or more isocyanate groups per molecule. Alternatively, the isocyanate-functional compound may have an average of two or more isocyanate groups per molecule. The isocyanate functional compound may have formula: R-(N=C=0)_m, where R is an organic group and subscript m is an integer representing the number of isocyanate groups per molecule, and m≥ 1 , alternatively m≥ 2.

[0066] The isocyanate-functional compound may be organic. Ingredient (B) is exemplified by monomeric isocyanates and polymeric isocyanates. Monomeric isocyanates include aromatic diisocyanates such as methylene bis(phenyl isocyanate), meta-tetramethyl xylene diisocyanate (TMXDI), toluene diisocyanate (TDI), and methylene diphenyl diisocyanate; and aliphatic and cycloaliphatic isocyanates such as hexamethylene diisocyanate (HDI), 1 -isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane

(isophorone diisocyanate, IPDI), and nonanetriisocyanate (TTI), phenylene diisocyanate, xylene diisocyanate, 1 ,5-naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, toluidine diisocyanate and alkylated benzene diisocyanates generally; methylene-interrupted aromatic diisocyanates such as methylene-diphenyl-diisocyanate, especially the 4,4'-isomer (MDI) including alkylated analogs such as 3,3'-dimethyl-4,4'-diphenyl-methane diisocyanate; such hydrogenated materials as cyclohexylene diisocyanate, 4,4'-methylenedicyclohexyl diisocyanate; mixed aralkyl diisocyanates such as the tetramethylxylyl diisocyanates,

OCNC(CH3)2C6H4C(CH3)2NCO, and polymethylene isocyanates such as 1 ,4- tetramethylene diisocyanate, 1 ,5-pentamethylene diisocyanate, 1 ,6-hexamethylene diisocyanate (HMDI), 1 ,7-heptamethylene diisocyanate, 2,2,4- and 2,4,4- trimethylhexamethylene diisocyanate, 1 ,10-decamethylene diisocyanate, and 2-methyl-1 ,5- pentamethylene diisocyanate; vinylisocyanate; and combinations thereof.

[0067] Polymeric isocyanates include isocyanurates (such as isocyanurate trimer), allophanate, or biuret compounds. Most of the isocyanates are difunctional, that is they have 2 isocyanate groups per molecule. An important exception to this is polymeric diphenylmethane diisocyanate, which is a mixture of molecules with two-, three-, and four- or more isocyanate groups, which may have an average functionality greater than two, commonly 2.7. Isocyanate functional compounds with isocyanate functionality greater than two may act as crosslinking sites. Commercially available isocyanate functional organic compounds are illustrated by Tolonate XI DT 70SB an isophorone diisocyanate trimer (70% solids, 12.3 wt% NCO) sold by Rhodia (Cranbury, NJ) and Desmodur N-100

polyisocyanate (available from Mobay Corp.).

[0068] Alternatively, the isocyanate-functional compound may be a polyorganosiloxane having one or more terminal and/or pendant isocyanate-functional group(s). Suitable polyorganosiloxanes for ingredient (B) may have unit formula [I]:

(R303SiO-|/2)a(R³¹2SiO2/2)b(R³²SiO3/2)c(SiO4/2)d- Each R³°, R³ , and R³² is independently a monovalent organic group, with the proviso that at least one, per molecule, of R³⁰, R³¹ , and R³² is present and is an isocyanate-functional group. Subscripts a, b, c, and d, represent the molar amounts of each siloxane unit present; subscript a≥ 0, subscript b≥ 0, subscript c≥ 0, and 0 < d < 1 ; with the proviso that 0 < (a+b+c+d) < 1 .

Other suitable monovalent organic groups for R³0, R³¹ , and R³² include hydrocarbon groups and halogenated hydrocarbon groups. The hydrocarbon groups include alkyl, alkenyl, aryl, and aralkyl. The halogenated hydrocarbon groups include haloalkyi groups. The alkyl groups may have 1 to 6 carbon atoms; and the haloalkyi groups may have 1 to 6 carbon atoms. Alternatively, the R³⁰, R³¹ and R³² groups other than the isocyanate- functional groups are each independently selected from alkyl groups, haloalkyi groups, aryl groups, and aralkyl groups.

[0069] Examples of suitable isocyanate-functional polyorganosiloxanes include, but are not limited to, polydiorganosiloxanes of formula [II], below, which may be endblocked with isocyanate functional organic groups.

[0070] Formula [II] is

, where subscript n is 1 to 200, each R³¹ may be an alkyl group, such as Me, each R³⁰ is selected from an isocyanate-functional group and an alkyl group, such as Me. Alternatively, two of R³⁰ on each end may be alkyl and the remaining R³⁰ on each end may be an iso-cyanate functional group, such as a diisocyanato-alkyl group. Exemplary diisocyanate-endblocked polydimethylsiloxanes are known, for example, in JP05-287839A.

[0071] Alternatively, the isocyanate-functional polyorganosiloxane may have a resinous structure, such as that disclosed in U.S. Patent 8,399,594. The isocyanate-functional groups bonded to the polyorganosiloxane may be blocked or unblocked. Exemplary resinous isocyanate-functional polyorganosiloxanes may have unit formula [I], above, with the proviso that (c + d) > 0. Other isocyanate-functional polyorganosiloxanes and methods for their preparation are disclosed, for example, in U.S. Patent 3,502,704.

[0072] Ingredient (B) may be one isocyanate-functional compound. Alternatively, ingredient (B) may be may be a mixture of two or more isocyanate-functional compounds that differ in at least one property selected from molecular weight, NCO content, and functional groups in addition to NCO. The amount of ingredient (B) depends on various factors including the desired form of the reaction product of the composition, the type and amounts of other ingredients of the composition. However, the amount of ingredient (B) may be 30% to 50% based on the total weight of all ingredients in the composition.

[0073] Ingredient (C) in the composition described above is a hydroxy-functional compound. The hydroxy-functional compound has at least one OH group per molecule. 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.

[0074] Ingredient (C) may be an organic hydroxy-functional compound. The organic hydroxy-functional compound may be 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, and a combination thereof.

[0075] 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 515g/mol carbon-bonded hydroxy) (Bayer, Pittsburgh, PA)

[0076] The 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 hydroxy-functional compound may be from 80 to 800, alternatively 100 to 600.

[0077] Alternatively, ingredient (C) may be a carbinol functional polyorganosiloxane. Exemplary carbinol functional polyorganosiloxanes may have unit formula [III]. Unit formula [III] is: (R4l 3Si0₁/2)e(R⁴²2Si02/2)f(R⁴³Si0₃/2)g(Si04/2)_h.

In unit formula [III], each R⁴¹ is 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 R⁴² is 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 R⁴³ is 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 .

[0078] 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,

. 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 R⁴⁴ is a divalent hydrocarbon group having at least 3 carbon atoms or divalent hydrocarbonoxy group having at least 3 carbon atoms.

The group R⁴⁴ is 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 to10. An aryl-containing carbinol group having at least 6 carbon atoms is illustrated by groups having the formula R⁴⁵OH wherein R⁴⁵ is 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.

[0079] The carbinol-functional polyorganosiloxane may be a carbinol-functional silicone resin. Suitable carbinol-functional silicone resins are exemplified by

carbinol-functional silicone resins comprising the units:

((CH^SiO!/^e

((R⁴6)CH₃Si0₂/2)f where R⁴⁶ = -(CH₂)3C₆H₄OH

((C₆H₅)CH₃Si02/2)f and

(C₆H₅Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((R⁴7)(CH₃)₂Si0₁/2)e where R⁴? = -(CH^Ce^OH and

(C₆H₅Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((R⁴7)(CH₃)₂Si0₁/2)e where R⁴? = -(CH^Ce^OH and

(CH₃Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((R⁴8)(CH₃)2SiO-|/2)e where R⁴8 = -(CH₂)30H and

(C₆H₅Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((R⁴9)(CH₃)2SiO-|/2)e where R⁴9 = -(CH₂)30H

(CH₃Si0₃/2)g and

(C₆H₅Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((CH^SiO!/^e

((R50)CH₃SiO₂/2)f where R⁵⁰ = -(CH₂)30H

((C₆H₅)CH₃Si02/2)f and (C₆H₅Si03/2)_g,

carbinol-functional silicone resins comprising the units:

((CH₃)₃Si0_{1 /2})_e

((R⁵¹ )(CH₃)₂Si0₁/2)e where R⁵¹ = -(CH₂)30H and

(C₆H₅Si0₃/2)g; and

carbinol-functional silicone resins comprising the units:

((R⁵²)(CH₃)₂Si0₁/2)e where R⁵² = -CH₂CH(CH₃)CH₂OH

((H)(CH₃)₂Si0_{1 /2})_e and

(C₆H₅Si0₃/₂)_g>

where subscript e has a total value in the resin of 0.2 to 0.4, f has a total value in the resin of zero to 0.4, and g has a total value in the resin of 0.3 to 0.8. Examples of such carbinol functional polyorganosiloxanes are disclosed in WO2008/088491 and U.S. Patent

7,452,956.

[0080] Ingredient (C) may be one hydroxy-functional compound. Alternatively, ingredient (C) may be may be a blend of two or more hydroxy-functional compounds that differ in at least one property selected from molecular weight, OH content, and functional groups in addition to OH. The amount of ingredient (C) depends on various factors including the desired form of the reaction product of the composition, and the type and amounts of other ingredients of the composition. However, the amount of ingredient (C) may be 40% to 65% based on the total weight of all ingredients in the composition.

[0081] Ingredients (B) and (C) are present in sufficient amounts to provide a molar ratio of isocyanate groups:OH groups (NCO:OH Ratio) from 0.1 :1 to 10:1 ; alternatively 0.5:1 to 2:1 ; and alternatively 1 :1 to 1 .1 :1 , in the composition. The reaction between the isocyanate groups on ingredient (B) and the OH groups on ingredient (C) makes a urethane linkage, -RNHCOOR'-, where R and R' are as described above, and this reaction is catalyzed by ingredient (A).

[0082] In one embodiment, ingredient (B) is an isocyanate-functional organic compound and ingredient (C) is a hydroxy-functional organic compound. In an alternative

embodiment, ingredient (B) is an isocyanate-functional organic compound and ingredient (C) is a hydroxy-functional polyorganosiloxane. In an alternative embodiment, ingredient (B) is an isocyanate-functional polyorganosiloxane and ingredient (C) is a hydroxy- functional polyorganosiloxane. In an alternative embodiment, ingredient (B) is an isocyanate-functional polyorganosiloxane and ingredient (C) is a hydroxy-functional organic compound. [0083] Alternatively, (X) the reactive component, may be (X2) an ester component comprising (Β') a carboxylic acid-functional compound (carboxylic acid and/or anhydride) or ester and (C) a hydroxy functional compound. Ingredient (Β') may have formula R-(C(=0)- OR")p, where R is an organic group, R" is H or a monovalent hydrocarbon group such as alkyl, and subscript p is 1 or more, alternatively 2 or more.

[0084] Ingredient (Β') in the ester component may be an organic carboxylic acid functional compound. Examples include monocarboxylic acids and polycarboxylic acids and anhydrides thereof. For example, the acids which may be used include acetic, acrylic, propionic, propiolic, isobutyric, methacrylic, n-butyric, pivalic, ethylmethylacetic, isovaleric, chloroacetic, a-chloropropionic, n-valeric, dichloroacetic, diethylacetic, isocaproic, a-ethyl- n-butyric, methoxyacetic, n-caproic, ethoxyacetic, bromoacetic, heptoic, a-ethyl-n-caproic, β-bromoisovaleric, hexahydrobenzoic, dibromoacetic, n-caprylic, a-phenylpropionic, undecanoic, β-phenylpropionic, mesitylenic, tricarballylic, α,β-dibromosuccinic, tartaric, 3,5- dinitrosalicylic, p-toluic, acetylenedicarboxylic, veratric (anhydrous), p-fluorobenzoic, 2,4- dinitrobenzoic, anisic, β-naphthoic, acetylanthranilic, camphoric, hippuric, succinic, aconitic, m-nitrocinnamic, 2-chloro-3,5-dinitrobenzoic, fumaric, m-hydroxybenzoic, p-coumaric, phthalic, o-coumaric, p-hydroxybenzoic, β-resorcylic, tetrachlorophthalic, p-bromobenzoic, isophthalic, terephthalic, trimesic, β-benzoylpropionic, p-isopropylbenzoic, benzoic, o- benzoylbenzoic, γ-benzoylbutyric, 2,4-dimethylbenzoic, maleic, o-(p-toluyl)-benzoic, 2,5- dimethylbenzoic, sebacic, mandelic, cinnamic, acetylsalicylic, phenylpropiolic, glutaconic (cis), glutaconic (trans), 2,6-dichlorobenzoic, o-chlorobenzoic, m-nitrobenzoic, meso- tartaric, suberic, furylacrylic, o-nitrophenylacetic, 3-nitrosalicylic, diphenylacetic, o- nitrobenzoic, phthalonic, p-hydroxyphenylacetic, o-bromobenzoic, benzilic, adipic, p- nitrophenylacetic, 2,5-dichlorobenzoic, citric, m-bromobenzoic, 2,4,6-trimethylbenzoic, salicylic, m-chlorobenzoic, 2,4-dichlorobenzoic, a-naphthoic, 2,3-dichlorobenzoic, 3,4- dimethylbenzoic, oleic, methacrylic, lactic, β-bromoisobutyric, thiobenzoic, undecylenic, undecanoic, hexahydrobenzoic, capric, pivalic, β-chloropropionic, lauric, angelic, dibromoacetic, β-phenylpropionic (hydrocinnamic), a -bromoisobutyric, bromoacetic, elaidic, γ-phenylbutyric, myristic, trichloroacetic, β-bromopropionic, palmitic, chloroacetic, α,β-dibromopropionic, cyanoacetic, stearic, crotonic (trans), phenylacetic, glycolic, citranconic, phenoxyacetic, phthalaldehydic, glutaric, o-methoxybenzoic, o-toluic, pimelic, azelaic, m-toluic, ethylmalonic, malonic, suberic, brassylic, thapsic, fumaric, glutaconic, a- hydromuconic, β-hydromuconic, a-butyl-a-ethyl glutaric, α,β-ethyl succinic, isophthalic, terephthalic, hemimellitic, 1 ,4-cyclohexane dicarboxylic, and a combination thereof.

[0085] Anhydrides of mono- and poly-functional acids can be used in addition to or instead of the acids as ingredient (Β'). Examples of such anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, citaconic anhydride, n-valeric anhydride, crotonic anhydride, n-heptoic anhydride, benzoic anhydride, chloroacetic anhydride, maleic anhydride, itaconic anhydride, 4-nitrophthalic anhydride, succinic anhydride, cinnamic anhydride, phthalic anhydride, 1 ,2-naphthalic anhydride, camphoric anhydride, 2,3-naphthalic anhydride, a -naphthoic anhydride, 1 ,8-naphthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and a combination thereof.

[0086] Ingredient (C) in the ester component may be exemplified by ingredient (C) described above for the urethane component. Ingredient (C) is exemplified by monohydric and polyhydric alcohols, which can be reacted with carboxylic acids and anhydrides, and include methyl alcohol, ethyl alcohol, isopropyl alcohol, tertbutyl alcohol, allyl alcohol, n- propyl alcohol, sec-butyl alcohol, tert-amyl alcohol, isobutyl alcohol,

methylisopropylcarbinol, n-butyl alcohol, diethylcarbinol, sec-amyl alcohol, ethylene monomethyl ether, 1 -chloro-2-propanol, sec-butylcarbinol, ethylene chlorohydrin, isoamyl alcohol, 4-methyl-2-pentanol, 2-chloro-1 -propanol, ethylene glycol monoethyl ether, 3- hexanol, methylisobutylcarbinol, n-amyl alcohol, cyclopentanol, 2-ethyl-1 -butanol, 2- bromoethanol, di-n-propylcarbinol, n-hexyl alcohol, 2-heptanol, 2-methylcyclohexanol, furfuryl alcohol, ethylene glycol mono-n-butyl ether, 4-methylcyclohexanol, 3- methylcyclohexanol, cyclohexanol, trichloroethyl alcohol, lauryl alcohol, cinnamyl alcohol, a-terpineol, o-tolylcarbinol, myristyl alcohol, menthol, anisyl alcohol, pinacol hydrate, p- tolylcarbinol, sorbitol, triphenylcarbinol, mannitol, benzopinacol, borneol, inositol, pentaerythritol, diisobutylcarbinol, n-heptyl alcohol, tetrahydrofurfuryl alcohol, 2-octanol, cyclohexylcarbinol, 2,3-dichloro-1 -propanol, 2-ethyl-1 -hexanol, propylene glycol, n-octyl alcohol, diethylene glycol monomethyl ether, ethylene glycol, diethylene glycol monoethyl ether, methylphenylcarbinol, benzyl alcohol, n-nonyl alcohol, trimethylene glycol, m- tolycarbinol, β-phenylethyl alcohol, ethylphenylcarbinol, diethylene glycol mono-n-butyl ether, n-decyl alcohol, γ-phenylpropyl alcohol, diethylene glycol, ethylene glycol monophenyl ether, cinnamyl alcohol, glycerol, benzohydrol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1 ,4-tetramethylene glycol, 1 ,2-butylene glycol, 1 ,4-butanediol, 1 ,3-butanediol, 1 ,5-pentanediol, 1 ,4-pentanediol, 1 ,3-butanediol, 1 ,6-hexanediol, 1 ,7- heptanediol, 1 ,1 ,1 -trimethylolpropane, 1 ,1 ,1 -trimethylolethane, hexane-1 ,2,6-triol, neopentyl glycol, 1 ,10-decanediol, and 2,2 bis(4-hydroxycyclohexyl) propane.

[0087] Alternatively, (X) the reactive component is a reactive component (X3) capable of producing a siloxane product via a condensation reaction, and the reactive component (X3) comprises ingredient (B") a silicon containing base polymer having an average, per molecule, of one or more hydrolyzable substituents and optionally (C") a crosslinker and/or (L") a chain lengthener. [0088] Ingredient (B") is a silicon containing base polymer (base polymer). Ingredient (B") comprises a polymer backbone having an average, per molecule, of one or more hydrolyzable substituents covalently bonded thereto. Alternatively, the one or more hydrolyzable substituents are hydrolyzable silyl substituents. The polymer backbone may be selected from a polyorganosiloxane such as a polydiorganosiloxane, an organic polymer backbone, or a silicone-organic copolymer backbone (having the one or more hydrolyzable silyl substituents covalently bonded to an atom in the polymer backbone). Alternatively, the polymer backbone of ingredient (B") may be a polyorganosiloxane backbone, or an organic backbone. Alternatively, the polymer backbone of ingredient (B") may be a polyorganosiloxane backbone. The hydrolyzable substituents are exemplified by hydrogen atoms; halogen atoms; amido groups such as acetamido groups, benzamido groups, or methylacetamido groups; acyloxy groups such as acetoxy groups;

hydrocarbonoxy groups such as alkoxy groups or alkenyloxy groups; amino groups;

aminoxy groups; hydroxyl groups; mercapto groups; oximo groups; ketoximo groups; alkoxysilylhydrocarbylene groups; or a combination thereof. Alternatively, ingredient (B") may have an average of two or more hydrolyzable substituents per molecule. The hydrolyzable substituent in ingredient (B") may be located at terminal, pendant, or both terminal and pendant positions on the polymer backbone. Alternatively, the hydrolyzable substituent in ingredient (B") may be located at one or more terminal positions on the polymer backbone. Ingredient (B") may comprise a linear, branched, cyclic, or resinous structure. Alternatively, ingredient (B") may comprise a linear, branched or cyclic structure. Alternatively, ingredient (B") may comprise a linear or branched structure. Alternatively, ingredient (B") may comprise a linear structure. Alternatively, ingredient (B") may comprise a linear structure and a resinous structure. Ingredient (B") may comprise a homopolymer or a copolymer or a combination thereof.

[0089] Ingredient (B") may have the hydrolyzable substituents contained in groups of the formula (ii):

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 and a divalent siloxane group; each X independently represents a hydrolyzable substituent; 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.

[0090] 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:

or . Alternatively, an instance of D may be an oxygen atom while a different instance of D is a divalent hydrocarbon group.

[0091] Alternatively, each X may be a hydrolyzable substituent independently selected from the group consisting of an alkoxy group; an alkenyloxy group; an amido group, such as an acetamido, a methylacetamido group, or benzamido group; an acyloxy group such as acetoxy; an amino group; an aminoxy group; a hydroxyl group; a mercapto group; an oximo group; a ketoximo group; and a halogen atom. Alternatively, each X may be independently selected from the group consisting of an alkoxy group, an amido group, an acyloxy group, an amino group, a hydroxyl group, and an oximo group.

[0092] 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.

[0093] Alternatively, subscript b may be 0.

[0094] Ingredient (B") 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 %.

[0095] Ingredient (B") may have a polyorganosiloxane backbone with a linear structure, i.e., a polydiorganosiloxane backbone. When ingredient (B") has a polydiorganosiloxane backbone, ingredient (B") may comprise an alkoxy-endblocked polydiorganosiloxane, an alkoxysilylhydrocarbylene-endblocked polydiorganosiloxane, a hydroxyl-endblocked polydiorganosiloxane, or a combination thereof.

[0096] Ingredient (B") may comprise a polydiorganosiloxane of formula (I):

where each R¹ is independently a hydrolyzable substituent, each R² is independently a monovalent organic group, each R³ is 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.

[0097] Suitable hydrolyzable substituents for R¹ include, but are not limited to, the hydrolyzable substituents described above for group X. Alternatively, the hydrolyzable substituents for R¹ may be selected from a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, and a methylacetamido group.

[0098] Suitable organic groups for R² include, but are not limited to, monovalent organic groups such as hydrocarbon groups and halogenated hydrocarbon groups. Examples of monovalent hydrocarbon groups for R² include, 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 aralkyi such as

2-phenylethyl. Examples of monovalent halogenated hydrocarbon groups for R² include, 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 R² include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyi, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyi and cyano-functional groups such as cyanoethyl and cyanopropyl. Alternatively, each R² may be an alkyl group such as methyl. [0099] Ingredient (B") may comprise an α,ω-difunctional-polydiorganosiloxane when, in formula (I) above, each subscript d is 1 and each R³ is an oxygen atom. For example, ingredient (B") may have formula (II): R¹ R² ₂SiO-(R²2SiO)_e'-SiR²2R¹ > where R¹ and R² are 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.

[0100] Alternatively, ingredient (B") may comprise a hydroxyl-functional

polydiorganosiloxane of formula (II) described above, in which each R¹ may be a hydroxyl group, each R² may be an alkyl group such as methyl, and subscript e' may have a value such that the hydroxyl 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 hydroxyl-endblocked polydiorganosiloxanes are hydroxyl-endblocked polydimethylsiloxanes. Hydroxyl-endblocked polydiorganosiloxanes suitable for use as ingredient (B") may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic

polydiorganosiloxanes.

[0101] Alternatively, ingredient (B") may comprise an alkoxysilylhydrocarbylene- endblocked polydiorganosiloxane, for example, when in formula (I) above each R³ is divalent hydrocarbon group or a combination of a divalent hydrocarbon group and a divalent siloxane group. Each R³ may be an alkylene group such as ethylene, propylene, such as:

Alternatively, each R¹ and each R² may be alkyl, each R³ may be alkylene such as ethylene, and each subscript d may be 3.

[0102] Alkoxysilylhydrocarbylene-endblocked polydiorganosiloxanes may be prepared by reacting a vinyl-terminated, polydimethylsiloxane with

(alkoxysilylhydrocarbyl)tetramethyldisiloxane.

[0103] Alternatively, ingredient (B") may comprise a moisture-curable, silane-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 moisture curable silyl groups containing hydrolyzable substituents bonded to silicon atoms. The organic polymer can, for example, be selected from hydrocarbon polymers, polyethers, acrylate polymers, polyurethanes and polyureas.

[0104] Ingredient (B") may be elastomeric, i.e., have a glass transition temperature (Tg) less than 0 ^eC. When ingredient (B") is elastomeric, ingredient (B") may be distinguished, based on the Tg, from semi-crystalline and amorphous polyolefins (e.g., alpha-olefins), commonly referred to as thermoplastic polymers.

[0105] Ingredient (B") 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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 allylchloride in presence of Na followed by hydrosilylation).

[0110] 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.

[0111 ] Alternatively, ingredient (B") may comprise a polyether. One type of polyether is a polyoxyalkylene polymer comprising recurring oxyalkylene units of the formula (-CtH2t-0-) where subscript t is an integer with a value ranging from 2 to 4. Polyoxyalkylene polymers typically have terminal hydroxyl groups, and can readily be terminated with silyl groups having hydrolyzable substituents bonded to silicon atoms, for example by reaction of the terminal hydroxyl groups with an excess of an alkyltrialkoxysilane to introduce terminal alkyldialkoxysilyl groups. Alternatively, polymerization may occur via a hydrosilylation type process. Polyoxyalkylenes comprising mostly oxypropylene units may have properties suitable for many sealant uses. Polyoxyalkylene polymers, particularly polyoxypropylenes, having terminal alkyldialkoxysilyl or trialkoxysilyl groups may react with each other in the presence of ingredient (A) and moisture. The composition containing these base polymers may optionally further comprise a crosslinker.

[0112] The organic polymer having hydrolysable silyl groups 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.

[0113] 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.

[0114] Alternatively, the base polymer 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 -(R⁴fSiO(4_f)/2)-_> ⁱⁿ which each R⁴ is 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.

[0115] Alternatively, each R⁴ may 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 R⁴ include 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. [0116] The organic blocks in the polymer backbone may comprise, for example, polystyrene and/or substituted polystyrenes such as poly(a-methylstyrene),

poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl-a- 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.

[0117] Alternatively, the organic polymer blocks in a siloxane organic block copolymer for ingredient (B") may be polyoxyalkylene based blocks comprising recurring oxyalkylene units, illustrated by the average formula (-CgH2g-0-)h where 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-

0-(-R⁶-0-)j-Pn-CR⁷2-Pn-0-(-R⁶-0-)j-R⁵]-, in which Pn is a 1 ,4-phenylene group, each R⁵ is the same or different and is a divalent hydrocarbon group having 2 to 8 carbon atoms, each R⁶ is the same or different and is an ethylene group or propylene group, each R⁷ is 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.

[0118] Alternatively, ingredient (B") may comprise a silicone resin, in addition to, or instead of, one of the polymers described above for ingredient (B"). Suitable silicone resins are exemplified by an MQ resin, which comprises siloxane units of the formulae:

R²⁹w^R30(3-w)SiO-|/2 and S1O4/2, where R²⁹ and R³⁰ are monovalent organic groups, such as monovalent hydrocarbon groups exemplified by 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; halogenated hydrocarbon group exemplified by 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; and other monovalent organic groups such as 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; and each instance of subscript w is 0, 1 , or 2. Alternatively, each R²⁹ and each R³⁰ may be an alkyl group. The MQ resin may have a molar ratio of M units to Q units (M:Q) ranging from 0.5:1 to 1 .5:1 . These mole ratios are conveniently measured by Si²⁹ NMR spectroscopy. This technique is capable of quantitatively determining the concentration of R²⁹3 S1O1 /2 ("M") and S1O4/2 ("Q") units derived from the silicone resin and from the neopentamer,

Si(OSiMe3)4, present in the initial silicone resin, in addition to the total hydroxyl content of the silicone resin.

[0119] The MQ silicone resin is soluble in solvents such as liquid hydrocarbons exemplified by benzene, toluene, xylene, and heptane, or in liquid organosilicon compounds such as a low viscosity cyclic and linear polydiorganosiloxanes.

[0120] The MQ silicone resin may contain 2.0 % or less, alternatively 0.7 % or less, alternatively 0.3 % or less, of terminal units represented by the formula X"Si03/2, where X" represents hydroxyl or a hydrolyzable group such as alkoxy such as methoxy and ethoxy; alkenyloxy such as isopropenyloxy; ketoximo such as methyethylketoximo; carboxy such as acetoxy; amidoxy such as acetamidoxy; and aminoxy such as N,N-dimethylaminoxy. The concentration of silanol groups present in the silicone resin can be determined using FTIR.

[0121 ] The Mn desired to achieve the desired flow characteristics of the MQ silicone resin can depend at least in part on the Mn of the silicone resin and the type of organic group, represented by R²⁹, that are present in this ingredient. The Mn of the MQ silicone resin is typically greater than 3,000, more typically from 4500 to 7500.

[0122] The MQ silicone resin can be prepared by any suitable method. Silicone resins of this type have reportedly been prepared by cohydrolysis of the corresponding silanes or by silica hydrosol capping methods known in the art. Briefly stated, the method involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a combination thereof, and recovering a product comprising M and Q units (MQ resin). The resulting MQ resins may contain from 2 to 5 percent by weight of silicon-bonded hydroxyl groups. [0123] The intermediates used to prepare the MQ silicone resin may be triorganosilanes of the formula R²⁹3SiX, where X represents a hydrolyzable group, as described above for ingredient (B"), and either a silane with four hydrolyzable groups such as halogen, alkoxy or hydroxyl, or an alkali metal silicate such as sodium silicate.

[0124] In some compositions, it may be desirable that the amount of silicon-bonded hydroxyl groups (i.e., HOR²⁹SiO-|/2 or HOS1O3/2 groups) in the silicone resin be below 0.7

% by weight of the total weight of the silicone resin, alternatively below 0.3 %. Silicon- bonded hydroxyl groups formed during preparation of the silicone resin are converted to trihydrocarbylsiloxy groups or a hydrolyzable group by reacting the silicone resin with a silane, disiloxane or disilazane containing the appropriate terminal group. Silanes containing hydrolyzable groups may be added in excess of the stoichiometric quantity of the silicon-bonded hydroxyl groups of the silicone resin.

[0125] Various suitable MQ resins are commercially available from sources such as Dow Corning Corporation of Midland, Ml, U.S.A., Momentive Performance Materials of Albany, N.Y., U.S.A., and Bluestar Silicones USA Corp. of East Brunswick, N.J., U.S.A. For example, DOW CORNING® MQ-1600 Solid Resin, DOW CORNING® MQ-1601 Solid Resin, and DOW CORNING® 1250 Surfactant, DOW CORNING® 7466 Resin, and DOW CORNING® 7366 Resin, all of which are commercially available from Dow Corning Corporation, are suitable for use in the methods described herein. Alternatively, a resin containing M, T, and Q units may be used, such as DOW CORNING® MQ-1640 Flake Resin, which is also commercially available from Dow Corning Corporation. Such resins may be supplied in organic solvent.

[0126] Alternatively, the silicone resin may comprise a silsesquioxane resin, i.e., a resin containing T units of formula (R31 S1O3/2). Each R31 may be independently selected from a hydrogen atom and a monovalent organic group, such as a monovalent hydrocarbon group exemplified by alkyl such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyi such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and benzyl; and aralkyl such as 2-phenylethyl; halogenated hydrocarbon group exemplified by chlorinated alkyl groups such as chloromethyl and chloropropyl groups; a fluorinated alkyl group 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 cycloalkyi groups such as 2,2- dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyi groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5- methylcycloheptyl; and another monovalent organic group such as a hydrocarbon group substituted with oxygen atoms such as glycidoxyalkyi, and a hydrocarbon group substituted with a nitrogen atom such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl. Silsesquioxane resins suitable for use herein are known in the art and are commercially available. For example, a methylmethoxysiloxane methylsilsesquioxane resin having a DP of 15 and a weight average molecular weight (Mw) of 1200 g/mol is commercially available as DOW CORNING® US-CF 2403 Resin from Dow Corning Corporation of Midland, Michigan, U.S.A. Alternatively, the silsesquioxane resin may have phenylsilsesquioxane units, methylsilsesquioxane units, or a combination thereof. Such resins are known in the art and are commercially available as DOW CORNING® 200 Flake resins, also available from Dow Corning Corporation. Alternatively, the silicone resin may comprise D units of formulae (R³¹2Si02/2) and/or (R³¹ R³²Si02/2) and T units of formulae (R³¹ Si03/2) and/or (R³²Si03/2), i.e., a DT resin, where R³¹ is as described above and R³² is a hydrolyzable group such as group X described above. DT resins are known in the art and are commercially available, for example, methoxy functional DT resins include DOW CORNING® 3074 and DOW CORNING® 3037 resins; and silanol functional resins include DOW CORNING® 800 Series resins, which are also

commercially available from Dow Corning Corporation. Other suitable resins include DT resins containing methyl and phenyl groups.

[0127] The amount of silicone resin added to the composition can vary depending on the end use of the composition. For example, when the reaction product of the composition is a gel, little or no silicone resin may be added. However, the amount of silicone resin in the composition may range from 0 % to 90 %, alternatively 0.1 % to 50 %, based on the weight of all ingredients in the composition.

[0128] The amount of ingredient (B") can depend on various factors including the end use of the reaction product of the composition, the type of base polymer selected for ingredient (B"), and the type(s) and amount(s) of any additional ingredient(s) present, if any. However, the amount of ingredient (B") may range from 0.01 % to 99 %, alternatively 10 % to 95 %, alternatively 10 % to 65 % of the composition.

[0129] Ingredient (B") can be one single base polymer or a combination comprising two or more base polymers that differ in at least one of the following properties: average molecular weight, hydrolyzable substituents, siloxane units, sequence, and viscosity. When one base polymer for ingredient (B") contains an average of only one to two hydrolyzable substituents per molecule, then the composition further may further comprise an additional base polymer having an average of more than two hydrolyzable substituents per molecule, or ingredient (C") a crosslinker, or both. [0130] The composition may optionally further comprise one or more additional ingredients, i.e., in addition to ingredients (A) and (X) and distinct from ingredients (A) and (X). The additional ingredient, if present, may be selected based on factors such as the method of use of the composition and/or the end use of the cured product of the composition.

[0131 ] The additional ingredient in component (X), particularly when component (X) is (X3), may be selected from (C") a crosslinker; (D") a drying agent; (E") an extender, a plasticizer, or a combination thereof; (F") a filler such as (f1 ") a reinforcing filler, (f2") an extending filler, (f3") a conductive filler (e.g., electrically conductive, thermally conductive, or both"); (G") a filler treating agent; (H") a biocide, such as (hi ") a fungicide, (h2") an herbicide, (h3") a pesticide, or (h4") an antimicrobial; (J") a flame retardant; (K") a surface modifier such as (k1 ") an adhesion promoter or (k2") a release agent; (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; (T") a tackifying agent; (U") a corrosion inhibitor; and a combination thereof. The additional ingredients are distinct from one another. In some embodiments at least one, alternatively each of additional ingredients (C") to (U"), and the combination thereof, does not completely prevent the condensation reaction of ingredient (B").

[0132] Ingredient (C") is a crosslinker that may be added to the composition, for example, when ingredient (B") contains an average of only one or two hydrolyzable substituents per molecule and/or to increase crosslink density of the reaction product prepared by condensation reaction of the composition. Generally, ingredient (C") is selected with functionality that can vary depending on the degree of crosslinking desired in the reaction product of the composition and such that the reaction product does not exhibit too much weight loss from by-products of the condensation reaction. Generally, the selection of ingredient (C") is made such that the composition remains sufficiently readable to be useful during storage for several months in a moisture impermeable package. Generally, ingredient (C") is selected such that the hydrolyzable substituents on ingredient (C") are reactive with ingredient (B"). For example, when X in ingredient (B") is a hydroxyl group, then the hydrolyzable substituent for ingredient (C") may be a hydrogen atom, a halogen atom ; a hydroxyl group, an amido group, an acyloxy group, a hydrocarbonoxy group, an amino group, an aminoxy group, a mercapto group, an oximo group, a ketoximo group, or an alkoxysilylhydrocarbylene group, or a combination thereof. The exact amount of ingredient (C") can vary depending on factors including the type of base polymer and crosslinker selected, the reactivity of the hydrolyzable substituents on the base polymer and crosslinker, and the desired crosslink density of the reaction product. However, the amount of crosslinker may range from 0.5 to 100 parts based on 100 parts by weight of ingredient (B").

[0133] Ingredient (C") may comprise a silane crosslinker having hydrolyzable groups or partial or full hydrolysis products thereof. Ingredient (C") has an average, per molecule, of greater than two substituents reactive with the hydrolyzable substituents on ingredient (B"). Examples of suitable silane crosslinkers for ingredient (C") may have the general formula

(III) R⁸kSi(R⁹)(4-k), where each R⁸ is independently a monovalent hydrocarbon group such as an alkyl group; each R⁹ is a hydrolyzable substituent, which may be the same as

X described above for ingredient (B"). Alternatively, each R⁹ may be, for example, a hydrogen atom, a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group; and each instance of subscript k may be 0, 1 , 2, or 3. For ingredient (C"), subscript k has an average value greater than 2. Alternatively, subscript k may have a value ranging from 3 to 4.

Alternatively, each R⁹ may be independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime. Alternatively, ingredient (C") may be selected from an acyloxysilane, an alkoxysilane, a ketoximosilane, and an oximosilane.

[0134] Ingredient (C") may comprise an alkoxysilane exemplified by a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or full hydrolysis products thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane,

methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively

methyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. The amount of the alkoxysilane that is used in the curable silicone composition may range from 0.5 to 15, parts by weight per 100 parts by weight of ingredient (B").

[0135] Ingredient (C") may comprise an acyloxysilane, such as an acetoxysilane.

Acetoxysilanes include a tetraacetoxysilane, an organotriacetoxysilane, a

diorganodiacetoxysilane, or a combination thereof. The acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3-trifluoropropyl. Exemplary acetoxysilanes include, but are not limited to, tetraacetoxysilane,

methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltnacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyl diacetoxysilane, tetraacetoxysilane, and combinations thereof. Alternatively, ingredient (C") may comprise organotriacetoxysilanes, for example mixtures comprising methyltriacetoxysilane and ethyltriacetoxysilane. The amount of the acetoxysilane that is used in the curable silicone composition may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (ET); alternatively 3 to 10 parts by weight of acetoxysilane per 100 parts by weight of ingredient (B").

[0136] Examples of silanes suitable for ingredient (C") containing both alkoxy and acetoxy groups that may be used in the composition include

methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane,

vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, metylacetoxydiethoxysilane, and combinations thereof.

[0137] Aminofunctional alkoxysilanes suitable for ingredient (C") are exemplified by H₂N(CH2)2Si(OCH₃)3, H₂N(CH2)2Si(OCH2CH₃)3, H₂N(CH2)3Si(OCH3)₃,

H2N(CH2)3Si(OCH₂CH3)3, CH₃NH(CH2)3Si(OCH₃)₃, CH₃NH(CH2)3Si(OCH2CH₃)₃, CH3NH(CH2)5Si(OCH3)3, CH₃NH(CH2)5Si(OCH2CH3)3,

H2N(CH2)2NH(CH2)3Si(OCH₃)₃, H2N(CH2)2NH(CH2)3Si(OCH2CH₃)₃,

CH₃NH(CH2)2NH(CH2)3Si(OCH₃)₃, CH₃NH(CH2)2NH(CH2)3Si(OCH2CH₃)₃,

C₄H₉NH(CH2)2NH(CH2)3Si(OCH3)3, C₄H₉NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH₃(OCH₃)2, H2N(CH2)2SiCH₃(OCH2CH₃)2, H2N(CH2)3SiCH₃(OCH₃)2, H2N(CH2)3SiCH₃(OCH2CH₃)2, CH₃NH(CH2)3SiCH₃(OCH₃)2,

CH₃NH(CH2)3SiCH3(OCH2CH₃)2, CH₃NH(CH2)5SiCH3(OCH₃)2,

CH₃NH(CH2)5SiCH3(OCH2CH₃)2, H₂N(CH2)2NH(CH2)3SiCH3(OCH₃)2,

H₂N(CH2)2NH(CH2)3SiCH3(OCH2CH₃)2, CH₃NH(CH2)2NH(CH2)3SiCH3(OCH₃)2, CH₃NH(CH2)2NH(CH2)3SiCH3(OCH2CH₃)2, C₄H₉NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C₄H₉NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and a combination thereof.

[0138] Suitable oximosilanes for ingredient (C") include alkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanes such as methoxytrioximosilane, ethoxytrioximosilane, and propoxytrioximosilane; or alkenyltrioximosilanes such as propenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanes such as vinyloximosilane;

alkenylalkyldioximosilanes such as vinyl methyl dioximosilane, vinyl ethyldioximosilane, vinyl methyldioximosilane, or vinylethyldioximosilane; or combinations thereof. [0139] Suitable ketoximosilanes for ingredient (C") include methyl tris(dimethylketoximo)silane, methyl tris(methylethylketoximo)silane, methyl

tris(methylpropylketoximo)silane, methyl tris(methylisobutylketoximo)silane, ethyl tris(dimethylketoximo)silane, ethyl tris(methylethylketoximo)silane, ethyl

tris(methylpropylketoximo)silane, ethyl tris(methylisobutylketoximo)silane, vinyl tris(dimethylketoximo)silane, vinyl tris(methylethylketoximo)silane, vinyl

tris(methylpropylketoximo)silane, vinyl tris(methylisobutylketoximo)silane,

tetrakis(dimethylketoximo)silane, tetrakis(methylethylketoximo)silane,

tetrakis(methylpropylketoximo)silane, tetrakis(methylisobutylketoximo)silane,

methylbis(dimethylketoximo)silane, methylbis(cyclohexylketoximo)silane,

triethoxy(ethylmethylketoxime)silane, diethoxydi(ethylmethylketoxime)silane,

ethoxytri(ethylmethylketoxime)silane, methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.

[0140] Alternatively, ingredient (C") may be polymeric. For example, ingredient (C") may comprise a disilane such as bis(triethoxysilyl)hexane), 1 ,4- bis[trimethoxysilyl(ethyl)]benzene, and bis[3-(triethoxysilyl)propyl] tetrasulfide

[0141] Ingredient (C") can be one single crosslinker or a combination comprising two or more crosslinkers that differ in at least one of the following properties: hydrolyzable substituents and other organic groups bonded to silicon, and when a polymeric crosslinker is used, siloxane units, structure, molecular weight, and sequence.

[0142] Ingredient (D") is a drying agent. The drying agent binds water from various sources. For example, the drying agent may bind by-products of the condensation reaction, such as water and alcohols.

[0143] Examples of suitable adsorbents for ingredient (D") may be inorganic particulates. The adsorbent may have a particle size of 10 micrometers or less, alternatively 5 micrometers or less. The adsorbent may have average pore size sufficient to adsorb water and alcohols, for example 10 A (Angstroms) or less, alternatively 5 A or less, and alternatively 3 A or less. Examples of adsorbents include zeolites such as chabasite, mordenite, and analcite; molecular sieves such as alkali metal alumino silicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof.

[0144] Examples of commercially available drying agents include dry molecular sieves, such as 3 A (Angstrom) molecular sieves, which are commercially available from Grace Davidson under the trademark SYLOSIV® and from Zeochem of Louisville, Kentucky, U.S.A. under the trade name PURMOL, and 4 A molecular sieves such as Doucil zeolite 4A available from Ineos Silicas of Warrington, England. Other useful molecular sieves include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A, all of which are commercially available from UOP of Illinois, U.S.A.; SILIPORITE NK 30AP and 65xP from Atofina of Philadelphia, Pennsylvania, U.S.A.; and molecular sieves available from W.R. Grace of Maryland, U.S.A.

[0145] Alternatively, the drying agent may bind the water and/or other by-products by chemical means. An amount of a silane crosslinker added to the composition (in addition to ingredient (C")) may function as a chemical drying agent. Without wishing to be bound by theory, it is thought that the chemical drying agent may be added to the dry part of a multiple part composition to keep the composition free from water after the parts of the composition are mixed together. For example, alkoxysilanes suitable as drying agents include vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof.

[0146] The amount of ingredient (D") depends on the specific drying agent selected. However, when ingredient (D") is a chemical drying agent, the amount may range from 0 parts to 5 parts, alternatively 0.1 parts to 0.5 parts. Ingredient (D") may be one chemical drying agent. Alternatively, ingredient (D") may comprise two or more different chemical drying agents.

[0147] Ingredient (E") is an extender and/or a plasticizer. An extender comprising a nonfunctional polyorganosiloxane may be used in the composition. For example, the nonfunctional polyorganosiloxane may comprise difunctional units of the formula R²²2Si02/2 and terminal units of the formula R²3gSiD'-, where each R²² and each R²3 are independently a monovalent organic group such as a monovalent hydrocarbon group exemplified by alkyl such as methyl, ethyl, propyl, and butyl; alkenyl such as vinyl, allyl, and hexenyl; aryl such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as phenylethyl; and D' is an oxygen atom or a divalent group linking the silicon atom of the terminal unit with another silicon atom (such as group D described above for ingredient (B")), alternatively D' is an oxygen atom. Non-functional polyorganosiloxanes are known in the art and are commercially available. Suitable non-functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxanes. Such polydimethylsiloxanes include DOW CORNING® 200 Fluids, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 50 cSt to 100,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 to 60,000 cSt.

[0148] An organic plasticizer may be used in addition to, or instead of, the non-functional polyorganosiloxane extender described above. Organic plasticizers are known in the art and are commercially available. The organic plasticizer may comprise a phthalate, a carboxylate, a carboxylic acid ester, an adipate or a combination thereof. The organic plasticizer may be selected from the group consisting of: bis(2-ethylhexyl) terephthalate; bis(2-ethylhexyl)-1 ,4-benzenedicarboxylate; 2-ethylhexyl methyl-1 ,4-benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear; bis(2-propylheptyl) phthalate; diisononyl adipate; and a combination thereof.

[0149] Th ticizer may have an average, per molecule, of at least one group

of formula

where R^{1 8} represents a hydrogen atom or a monovalent organic group. Alternatively, R^{1 8} may represent a branched or linear monovalent hydrocarbon group. The monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms. Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.

[0150] Alternatively, the organic plasticizer may have an average, per molecule, of at least two groups of the formula above bonded to carbon atoms in a cyclic hydrocarbon. The organic plasticizer may have general formula:

In this formula, group Z represents a carbocyclic group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms. Subscript s may have a value ranging from 1 to 12.

Group Z may be saturated or aromatic. Each R²⁰ is independently a hydrogen atom or a branched or linear monovalent organic group. The monovalent organic group for R^{1 9} may be an alkyl group such as methyl, ethyl, or butyl. Alternatively, the monovalent organic group for R²⁰ may be an ester functional group. Each R^{1 9} is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.

[0151] Suitable organic plasticizers are known in the art and are commercially available. The plasticizer may comprise a phthalate, such as: a dialkyl phthalate such as dibutyl phthalate (Eastman™ DBP Plasticizer), diheptyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate (BASF Palatinol® DPHP) , di(2- ethylhexyl) phthalate (Eastman™ DOP Plasticizer), dimethyl phthalate (Eastman™ DMP Plasticizer); diethyl phthalate (Eastman™ DMP Plasticizer); butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate (Eastman™ 425 Plasticizer); a dicarboxylate such as Benzyl, C7-C9 linear and branched alkyl esters, 1 , 2, benzene dicarboxylic acid (Ferro SANTICIZER® 261 A), 1 ,2,4-benzenetricarboxylic acid (BASF Palatinol® TOTM-I), bis(2- ethylhexyl)-1 ,4-benzenedicarboxylate (Eastman™ 168 Plasticizer); 2-ethylhexyl methyl- 1 ,4-benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear (BASF Hexamoll ^*DINCH); diisononyl adipate; trimellitates such as trioctyl trimellitate (Eastman™ TOTM Plasticizer); triethylene glycol bis(2-ethylhexanoate) (Eastman™ TEG-EH Plasticizer); triacetin (Eastman™ Triacetin); nonaromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexyl) adipate (Eastman™ DOA Plasticizer and Eastman™ DOA Plasticizer, Kosher), di-2-ethylhexyladipate (BASF Plastomoll® DOA), dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl recinolate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris(2-ethylhexyl) ester; a fatty acid ester; and a combination thereof. Examples of other suitable plasticizers and their commercial sources include BASF Palamoll® 652 and Eastman 168 Xtreme™ Plasticizer.

[0152] Alternatively, a polymer plasticizer can be used. Examples of the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethers including polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha- methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, and polychloroprene.

[0153] When the organic plasticizer is present, the amount of the organic plasticizer may range from 5 to 150 parts by weight based on the combined weights of all ingredients in the composition.

[0154] The polyorganosiloxane extenders and organic plasticizers described above for ingredient (E") may be used either each alone or in combinations of two or more thereof. A low molecular weight organic plasticizer and a higher molecular weight polymer plasticizer may be used in combination. The exact amount of ingredient (E") used in the composition can depend on various factors including the desired end use of the composition and the cured product thereof. However, the amount of ingredient (E") may range from 0.1 % to 10 % based on the combined weights of all ingredients in the composition.

[0155] Ingredient (F") is a filler. The filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof. For example, the composition may optionally further comprise ingredient (f1 "), a reinforcing filler, which when present may be added in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, based on the weight of the composition. The exact amount of ingredient (f1 ") depends on various factors including the form of the reaction product of the composition and whether any other fillers are added. Examples of suitable reinforcing fillers include reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; e.g., fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.

[0156] The composition may optionally further comprise ingredient (f2") an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition. Examples of extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate such as precipitated calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof. Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV. Suitable precipitated calcium carbonates included Winnofil® SPM from Solvay and Ultrapflex® and Ultrapflex® 100 from SMI.

[0157] The composition may optionally further comprise ingredient (f3") a conductive filler. Conductive fillers may be thermally conductive, electrically conductive, or both. Conductive fillers are known in the art and are exemplified by metal particulates (such as aluminum, copper, gold, nickel, silver, and combinations thereof); such metals coated on nonconductive substrates; metal oxides (such as aluminum oxide, beryllium oxide, magnesium oxide, zinc oxide, and combinations thereof), meltable fillers (e.g., solder), aluminum nitride, aluminum trihydrate, barium titanate, boron nitride, carbon fibers, diamond, graphite, magnesium hydroxide, onyx, silicon carbide, tungsten carbide, and a combination thereof.

[0158] Alternatively, other fillers may be added to the composition, the type and amount depending on factors including the end use of the cured product of the composition.

Examples of such other fillers include magnetic particles such as ferrite; and dielectric particles such as fused glass microspheres, titania, and calcium carbonate. [0159] The composition may optionally further comprise ingredient (G") a treating agent. The amount of ingredient (G") can vary depending on factors such as the type of treating agent selected and the type and amount of particulates to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ. However, ingredient (G") may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of the composition. Particulates, such as the filler, the physical drying agent, certain flame retardants, certain pigments, and/or certain water release agents, when present, may optionally be surface treated with ingredient (G"). Particulates may be treated with ingredient (G") before being added to the composition, or in situ. Ingredient (G") may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid. Examples of fatty acids include stearates such as calcium stearate.

[0160] Some representative organosilicon filler treating agents that can be used as ingredient (G") include compositions normally used to treat silica fillers such as

organochlorosilanes, organosiloxanes, organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanes such as ΟβΗΐ

C8H-_| 7Si(OC2H5)3,

C_{1 0}H2i Si(OCH₃)3, C_{1 2}H25Si(OCH₃)3, C_{1 4}H29Si(OC₂H5)3, and

C6H5CH2CH2Si(OCH3)3. Other treating agents that can be used include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.

[0161] Alternatively, ingredient (G") may comprise an alkoxysilane having the formula: R^{1 3} ₀Si(OR^{1 4})(4-p), where subscript p may have a value ranging from 1 to 3, alternatively subscript p is 3. Each R¹³ is independently a monovalent organic group, such as a monovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to 30 carbon atoms, alternatively 8 to 18 carbon atoms. R^{1 3} is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; and aromatic groups such as benzyl and phenylethyl. R^{1 3} may be saturated or unsaturated, and branched or unbranched. Alternatively, R^{1 3} may be saturated and unbranched.

[0162] Each R¹⁴ is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Ingredient (G") is exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane,

tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof. [0163] Alkoxy-functional oligosiloxanes may also be used as treating agents. For example, suitable alkoxy-functional oligosiloxanes include those of the formula

(R^{1 5}0)qSi(OSiR^{1 6}2R^{1 7})(4-q)- In this formula, subscript q is 1 , 2 or 3, alternatively subscript q is 3. Each R^{1 5} may be an alkyl group. Each R^{1 6} may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms. Each R^{1 7} may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.

[0164] Certain particulates, such as metal fillers may be treated with alkylthiols such as octadecyl mercaptan; fatty acids such as oleic acid and stearic acid; and a combination thereof.

[0165] Other treating agents include alkenyl functional polyorganosiloxanes. Suitable alkenyl functional polyorganosiloxanes include, but are not limited to:

CH3 CH3 CH3, where subscript r has a value up to 1 ,500.

[0166] Alternative, a polyorganosiloxane capable of hydrogen bonding is useful as a treating agent. This strategy to treating surface of a filler takes advantage of multiple hydrogen bonds, either clustered or dispersed or both, as the means to tether the compatibilization moiety to the filler surface. The polyorganosiloxane capable of hydrogen bonding has an average, per molecule, of at least one silicon-bonded group capable of hydrogen bonding. The group may be selected from: an organic group having multiple hydroxyl functionalities or an organic group having at least one amino functional group. The polyorganosiloxane capable of hydrogen bonding means that hydrogen bonding is the primary mode of attachment for the polyorganosiloxane to a filler. The polyorganosiloxane may be incapable of forming covalent bonds with the filler. The polyorganosiloxane may be free of condensable silyl groups e.g., silicon bonded alkoxy groups, silazanes, and silanols. The polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide-siloxane polymer, an amino-functional

polyorganosiloxane, and a combination thereof. Alternatively, the polyorganosiloxane capable of hydrogen bonding may be a saccharide-siloxane polymer.

[0167] Ingredient (H") is a biocide. The amount of ingredient (H") can vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of ingredient (H") may range from greater than 0 % to 5 % based on the weight of all ingredients in the composition. Ingredient (H") is exemplified by (hi ") a fungicide, (h2") an herbicide, (h3") a pesticide, (h4") an antimicrobial, or a combination thereof. [0168] Ingredient (hi ") is a fungicide, for example, these include N-substituted benzimidazole carbamate, benzimidazolyl carbamate such as methyl 2- benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl 2- benzimidazolylcarbamate, methyl N-{2-[1 -(N,N- dimethylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-5- methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N-methylcarbamoyl)benzimidazolyl] Jcarbamate, methyl N-{2-[1 -(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1 - (N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[2-(N- methylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, ethyl N-{2-[1 -(N-methylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, isopropyl N-{2-[1 -(N,N- dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropyl N-{2-[1 -(N- methylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{1 -(N,N- dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[N- methylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- butylcarbamoyloxy)benzoimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- butylcarbamoyloxy)benzoimidazolyl]}carbamate, methyl N-{2 -[1 -(N,N-dimethylcarbamoyl)- 6-chlorobenzimidazolyl]}carbamate, and methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- nitrobenzimidazolyl]}carbamate; 10, 10'-oxybisphenoxarsine (trade name: Vinyzene, OBPA), di-iodomethyl-para-tolylsulfone, benzothiophene-2-cyclohexylcarboxamide-S,S- dioxide, N-(fluordichloridemethylthio)phthalimide (trade names: Fluor-Folper, Preventol A3); methyl-benzimideazol-2-ylcarbamate (trade names: Carbendazim, Preventol BCM), Zinc-bis(2-pyridylthio-1 -oxide) (zinc pyrithion) 2-(4-thiazolyl)-benzimidazol, N-phenyl- iodpropargylcarbamate, N-octyl-4-isothiazolin-3-on, 4,5-dichloride-2-n-octyl-4-isothiazolin- 3-on, N-butyl-1 ,2-benzisothiazolin-3-on and/or Triazolyl-compounds, such as tebuconazol in combination with zeolites containing silver. [0169] Ingredient (h2") is an herbicide, for example, suitable herbicides include amide herbicides such as allidochlor N,N-diallyl-2-chloroacetamide; CDEA 2-chloro-N,/V- diethylacetamide; etnipromid (/¾)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-N- ethylpropionamide; anilide herbicides such as cisanilide c/s-2,5-dimethylpyrrolidine-1 - carboxanilide; flufenacet 4'-fluoro-N-isopropyl-2-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2- yloxy]acetanilide; naproanilide (/¾>)-a-2-naphthoxypropionanilide; arylalanine herbicides such as benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine; flamprop-M N-benzoyl- N-(3-chloro-4-fluorophenyl)-D-alanine; chloroacetanilide herbicides such as butachlor N- butoxymethyl-2-chloro-2',6'-diethylacetanilide; metazachlor 2-chloro-N-(pyrazol-1 - ylmethyl)acet-2',6'-xylidide; prynachlor (flS)-2-chloro-N-(1 -methylprop-2-ynyl)acetanilide; sulphonanilide herbicides such as cloransulam 3-chloro-2-(5-ethoxy-7- fluoro[1 ,2,4]triazolo[1 ,5-c]pyrimidin-2-ylsulphonamido)benzoic acid; metosulam 2',6'- dichloro-5,7-dimethoxy-3'-methyl[1 ,2,4]triazolo[1 ,5-a]pyrimidine-2-sulphonanilide; antibiotic herbicides such as bilanafos 4-[hydroxy(methyl)phosphinoyl]-L-homoalanyl-L-alanyl-L- alanine; benzoic acid herbicides such as chloramben 3-amino-2,5-dichlorobenzoic acid; 2,3,6-TBA 2,3,6-trichlorobenzoic acid; pyrimidinyloxybenzoic acid herbicides such as bispyribac 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac 2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid; phthalic acid herbicides such as chlorthal tetrachloroterephthalic acid; picolinic acid herbicides such as aminopyralid 4-amino-3,6-dichloropyridine-2-carboxylic acid;

quinolinecarboxylic acid herbicides such as quinclorac 3,7-dichloroquinoline-8-carboxylic acid; arsenical herbicides such as CMA calcium bis(hydrogen methylarsonate); MAMA ammonium hydrogen methylarsonate; sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1 ,3-dione;

benzofuranyl alkylsulphonate herbicides such as benfuresate 2,3-dihydro-3,3- dimethylbenzofuran-5-yl ethanesulphonate; carbamate herbicides such as carboxazole methyl 5-feri-butyl-1 ,2-oxazol-3-ylcarbamate; fenasulam methyl 4-[2-(4-chloro-o- tolyloxy)acetamido]phenylsulphonylcarbamate; carbanilate herbicides such as BCPC (RS)- sec-butyl 3-chlorocarbanilate; desmedipham ethyl 3-phenylcarbamoyloxyphenylcarbamate; swep methyl 3,4-dichlorocarbanilate; cyclohexene oxime herbicides such as butroxydim ( S)-(£Z)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1 -ethoxyiminopropyl)-3-hydroxycyclohex-2- en-1 -one; tepraloxydim (/¾>)-( EZ)-2-{1 -[(2£)-3-chloroallyloxyimino]propyl}-3-hydroxy-5- perhydropyran-4-ylcyclohex-2-en-1 -one; cyclopropylisoxazole herbicides such as isoxachlortole 4-chloro-2-mesylphenyl 5-cyclopropyl-1 ,2-oxazol-4-yl ketone; dicarboximide herbicides such as flumezin 2-methyl-4-(a,a,a-trifluoro-m-tolyl)-1 ,2,4-oxadiazinane-3,5- dione; dinitroaniline herbicides such as ethalfluralin N-ethyl-a,a,a-trifluoro-/V-(2-methylallyl)- 2,6-dinitro-p-toluidine; prodiamine 5-dipropylamino-a,a,a-trifluoro-4,6-dinitro-o-toluidine; dinitrophenol herbicides such as dinoprop 4,6-dinitro-o-cymen-3-ol; etinofen oethoxy-4,6- dinitro-o-cresol; diphenyl ether herbicides such as ethoxyfen 0-[2-chloro-5-(2-chloro-a,a,a- trifluoro-p-tolyloxy)benzoyl]-L-lactic acid; nitrophenyl ether herbicides such as aclonifen 2- chloro-6-nitro-3-phenoxyaniline; nitrofen 2,4-dichlorophenyl 4-nitrophenyl ether;

dithiocarbamate herbicides such as dazomet 3,5-dimethyl-1 ,3,5-thiadiazinane-2-thione; halogenated aliphatic herbicides such as dalapon 2,2-dichloropropionic acid; chloroacetic acid; imidazolinone herbicides such as imazapyr (flS)-2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)nicotinic acid; inorganic herbicides such as disodium tetraborate decahydrate; sodium azide; nitrile herbicides such as chloroxynil 3,5-dichloro-4- hydroxybenzonitrile; ioxynil 4-hydroxy-3,5-di-iodobenzonitrile; organophosphorus herbicides such as anilofos S-4-chloro-N-isopropylcarbaniloylmethyl 0,0-dimethyl phosphorodithioate; glufosinate 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine; phenoxy herbicides such as clomeprop (ftS)-2-(2,4-dichloro-m-tolyloxy)propionanilide; fenteracol 2- (2,4,5-trichlorophenoxy)ethanol; phenoxyacetic herbicides such as MCPA (4-chloro-2- methylphenoxy)acetic acid; phenoxybutyric herbicides such as MCPB 4-(4-chloro-o- tolyloxy)butyric acid; phenoxypropionic herbicides such as fenoprop (ftS)-2-(2,4,5- trichlorophenoxy)propionic acid; aryloxyphenoxypropionic herbicides such as isoxapyrifop ( S)-2-[2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl]isoxazolidine; phenylenediamine herbicides such as dinitramine Λ/¹ ,N¹ -diethyl-2,6-dinitro-4-trifluoromethyl-m- phenylenediamine, pyrazolyloxyacetophenone herbicides such as pyrazoxyfen 2-[4-(2,4- dichlorobenzoyl)-1 ,3-dimethylpyrazol-5-yloxy]acetophenone; pyrazolylphenyl herbicides such as pyraflufen 2-chloro-5-(4-chloro-5-difluoromethoxy-1 -methylpyrazol-3-yl)-4- fluorophenoxyacetic acid; pyridazine herbicides such as pyridafol 6-chloro-3- phenylpyridazin-4-ol; pyridazinone herbicides such as chloridazon 5-amino-4-chloro-2- phenylpyridazin-3(2/-/)-one; oxapyrazon 5-bromo-1 ,6-dihydro-6-oxo-1 -phenylpyridazin-4- yloxamic acid; pyridine herbicides such as fluroxypyr 4-amino-3,5-dichloro-6-fluoro-2- pyridyloxyacetic acid; thiazopyr methyl 2-difluoromethyl-5-(4,5-dihydro-1 ,3-thiazol-2-yl)-4- isobutyl-6-trifluoromethylnicotinate; pyrimidinediamine herbicides such as iprymidam 6- chloro-^-isopropylpyrimidine-2,4-diamine; quaternary ammonium herbicides such as diethamquat 1 ,1 '-bis(diethylcarbamoylmethyl)-4,4'-bipyridinium; paraquat 1 ,1 '-dimethyl-4,4'- bipyridinium; thiocarbamate herbicides such as cycloate S-ethyl

cyclohexyl(ethyl)thiocarbamate; tiocarbazil S-benzyl di-sec-butylthiocarbamate;

thiocarbonate herbicides such as EXD Ο,Ο-diethyl dithiobis(thioformate); thiourea herbicides such as methiuron 1 ,1 -dimethyl-3-m-tolyl-2-thiourea; triazine herbicides such as triaziflam (f?S)-N-[2-(3,5-dimethylphenoxy)-1 -methylethyl]-6-(1 -fluoro-1 -methylethyl)-1 ,3,5- triazine-2,4-diamine; chlorotriazine herbicides such as cyprazine e-chloro-W^cyclopropyl- Λ/4-isopropyl-l ,3,5-triazine-2,4-diamine; propazine G-chloro-^./V^-di-isopropyl-l ,3,5- triazine-2,4-diamine; methoxytriazine herbicides such as prometon W^/Vl-di-isopropyl-G- methoxy-1 ,3,5-triazine-2,4-diamine; methylthiotriazine herbicides such as cyanatryn 2-(4- ethylamino-6-methylthio-1 ,3,5-triazin-2-ylamino)-2-methylpropionitrile; triazinone herbicides such as hexazinone 3-cyclohexyl-6-dimethylamino-1 -methyl-1 ,3,5-triazine-2,4(1 H,3H)- dione; triazole herbicides such as epronaz N-ethyl-/V-propyl-3-propylsulphonyl-1 HA ,2,4- triazole-1 -carboxamide; triazolone herbicides such as carfentrazone (/¾>)-2-chloro-3-{2- chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1 HA ,2,4-triazol-1 -yl]-4- fluorophenyljpropionic acid; triazolopyrimidine herbicides such as florasulam 2',6',8- trifluoro-5-methoxy[1 ,2,4]triazolo[1 ,5-c]pyrimidine-2-sulphonanilide; uracil herbicides such as flupropacil isopropyl 2-chloro-5-(1 ,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- trifluoromethylpyrimidin-1 -yl)benzoate; urea herbicides such as cycluron 3-cyclo-octyl-1 ,1 - dimethylurea; monisouron 1 -(5-feri-butyl-1 ,2-oxazol-3-yl)-3-methylurea; phenylurea herbicides such as chloroxuron 3-[4-(4-chlorophenoxy)phenyl]-1 ,1 -dimethylurea; siduron 1 - (2-methylcyclohexyl)-3-phenylurea; pyrimidinylsulphonylurea herbicides such as flazasulphuron 1 -(4,6-dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulphonyl)urea; pyrazosulphuron 5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulphamoyl]-1 -methylpyrazole- 4-carboxylic acid; triazinylsulphonylurea herbicides such as thifensulphuron 3-(4-methoxy- 6-methyl-1 ,3,5-triazin-2-ylcarbamoylsulphamoyl)thiophene-2-carboxylic acid;

thiadiazolylurea herbicides such as tebuthiuron 1 -(5-feri-butyl-1 ,3,4-thiadiazol-2-yl)-1 ,3- dimethylurea; and/or unclassified herbicides such as chlorfenac (2,3,6- trichlorophenyl)acetic acid; methazole 2-(3,4-dichlorophenyl)-4-methyl-1 ,2,4- oxadiazolidine-3,5-dione; tritac (ftS)-1 -(2,3,6-trichlorobenzyloxy)propan-2-ol; 2,4-D, chlorimuron, and fenoxaprop; and combinations thereof.

[0170] Ingredient (h3") is a pesticide. Suitable pesticides are exemplified by atrazine, diazinon, and chlorpyrifos. For purposes of this application, pesticide includes insect repellents such as Ν,Ν-diethyl-meta-toluamide and pyrethroids such as pyrethrin.

[0171] Ingredient (h4") is an antimicrobial agent. Suitable antimicrobials are commercially available, such as DOW CORNING® 5700 and DOW CORNING® 5772, which are from Dow Corning Corporation of Midland, Michigan, U.S.A.

[0172] Alternatively, ingredient (H") may comprise a boron containing material, e.g., boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as a pesticide, fungicide, and/or flame retardant.

[0173] Ingredient (J") is a flame retardant. Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds. Alternatively, the flame retardant may be selected from halogen based flame-retardants such as decabromodiphenyloxide, octabromordiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyoxybenzene, ethylene bis- tetrabromophthalmide, pentabromoethyl benzene, pentabromobenzyl acrylate, tribromophenyl maleic imide, tetrabromobisphenyl A, bis-(tribromophenoxy) ethane, bis- (pentabromophenoxy) ethane, polydibomophenylene oxide, tribromophenylallyl ether, bis- dibromopropyl ether, tetrabromophthalic anhydride, dibromoneopentyl gycol, dibromoethyl dibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene,

pentabromochlorocyclohexane, tetrabromoxylene, hexabromocyclododecane, brominated polystyrene, tetradecabromodiphenoxybenzene, trifluoropropene and PVC. Alternatively, the flame retardant may be selected from phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cyclic phosphates, triaryl phosphate, bis- melaminium pentate, pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricreyl, trixylenyl, isodecyl diphenyl, ethylhexyl diphenyl, phosphate salts of various amines such as ammonium phosphate, trioctyl, tributyl or tris-butoxyethyl phosphate ester. Other flame retardants may include tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.

[0174] The amount of flame retardant can vary depending on factors such as the flame retardant selected and whether solvent is present. However, the amount of flame retardant in the composition may range from greater than 0 % to 10 % based on the combined weight of all ingredients in the composition.

[0175] Ingredient (K") is a surface modifier. Suitable surface modifiers are exemplified by (k1 ") an adhesion promoter or (k2") a release agent. Suitable adhesion promoters for ingredient (k1 ") may comprise a transition metal chelate, a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional

polyorganosiloxane, an aminofunctional silane, or a combination thereof. Adhesion promoters are known in the art and may comprise silanes having the formula

R²⁴tR²⁵ _uSi(OR²⁶)4-(t + u) where each R²⁴ is independently a monovalent organic group having at least 3 carbon atoms; R²⁵ contains at least one SiC bonded substituent having an adhesion-promoting group, such as amino, epoxy, mercapto or acrylate groups;

subscript t has a value ranging from 0 to 2; subscript u is either 1 or 2; and the sum of (t + u) is not greater than 3. Alternatively, the adhesion promoter may comprise a partial condensate of the above silane. Alternatively, the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0176] Alternatively, the adhesion promoter may comprise an unsaturated or epoxy- functional compound. The adhesion promoter may comprise an unsaturated or epoxy- functional alkoxysilane. For example, the functional alkoxysilane can have the formula

R²⁷ _vSi(OR²⁸)(4_-v), where subscript v is 1 , 2, or 3, alternatively subscript v is 1. Each R²⁷ is independently a monovalent organic group with the proviso that at least one R²⁷ is an unsaturated organic group or an epoxy-functional organic group. Epoxy-functional organic groups for R²⁷ are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.

Unsaturated organic groups for R²⁷ are exemplified by 3-methacryloyloxypropyl, 3- acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl. Each R²⁸ is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. R²⁸ is exemplified by methyl, ethyl, propyl, and butyl.

[0177] Examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,

(epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examples of suitable unsaturated alkoxysilanes include

vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.

[0178] Alternatively, the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy- functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane. The adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion promoter is exemplified by a mixture of 3- glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated

methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated

methylvinyl/dimethylsiloxane copolymer.

[0179] Alternatively, the adhesion promoter may comprise an aminofunctional silane, such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3, H₂N(CH2)2Si(OCH2CH3)_3j H₂N(CH2)3Si(OCH3)_3j H₂N(CH2)3Si(OCH2CH₃)3, CH₃NH(CH2)3Si(OCH3)_3j CH₃NH(CH2)3Si(OCH2CH3)_3j CH₃NH(CH2)5Si(OCH3)_3j CH₃NH(CH2)5Si(OCH2CH3)_3j H₂N(CH2)2NH(CH2)3Si(OCH₃)3,

Η2Ν(0Η2)2ΝΗ(0Η2)38ί(Ο0Η20Η3)3, 0Η₃ΝΗ(0Η2)2ΝΗ(0Η2)38ί(Ο0Η3)3,

CH₃NH(CH2)2NH(CH2)3Si(OCH2CH3)_3j C₄H9NH(CH2)2NH(CH2)3Si(OCH3)_3j C₄H9NH(CH2)2NH(CH2)3Si(OCH2CH3)_3j H2N(CH2)2SiCH₃(OCH₃)2,

H2N(CH2)2SiCH₃(OCH2CH₃)2, H2N(CH2)3SiCH₃(OCH₃)2,

H2N(CH2)3SiCH₃(OCH2CH₃)2, CH₃NH(CH2)3SiCH3(OCH₃)2,

CH₃NH(CH2)3SiCH3(OCH2CH₃)2, CH₃NH(CH2)5SiCH3(OCH₃)2,

CH₃NH(CH2)5SiCH3(OCH2CH₃)2, H2N(CH2)2NH(CH2)3SiCH₃(OCH₃)2,

H2N(CH2)2NH(CH2)3SiCH₃(OCH2CH₃)2, CH₃NH(CH2)2NH(CH2)3SiCH3(OCH₃)2, CH₃NH(CH2)2NH(CH2)3SiCH3(OCH2CH₃)2, C₄H₉NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C₄H₉NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and a combination thereof.

[0180] Alternatively, the adhesion promoter may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof.

[0181 ] Ingredient (k2") is a release agent. Suitable release agents are exemplified by fluorinated compounds, such as fluoro-functional silicones, or fluoro-functional organic compounds.

[0182] Alternatively, the surface modifier for ingredient (K") may be used to change the appearance of the surface of a reaction product of the composition. For example, surface modifier may be used to increase gloss of the surface of a reaction product of the composition. Such a surface modifier may comprise a polydiorganosiloxane with alkyl and aryl groups. For example, DOW CORNING® 550 Fluid is a trimethylsiloxy-terminated poly(dimethyl/methylphenyl)siloxane with a viscosity of 125 cSt that is commercially available from Dow Corning Corporation.

[0183] Alternatively, ingredient (K") may be a natural oil obtained from a plant or animal source, such as linseed oil, tung oil, soybean oil, castor oil, fish oil, hempseed oil, cottonseed oil, oiticica oil, and rapeseed oil.

[0184] The exact amount of ingredient (K") depends on various factors including the type of surface modifier selected as ingredient (K") and the end use of the composition and its reaction product. However, ingredient (K"), when present, may be added to the composition in an amount ranging from 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts. Ingredient (K") may be one adhesion promoter. Alternatively, ingredient (K") may comprise two or more different surface modifiers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.

[0185] Chain lengtheners may include difunctional silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crosslinking occurs. Chain lengtheners may be used to reduce the modulus of elongation of the cured product. Chain lengtheners and crosslinkers compete in their reactions with the hydrolyzable substituents in ingredient (B"). To achieve noticeable chain extension, the difunctional silane has substantially higher reactivity than the trifunctional crosslinker with which it is used.

Suitable chain lengtheners include diamidosilanes such as dialkyldiacetamidosilanes or alkenylalkyldiacetamidosilanes, particularly methylvinyldi(N-methylacetamido)silane, or dimethyldi(N-methylacetamido)silane, diacetoxysilanes such as dialkyldiacetoxysilanes or alkylalkenyldiacetoxysilanes, diaminosilanes such as dialkyldiaminosilanes or

alkylalkenyldiaminosilanes, dialkoxysilanes such as dimethyldimethoxysilane,

dimethyldiethoxysilane and oaminoalkyldialkoxyalkylsilanes, polydialkylsiloxanes having a degree of polymerization of from 2 to 25 and having an average per molecule of at least two hydrolyzable groups, such as acetamido or acetoxy or amino or alkoxy or amido or ketoximo substituents, and diketoximinosilanes such as dialkylkdiketoximinosilanes and alkylalkenyldiketoximinosilanes. Ingredient (L") may be one chain lengthener.

Alternatively, ingredient (L") may comprise two or more different chain lengtheners that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.

[0186] Ingredient (M") is and endblocker comprising an M unit, i.e., a siloxane unit of formula R²⁹3SiO-|/2, where each R²⁹ independently represents a monovalent organic group unreactive ingredient (B"), such as a monovalent hydrocarbon group. Ingredient (M") may comprise polyorganosiloxanes endblocked on one terminal end by a triorganosilyl group, e.g., (CH3)3SiO-, and on the other end by a hydroxyl group. Ingredient (M") may be a polydiorganosiloxane such as a polydimethylsiloxane. The polydiorganosiloxanes having both hydroxyl end groups and triorganosilyl end groups, may have more than 50 %, alternatively more than 75 %, of the total end groups as hydroxyl groups. The amount of triorganosilyl group in the polydimethylsiloxane may be used to regulate the modulus of the reaction product prepared by condensation reaction of the composition. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups may provide a lower modulus in certain cured products. Ingredient (M") may be one endblocker. Alternatively, ingredient (M") may comprise two or more different endblockers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.

[0187] Ingredient (N") is a non-reactive, elastomeric, organic polymer, i.e., an elastomeric organic polymer that does not react with ingredient (B"). Ingredient (N") is compatible with ingredient (B"), i.e., ingredient (N") does not form a two-phase system with ingredient (B"). Ingredient (N") may have low gas and moisture permeability. Ingredient (N") may have Mn ranging from 30,000 to 75,000. Alternatively, ingredient (N") may be a blend of a higher molecular weight, non-reactive, elastomeric, organic polymer with a lower molecular weight, non-reactive, elastomeric, organic polymer. In this case, the higher molecular weight polymer may have Mn ranging from 100,000 to 600,000 and the lower molecular weight polymer may have Mn ranging from 900 to 10,000, alternatively 900 to 3,000. The value for the lower end of the range for Mn may be selected such that ingredient (N") has compatibility with ingredient (B") and the other ingredients of the composition.

[0188] Ingredient (N") may comprise a polyisobutylene. Polyisobutylenes are known in the art and are commercially available. Examples suitable for use as ingredient (N") include polyisobutylenes marketed under the trademark OPPANOL® by BASF Corporation of Germany.

[0189] Other polyisobutylenes include different Parleam grades such as highest molecular weight hydrogenated polyisobutene PARLEAM® SV (POLYSYNLANE SV) from NOF CORPORATION Functional Chemicals & Polymers Div., Yebisu Garden Place Tower, 20-3 Ebisu 4-chome, Shibuya-ku, Tokyo 150-6019, Japan (Kinematic Viscosity (98.9 ) 4700). Other polyisobutylenes are commercially available from ExxonMobil Chemical Co. of Baytown, Texas, U.S.A. and include polyisobutylenes marketed under the trademark VISTANEX®, such as MML-80, MML-100, MML-120, and MML-140.

VISTANEX® polyisobutylenes are paraffinic hydrocarbon polymers, composed of long, straight-chain macromolecules containing only chain-end olefinic bonds. VISTANEX® MM polyisobutylenes have viscosity average molecular weight ranging from 70,000 to 90,000. Lower molecular weight polyisobutylenes include VISTANEX® LM, such as LM-MS (viscosity average molecular weight ranging from 8,700 to 10,000 also made by

ExxonMobil Chemical Co.) and VISTANEX LM-MH (viscosity average molecular weight of 10,000 to 1 1 ,700) as well as Soltex PB-24 (Mn 950) and Indopol® H-100 (Mn 910) and Indopol® H-1200 (Mn 2100) from Amoco. Other polyisobutylenes are marketed under the trademarks NAPVIS® and HYVIS® by BP Chemicals of London, England. These polyisobutylenes include NAPVIS® 200, D10, and DE3; and HYVIS® 200. The NAPVIS® polyisobutylenes may have Mn ranging from 900 to 1300. [0190] Alternatively, ingredient (N") may comprise butyl rubber. Alternatively, ingredient (N") may comprise a styrene-ethylene/butylene-styrene (SEBS) block copolymer, a styrene-ethylene/propylene-styrene (SEPS) block copolymer, or a combination thereof. SEBS and SEPS block copolymers are known in the art and are commercially available as Kraton® G polymers from Kraton Polymers U.S. LLC of Houston, Texas, U.S.A., and as Septon polymers from Kuraray America, Inc., New York, NY, U.S.A. Alternatively, ingredient (N") may comprise a polyolefin plastomer. Polyolefin plastomers are known in the art and are commercially available as AFFINITY® GA 1900 and AFFINITY® GA 1950 from Dow Chemical Company, Elastomers & Specialty Products Division, Midland, Michigan, U.S.A.

[0191] The amount of ingredient (N") may range from 0 parts to 50 parts, alternatively 10 parts to 40 parts, and alternatively 5 parts to 35 parts, based on the weight of the composition. Ingredient (N") may be one non-reactive, elastomeric, organic polymer. Alternatively, ingredient (N") may comprise two or more non-reactive, elastomeric, organic polymers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence. Alternatively, ingredient (N") may be added to the composition when ingredient (B") comprises a base polymer with an organic polymer backbone.

[0192] Ingredient (O") is an anti-aging additive. The anti-aging additive may comprise an antioxidant, a UV absorber, a UV stabilizer, a heat stabilizer, or a combination thereof. Suitable antioxidants are known in the art and are commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols. Alternatively, the stabilizer may be a sterically hindered amine such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals, U.S.A. I RGANOX® 1010 comprises pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Examples of UV absorbers include phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (TINUVIN® 571 ). Examples of UV stabilizers include bis(1 ,2,2,6,6-pentamethyl-4- piperidyl) sebacate; methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272). These and other TINUVIN® additives, such as TINUVIN® 765 are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A. Other UV and light stabilizers are commercially available, and are exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from E. I. du Pont de Nemours and Company of Delaware, U.S.A. Oligomeric (higher molecular weight) stabilizers may alternatively be used, for example, to minimize potential for migration of the stabilizer out of the composition or the cured product thereof. An example of an oligomeric antioxidant stabilizer (specifically, hindered amine light stabilizer (HALS)) is Ciba TINUVIN® 622, which is a dimethylester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6- tetramethyl-1 -piperidine ethanol. Heat stabilizers may include iron oxides and carbon blacks, iron carboxylate salts, cerium hydrate, barium zirconate, cerium and zirconium octoates, and porphyrins.

[0193] The amount of ingredient (O") depends on various factors including the specific anti-aging additive selected and the anti-aging benefit desired. However, the amount of ingredient (O") may range from 0 to 5 weight %, alternatively 0.1 % to 4 %, and

alternatively 0.5 % to 3 %, based on the weight of the composition. Ingredient (O") may be one anti-aging additive. Alternatively, ingredient (O") may comprise two or more different anti-aging additives.

[0194] Ingredient (P") is a water release agent that releases water over an application temperature range. Ingredient (P") is selected such that ingredient (P") contains an amount of water sufficient to partially or fully react the composition and such that ingredient (P") releases the sufficient amount of water when exposed for a sufficient amount of time to a use temperature (i.e., a temperature at which the composition is used). However, ingredient (P") binds the water sufficiently to prevent too much water from being released during the method for making the composition and during storage of the composition. For example, ingredient (P") binds the water sufficiently during compounding of the

composition such that sufficient water is available for condensation reaction of the composition during or after the application process in which the composition is used. This "controlled release" property also may provide the benefit of ensuring that not too much water is released too rapidly during the application process, since this may cause bubbling or voiding in the reaction product formed by condensation reaction of the composition. Precipitated calcium carbonate may be used as ingredient (P") when the application temperature ranges from 80 °C to 120 °C, alternatively 90 °C to 1 10 °C, and alternatively 90 °C to 100 ^<€. However, when the composition is prepared on a continuous (e.g., twin- screw) compounder, the ingredients may be compounded at a temperature 20 °C to 30 °C above the application temperature range for a short amount of time. Therefore, ingredient (P") is selected to ensure that not all of the water content is released during compounding; however ingredient (P") releases a sufficient amount of water for condensation reaction of the composition when exposed to the application temperature range for a sufficient period of time.

[0195] Examples of suitable water release agents are exemplified by metal salt hydrates, hydrated molecular sieves, and precipitated calcium carbonate, which is available from Solvay under the trademark WINNOFIL® SPM. The water release agent selected can depend on various factors including the other ingredients selected for the composition, including catalyst type and amount; and the process conditions during compounding, packaging, and application. In a twin-screw compounder, residence time may be less than a few minutes, typically less than 1 to 2 minutes. The ingredients are heated rapidly because the surface area/volume ratio in the barrels and along the screw is high and heat is induced by shearing the ingredients. How much water is removed from ingredient (P") depends on the water binding capabilities, the temperature, the exposure time (duration), and the level of vacuum used to strip the composition passing through the compounder. Without wishing to be bound by theory, it is thought that with a twin screw compounding temperature of 120 °C there would remain enough water on the precipitated CaC03 to cause the composition to react by condensation reaction over a period of 1 to 2 weeks at room temperature when the composition has been applied at 90 °C.

[0196] A water release agent may be added to the composition, for example, when the base polymer has low water permeability (e.g., when the base polymer has an organic polymer backbone) and/or the amount of ingredient (P") in the composition depends on various factors including the selection of ingredients (A), (B") and (C") and whether any additional ingredients are present, however the amount of ingredient (P") may range from 5 to 30 parts based on the weight of the composition.

[0197] Without wishing to be bound by theory, it is thought when the composition is heated to the application temperature, the heat would liberate the water, and the water would react with the hydrolyzable groups on ingredient (B") to react the composition. Byproducts such as alcohols and/or water left in the composition may be bound by a drying agent, thereby allowing the condensation reaction (which is an equilibrium reaction) to proceed toward completion.

[0198] Ingredient (Q") is a pigment. For purposes of this application, the term 'pigment' includes any ingredient used to impart color to a reaction product of a composition described herein. The amount of pigment depends on various factors including the type of pigment selected and the desired degree of coloration of the reaction product. For example, the composition may comprise 0 to 20 %, alternatively 0.001 % to 5 %, of a pigment based on the weight of all ingredients in the composition.

[0199] Examples of suitable pigments include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from PolyOne) and carbon black. Representative, non-limiting examples of carbon black include Shawinigan Acetylene black, which is commercially available from Chevron Phillips Chemical Company LP; SUPERJET® Carbon Black (LB-101 1 ) supplied by Elementis Pigments Inc., of Fairview Heights, IL U.S.A.; SR 51 1 supplied by Sid Richardson Carbon Co, of Akron, OH U.S.A.; and N330, N550, N762, N990 (from Degussa Engineered Carbons of Parsippany, NJ, U.S.A.).

[0200] The composition may optionally further comprise up to 5 %, alternatively 1 % to 2 % based on the weight of the composition of ingredient (R") a rheological additive for modifying rheology of the composition. Rheological additives are known in the art and are commercially available. Examples include polyamides, Polyvest, which is commercially available from Evonik, Disparlon from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogel from Lubrizol. Other suitable rheological additives include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.

[0201] Alternatively, ingredient (R") may comprise a microcrystalline wax that is a solid at 25 °C (wax). The melting point may be selected such that the wax has a melting point at the low end of the desired application temperature range. Without wishing to be bound by theory, it is thought that ingredient (R") acts as a process aid that improves flow properties while allowing rapid green strength development (i.e., a strong increase in viscosity, corresponding to increase in the load carrying capability of a seal prepared from the composition, with a temperature drop) upon cooling the composition a few degrees, for example, after the composition is applied to a substrate. Without wishing to be bound by theory, it is thought that incorporation of wax may also facilitate incorporation of fillers, compounding and de-airing (during production of the composition), and mixing (static or dynamic mixing during application of parts of a multiple-part composition). It is thought that the wax, when molten, serves as a process aid, substantially easing the incorporation of filler in the composition during compounding, the compounding process itself, as well as in during a de-airing step, if used. The wax, with a melt temperature below 100 °C, may facilitate mixing of the parts of a multiple part composition before application, even in a simple static mixer. The wax may also facilitate application of the composition at temperatures ranging from 80 °C to 1 10 °C, alternatively 90 °C to 100 °C with good rheology.

[0202] Waxes suitable for use as ingredient (R") may be non-polar hydrocarbons. The waxes may have branched structures, cyclic structures, or combinations thereof. For example, petroleum microcrystalline waxes are available from Strahl & Pitsch, Inc., of West Babylon, NY, U.S.A. and include SP 96 (melting point ranging from 62 ^eC to 69 ^eC), SP 18 (melting point ranging from 73 ^eC to 80 ^eC), SP 19 (melting point ranging from 76 ^eC to 83 ^eC), SP 26 (melting point ranging from 76 ^eC to 83 ^eC), SP 60 (melting point ranging from 79 ^eC to 85 ^eC), SP 617 (melting point ranging from 88 ^eC to 93 ^eC), SP 89 (melting point ranging from 90 ^eC to 95 ^eC), and SP 624 (melting point ranging from 90 ^eC to 95 ^eC). Other petroleum microcrystalline waxes include waxes marketed under the trademark Multiwax® by Crompton Corporation of Petrolia, Pennsylvania, U.S.A. These waxes include 180-W, which comprises saturated branched and cyclic non-polar hydrocarbons and has melting point ranging from 79 ^eC to 87 ^eC; Multiwax® W-445, which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 76 °C to 83 ^eC; and Multiwax® W-835, which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 73 ^eC to 80 ^eC.

[0203] The amount of ingredient (R") depends on various factors including the specific rheological additive selected and the selections of the other ingredients of the composition. However, the amount of ingredient (R") may range from 0 parts to 20 parts, alternatively 1 part to 15 parts, and alternatively 1 part to 5 parts based on the weight of the composition. Ingredient (R") may be one rheological additive. Alternatively, ingredient (R") may comprise two or more different rheological additives.

[0204] Ingredient (S") is a vehicle (e.g., a solvent and/or diluent) that may be used in the composition. The vehicle may facilitate flow of the composition and introduction of certain ingredients, such as silicone resin and/or fillers. Vehicles used herein are those that help fluidize the ingredients of the composition but essentially do not react with any of these ingredients. Vehicle may be selected based on solubility the ingredients in the composition and volatility. The solubility refers to the vehicle being sufficient to dissolve and/or disperse ingredients of the composition. Volatility refers to vapor pressure of the vehicle. If the vehicle is too volatile (having too high vapor pressure) bubbles may form in the

composition at the application temperature, and the bubbles may cause cracks or otherwise weaken or detrimentally affect properties of the cured product. However, if the vehicle is not volatile enough (too low vapor pressure) the vehicle may remain as a plasticizer in the reaction product of the composition, or the amount of time for the reaction product to develop physical properties may be longer than desired.

[0205] Suitable vehicles include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5 to 1 .5 centiStoke (cSt) Dow Corning® 200 Fluids and DOW CORNING® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.

[0206] Alternatively, the vehicle may be an organic solvent. The organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n- butyl ether, a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform ; dimethyl sulfoxide; dimethyl formamide, acetonitrile;

tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof.

[0207] The amount of vehicle can depend on various factors including the type of vehicle selected and the amount and type of other ingredients selected for the composition.

However, the amount of vehicle may range from 1 % to 99%, alternatively 2 % to 50 %, based on the weight of the composition.

[0208] The composition may optionally further comprise ingredient (T") a tackifying agent. The tackifying agent may comprise an aliphatic hydrocarbon resin such as a hydrogenated polyolefin having 6 to 20 carbon atoms, a hydrogenated terpene resin, a rosin ester, a hydrogenated rosin glycerol ester, or a combination thereof. Tackifying agents are commercially available. Aliphatic hydrocarbon resins are exemplified by ESCOREZ 1 102, 1304, 1310, 1315, and 5600 from Exxon Chemical and Eastotac resins from Eastman, such as Eastotac H-100 having a ring and ball softening point of 100 °C, Eastotac H-1 15E having a ring and ball softening point of 1 15 °C, and Eastotac H-130L having a ring and ball softening point of 130 °C. Hydrogenated terpene resins are exemplified by Arkon P 100 from Arakawa Chemicals and Wingtack 95 from Goodyear. Hydrogenated rosin glycerol esters are exemplified by Staybelite Ester 10 and Foral from Hercules. Examples of commercially available polyterpenes include Piccolyte A125 from Hercules. Examples of aliphatic/aromatic or cycloaliphatic/aromatic resins include ECR 149B or ECR 179A from Exxon Chemical. Alternatively, a solid tackifying agent (i.e., a tackifying agent having a ring and ball softening point above 25 °C), may be added.

Suitable tackifying agents include any compatible resins or mixtures thereof such as (1 ) natural or modified rosins such, for example, as gum rosin, wood rosin, tall-oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural or modified rosins, such, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic- modified pentaerythritol ester of rosin; (3) copolymers and terpolymers of natural terpenes, e.g., styrene/terpene and alpha methyl styrene/terpene; (4) polyterpene resins having a softening point, as determined by ASTM method E28,58T, ranging from 60 ¾ to 150 °C; the latter polyterpene resins generally resulting from the polymerization of terpene hydrocarbons, such as the bicyclic monoterpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures; also included are the hydrogenated polyterpene resins; (5) phenolic modified terpene resins and hydrogenated derivatives thereof, for example, as the resin product resulting from the condensation, in an acidic medium, of a bicyclic terpene and phenol; (6) aliphatic petroleum hydrocarbon resins having a ring and ball softening point ranging from 60 °C to 135 °C; the latter resins resulting from the polymerization of monomers consisting of primarily of olefins and diolefins; also included are the hydrogenated aliphatic petroleum hydrocarbon resins; (7) alicyclic petroleum hydrocarbon resins and the hydrogenated derivatives thereof; and (8) aliphatic/ aromatic or cycloaliphatic/aromatic copolymers and their hydrogenated derivatives. The amount of tackifying agent depends on various factors including the specific tackifying agent selected and the selection the other ingredients in the

composition. However, the amount of tackifying agent may range from 0 parts to 20 parts based on the weight of the composition.

[0209] The composition may optionally further comprise ingredient (U"), a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazole,

mercaptabenzotriazole and commercially available corrosion inhibitors such as 2,5- dimercapto-1 ,3,4-thiadiazole derivative (CUVAN® 826) and alkylthiadiazole (CUVAN® 484) from R. T. Vanderbilt of Norwalk, Connecticut, U.S.A. When present, the amount of ingredient (U") may range from 0.05 % to 0.5 % based on the weight of the composition.

[0210] When selecting ingredients for the composition described above, there may be overlap between types of ingredients because certain ingredients described herein may have more than one function. For example, certain alkoxysilanes may be useful as filler treating agents and as adhesion promoters, certain fatty acid esters may be useful as plasticizers and may also be useful as filler treating agents, carbon black may be useful as a pigment, a flame retardant, and/or a filler, and nonreactive polydiorganosiloxanes such as polydimethylsiloxanes may be useful as extenders and as solvents.

[0211 ] The composition described above may be prepared as a one part composition, for example, by combining all ingredients by any convenient means, such as mixing. For example, a one-part composition may be made by optionally combining (e.g., premixing) the base polymer (B") and an extender (E") and mixing the resulting extended base polymer with all or part of the filler (F"), and mixing this with a pre-mix comprising the crosslinker (C") and ingredient (A). Other additives such as (O") the anti-aging additive and (Q") the pigment may be added to the mixture at any desired stage. A final mixing step may be performed under substantially anhydrous conditions, and the resulting

compositions are generally stored under substantially anhydrous conditions, for example in sealed containers, until ready for use. [0212] Alternatively, the composition may be prepared as a multiple part (e.g., 2 part) composition when a crosslinker is present. In this instance the catalyst and crosslinker are stored in separate parts, and the parts are combined shortly before use of the composition. For example, a two part curable composition may be prepared by combining ingredients comprising (B") and (C") to form a first (curing agent) part by any convenient means such as mixing. A second (base) part may be prepared by combining ingredients comprising (A) and (B") by any convenient means such as mixing. The ingredients may be combined at ambient or elevated temperature and under ambient or anhydrous conditions, depending on various factors including whether a one part or multiple part composition is selected. The base part and curing agent part may be combined by any convenient means, such as mixing, shortly before use. The base part and curing agent part may be combined in relative amounts of base: curing agent ranging from 1 :1 to 10:1 .

[0213] The equipment used for mixing the ingredients is not specifically restricted.

Examples of suitable mixing equipment may be selected depending on the type and amount of each ingredient selected. For example, agitated batch kettles may be used for relatively low viscosity compositions, such as compositions that would react to form gums or gels. Alternatively, continuous compounding equipment, e.g., extruders such as twin screw extruders, may be used for more viscous compositions and compositions containing relatively high amounts of particulates. Exemplary methods that can be used to prepare the compositions described herein include those disclosed in, for example, U.S. Patent Publications US 2009/0291238 and US 2008/0300358.

[0214] These compositions made as described above may be stable when the stored in containers that protect the compositions from exposure to moisture, but these compositions may react via condensation reaction when exposed to atmospheric moisture. Alternatively, when a low permeability composition is formulated, the composition may cure to form a cured product when moisture is released from a water release agent.

[0215] Compositions prepared as described above, and the reaction products thereof, have various uses. The ingredients described above may be used to prepare various types of composition comprising ingredients (A) and (B"). The composition may further comprise one or more of the additional ingredients described above, depending on the type of composition and the desired end use of the composition and/or the reaction product of the composition. For example, the ingredients and methods described above may be used for chain extension processes to increase viscosity of the base polymer and/or form a gum, for example, when the base polymer has an average of one to two hydrolyzable groups per molecule. Alternatively, the ingredients and methods described above may be used to formulate curable compositions, for example, when the base polymer has two or more hydrolyzable groups per molecule and/or a crosslinker is present in the composition. The compositions described herein may be reacted by condensation reaction by exposure to moisture. For example, the compositions may react via condensation reaction when exposed to atmospheric moisture. Alternatively, the composition react moisture is released from a water release agent, when a water release agent is present. Each composition described herein reacts to form a reaction product. The reaction product may have a form selected from a gum, a gel, a rubber, or a resin.

[0216] Alternatively, when (X) the reactive component in the composition described above is (X1 ) a urethane component, the composition may optionally further comprise an additional ingredient that is distinct from ingredients (A), (B), and (C), described above. The additional ingredient in the urethane component may be selected from (D) a blowing agent, (E) a surfactant, (F) a vehicle, (G) a filler, (H) a pigment, (I) a flame retardant, (J) a cell stabilizer, and a combination thereof.

[0217] Ingredient (D) is a blowing agent that may be added to the composition to cause the reaction product of the composition to be a foam. The blowing agent may be liquid carbon dioxide, CFCs, HCFCs, HFCs, and pentane, alternatively, water or a mixture of water and HCFC. Alternatively, the blowing agent may be water. When water is added, then additional isocyanate functional compound may be added so that the isocyanate groups react with water to form a urea linkage and carbon dioxide gas, and the resulting reaction product contains both urethane and urea linkages. Alternatively, the blowing agent may be added as a gas or produced by boiling volatile liquids. In the latter case heat generated by the reaction between the isocyanate groups on ingredient (B) and the OH groups on ingredient (C) causes the volatile liquid to vaporize. The volatile liquids is exemplified by halogenated hydrocarbons, such as 1 ,1 ,1 ,3,3-pentafluoropropane and 1 ,1 ,1 ,2-tetrafluoroethane; and hydrocarbons such as n-pentane. A cell stabilizer may optionally also be added. The cell stabilizers are illustrated by silicones, alternatively silicone polyethers.

[0218] Ingredient (E) is a surfactant. A surfactant may be added to the composition to modify the characteristics of both foam and non-foam polyurethane reaction products. Exemplary surfactants include polydimethylsiloxane-polyoxyalkylene block copolymers, nonylphenol ethoxylates, silicone oils, and organic compounds. The silicone oil may be DOW CORNING® 200 Fluid, which is commercially available from Dow Corning

Corporation of Midland, Michigan, U.S.A. In foams, surfactants are used to emulsify the liquid components, regulate cell size, and stabilize the cell structure to prevent collapse and sub-surface voids. In non-foam applications they are used as air release and anti- foaming agents, as wetting agents, and are used to eliminate surface defects. When present, the amount of surfactant may be 0.5% to 1 .5% based on the combined weights of all ingredients in the composition.

[0219] Ingredient (F) is a vehicle, i.e., a solvent or diluent, which is exemplified by the vehicle described above for ingredient (S"). The vehicle may facilitate flow of the composition and introduction of certain ingredients, such as fillers.

[0220] Alternatively, the vehicle may be an organic solvent in the urethane composition. The organic solvent can be an a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile; tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof.

[0221 ] The amount of vehicle can depend on various factors including the type of vehicle selected and the amount and type of other ingredients selected for the composition.

However, the amount of vehicle may range from 1 % to 99%, alternatively 2 % to 50 %, based on the weight of the urethane composition.

[0222] Alternatively, when the reactive component in the composition described above is (X2) an ester component, then the composition may optionally further comprise an additional ingredient that is distinct from ingredients (A), (Β'), and (C), described above. The additional ingredient in the ester component may be selected from a filler, a stabilizer, a flame retardant, an impact modifier, a pigment, a cobinder, a hardner, or a combination thereof. Examples of such additional ingredients are as described above.

[0223] When selecting ingredients for the composition described above, there may be overlap between types of ingredients because certain ingredients described herein may have more than one function. For example, certain cell stabilizers (e.g., some silicone oils) may also be useful as surfactants. When adding additional ingredients to the composition, the additional ingredients are distinct from one another.

[0224] The composition described above may be prepared by mixing ingredients comprising (A) and (X) and optionally one or more of the additional ingredients described above. The composition may be produced as a one part system, or as a multiple part system, such as a two part composition, in which one part (Part B) includes ingredient (B), and another part (Part A) includes ingredients (A) and (C). The reaction product may then be prepared by mixing Part A and Part S of the composition.

EXAMPLES

[0225] In example 1 , catalysts were prepared as follows: 4.85 g of Iron(lll) (2- ethylhexanoate)3 (corresponding to 5 mmole) at 50% in mineral spirits was mixed with 100 ml_ toluene to make a 0.05 M iron precursor solution. A ligand from Table 2, above, in an amount of 1 .28 g ( corresponding to 10 mmole) was added into the iron precursor solution slowly over a period of 20 minutes. The mixture was heated at 70 °C for 2 hours followed by stripping in vacuum to remove toluene to form a Fe-ligand catalyst.

[0226] In example 2, the Fe-ligand catalysts prepared in example 1 were used to catalyze reactions for polyurethane formation. Glycerol propoxylate with a molecular weight of 1500 (5.0 g), silicone oil (0.1 g) and a Fe-ligand catalyst prepared above in example 1 (0.05 g to 0.6 g) were loaded in a cup (4 cm id and 4 cm depth) and mixed by a magnetic stir bar. Next, 3.7 g 4,4'-methylenediphenyldiisocyanate (MDI) was added to react with the glycerol propoxylate. The elapsed time from MDI addition until the magnetic bar stopped due to a viscosity increase of the contents of the cup was measured. This elapsed time was used to estimate the rate of polyurethane formation from the glycerol propoxylate and MDI. Table 2, below, lists the reaction catalyzed by different amounts of Fe-ligand catalysts with three different ligands. As control samples, a tin catalyst and the metal precursor (without reacting with a ligand according to example 1 ) were used under the same conditions as this example 2. The ligand used, the amount, elapsed time, and temperature is shown below in Table 3.

Table 3

propane am ne s

In Table 3, ND means no data was recorded.

[0227] In example 3, catalyst samples were prepared using different metal precursors. A metal precursor from Table 4, below, in an amount of 10 mmole was mixed with 200 ml_ toluene to make a 0.05 M metal precursor solution. A ligand from Table 2 was added to the metal precursor solution slowly over a period of 20 minutes. The resulting mixture was heated at 70 °C for 2 hours followed by stripping in vacuum to remove toluene and form a metal-ligand catalyst.

Table 4 - Ligands used in Examples 1 and 3

[0228] In example 4, the samples prepared in example 3 were used to catalyze reactions for polyurethane formation. Glycerol propoxylate (5.0 g), silicone oil (0.1 g) and a catalyst prepared in Example 3 (0.046 g to 0.4 g) were loaded in a cup (4 cm id and 4 cm depth) and mixed by a magnetic stir bar. Next, 3.7 g MDI was added to the cup. The elapsed time from MDI addition to when the magnetic stir bar stopped due to viscosity increase of the contents of the cup was measured with a stopwatch. This elapsed time was used to estimate the rate of polyurethane formation from the glycerol propoxylate and MDI. Table 5, below, summarizes the reactions catalyzed by different amount of metal-ligand catalysts with three different kinds of ligands. As controls, the precursor only and a tin catalyst were also tested according to the method of this example 4. Table 5 - Catalysts for polyurethane

In Table 4, ND means not determined because the catalyst was a solid.

[0229] In example 5, polyester compositions were prepared by combining 165 g of a fatty acid solution in soya oil and 55 g of phthalic anhydride with 47 g of pentaerythritol. In the control samples, 0.35 g of a commercially available tin catalyst (FASCAT 4204) was added. In the examples of the invention, the catalyst was 0.23 g of the reaction product of Ti(OEt)4 and 2-thiophene acetic acid, described above. Table 6, below, shows the fatty acids and their percentage in soya oil used to prepare the samples.

Table 6

[0230] Polyester syntheses were evaluated by measuring the production of water versus time of reaction. Samples were taken periodically from 60 to 500 minutes. No statistically significant difference in the amounts of water produced over time was observed when samples containing tin catalyst were compared to the samples containing the reaction product of Ti(OEt)4 and 2-thiophene acetic acid. Without wishing to be bound by theory, it is thought that the effect of catalysts in such reaction was linked to the transesterifica^tinn process that lead to higher molecular weight and longer polymeric chains without ser impact on water production. However, the comparative samples made with the tin CE showed an unacceptably higher viscosity (with no dilution), presuming a higher mass, than the samples with the reaction product of Ti(OEt)4 and 2-thiophene acetic acid. IR and

DSC analyses showed that the alkyd resin produced with the tin catalyst obtained was linked to a over-condensation of the multiple OH groups of pentaerythritol resulting in higher network building that caused no solubility in any solvent.

[0231] Additional tests were performed on the alkyd resins produced by curing the polyester compositions. Viscosity was measured using a rotational Brookfield viscometer at room temperature (25 °C) and 50 rpm. The spindle used was S02. Please provide a test method, with temperature. GPC was used to determine number average molecular weight (Mw). The results are in Table 7.

Table 7 Catalyst Viscosity 50 RPM GPC Remark

60% in xylene (Mw)

No catalyst (comparative) 190 cP 15700 Appearance ok

Reaction product of Ti(OEt)4 and 262 cP 48600 Appearance ok

2-thiophene acetic acid

FASCAT 4204 (comparative, tin No dilution possible 156100 Gel

catalyst)

[0232] These results showed that the tin-free catalyst, which is a reaction product of Ti(OEt)4 and 2-thiophene acetic acid, had catalytic activity for ester linkage formation.

[0233] In example 6, samples were prepared by combining a catalyst prepared as described above and a commercially available polyorganosiloxane resin comprising T units having methoxy and methyl groups. The resin was US-CF-2403, which is available from Dow Corning Corporation of Midland, Michigan, U.S.A. The solution of resin and catalyst contained 5% of the catalyst to be tested, or a combination of 1 % TNBT and 1 % catalyst of the catalyst to be tested, and xylene was added as a solvent, if needed to make the sample in the form of a solution.

[0234] Samples of the solutions were applied on glass panels at 75μ wet film thickness. The samples were allowed to dry and cure at room temperature (25 °C) under ambient air conditions. The coated pieces of glass were set on an automatic drying time recorder, and needles fixed on holders were put in contact with the coating. The needle holder moved along the glass substrate slowly until it reached the end of its courses. The time for the needle to cover the length of the substrate was varied from 6 to 24 hours. By analyzing the impression left by the needle on the dried coating, it was possible to define the film drying time. The final drying time was achieved when no scratch was seen anymore. This time was expressed in hours knowing the time for the needle to reach the end of the pane the distance from the beginning of the panel to the no scratch zone.

[0235] Pendulum hardness was measured using an Koenig pendulum instrument that consists of a pendulum which is free to swing on two balls resting on a coated test panel. The pendulum hardness test was based on the principle that the amplitude of the pendulum's oscillation will decrease more quickly when supported on a softer surface. The hardness of any given coating is given by the number of oscillations made by the pendulum within the specified limits of amplitude determined by accurately positioned photo sensors. An electronic counter recorded the number of swings made by the pendulum. The test involved noting the number of oscillations for the amplitude of swing to decrease from either 6 to 3 degrees and the time to form a hard coating.

[0236] Final drying times and Koenig hardnesses of the polyorganosiloxane resin samples are shown below in Table 8. Table 8

[0237] TNBT' means tetran-n-butyl titanate. 'SnOct' means tin octoate.

[0238] Dow Corning-1 was a reaction product of iron (III) 2-ethylhexanoate and ethyl 4- chloroacetoacetate.

[0239] Dow Corning-10 was a reaction product of Ti(OEt)4 and 2-2-thiophene acetic acid.

[0240] Dow Corning-12 was a reaction product of iron (III) 2-ethylhexanoate and trimethylsilyloxy-3-penten-2-one.

[0241] Dow Corning -13 was a reaction product of iron (III) 2-ethylhexanoate and ethyl 3- oxopentanoate.

[0242] The use of Dow Corning-10 gave short final drying time (cure time). Withou wishing to be bound by theory, it is thought that because this catalyst showed a compatibility issue with the resin, this may have adversely affected the Koenig Hardness results. Dow Corning-1 was also found promising because the sample containing the combination of Dow Corning-1 and TNBT showed an interesting value for final drying time time of and Koenig's hardness relatively close to reference values.

[0243] The final drying time was then evaluated as described above for a sample of the same silicone resin with differing amounts of Dow Corning-1. The results are shown in table 9.

Table 9

Yes TNBT (1 %) 23

No Dow Corning-1 (1 .5%) 17

No Dow Corning-1 (2%) 15

No Dow Corning-1 (2.5%) 9

[0244] This showed that curing time of combination 1 % TNBT and 1 % Sn Octoate was similar to 1 % TNBT and 2.5% Dow Corning-1 . Without wishing to be bound by theory, it is thought that it is possible to replace the 1 % tin catalyst with 2.5% tin-free Dow Corning-1 , and a tin free solution is possible for a self-condensation system.

[0245] In example 7, a different polyorganosiloxane resin was catalyzed. Dow Corning® 3074 was a DT methoxy phenyl/methyl siloxane, which can be used in protective coatings with excellent weather resistance. This resin showed a low reactivity and a high viscosity. The resin was self-condensing at high temperatures or at room temperature (RT) when combined with silanes. Decreasing the viscosity had a sensitive and positive impact on the cure time at RT (from more than 1 week to 3 days by dilution with 25% xylene).

[0246] Drying time measurements were not possible anymore as the curing occurred in an oven for 10 minutes at 200 °C, so tackiness after curing and the Koenig's hardness were evaluated.

[0247] The reference catalyst system (control) was 2% TNBT combined with 0.5% Tin Octoate (SnOct) as a control in a composition with Dow Corning® 3074. At that level of catalyst, the films formed were not tacky and surface aspect was good. The new catalysts were screened in combination with 2% TNBT, with the same 0.5% ratio. Koenig's hardness was measured for each system. The measurements were done at day of application/curing + 1 day (D+1 ) and 7 days after curing (D+7).

[0248] The films formed were tacky just after the oven, and it was found that 24 ho were needed to achieve a fully dried surface, even if hardness appeared to be clearly higher than the control samples' values. The results are in Table 10.

Table 10 Koenig Hardness of sample with 2% TNBT Plus Catalyst in Table below

Comparative? Catalyst Koenig Hardness (h)

Yes Zn (0.5%) 46

2% TNBT was the only sample in this catalyst

[0249] Because Dow Corning-1 and Dow Corning-10 they showed good results above, additional tests were performed with higher amounts of these catalysts to get the same tackiness after oven than reference. The results are in Table 1 1 .

Table 1 1

[0250] These results showed that with a ratio of 1 .5% Dow Corning-1 combined with TNBT, the same surface aspect is achieved; with Dow Corning-10, levels >1 .5% will be needed for the same result. Without wishing to be bound by theory, it is thought that Dow Corning-1 and Dow Corning-10 are good candidates for tin replacement in catalysts for silanols condensation.

[0251 ] In example 8, condensation reaction curable polyorganosiloxane samples were prepared and evaluated as follows. Samples of catalysts were prepared in vials as described above. The catalysts were then tested for activity by performing a model cure test. The model cure test was performed at two concentrations by adding 2240 μΙ_ of mixture of 20g methyltrimethoxysilane and 31 Og of a silanol terminated

polydimethylsiloxane having a viscosity of 90-120cst (MTM/diol mix) to each flask, and then adding in 120μΙ_ of a dilute catalyst mixture for the low concentration or 240μΙ_ of the same dilute catalyst mixture for the high concentration. These flasks were then tilted slightly in a humidity chamber set at room temperature (25 °C) and 50% relative humidity. Typically, the dilute catalyst mixture was 0.025M catalyst in toluene.

[0252] After 48 hours in the humidity oven, the flasks were removed from the humidity oven, and visual viscosity observations were recorded at room temperature. The 48 hour visual viscosity measurements were determined by side to side visual comparison of the samples with vials containing different viscosity reference standards. The measurements were performed 16, 48, and 96 hours after the samples were first exposed to moisture. The visual viscosity measurement value of each sample was assigned based on the vial of the reference standard it most closely matched. The reference standards were DOW

CORNING® 200 fluids ("200 Fluid") of different viscosities, which were commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. The visual viscosity description and standard to which it corresponded are shown below in Table 12. A value of 0 or 1 indicated that the sample did not exhibit condensation reaction in the 48 hours. A value of 2 to 5 indicated that condensation reaction increasingly occurred. Replicate experiments were subject to normal variation due to various factors, such as the operator performing the visual viscosity measurement and whether the replicate experiments were performed at different times.

Table 12 - Visual Viscosity Measurement

[0253] Table 13 showed the ligand, metal precursor Ligand : Metal Ratio, reaction conditions (time and temperature), and results (Visual Viscosity and Appearance) for the samples prepared according to example 8.

Table 13

[0254] Each value in Table 13 is an average of 2 repeated experiments. The '^*' denotes that measurement was made at 135.5 hours instead of 96 hours. Dow Corning-1 , Dow Corning-10, and Dow Corning-13 are as described above.

[0255] Dow Corning-12 and DC1 -16 were also evaluated as described above, except at different times. Dow Corning-12 was as described above. Dow Corning-16 was a reaction product of iron (III) 2-ethylhexanoate and 2-thiopheneacetic acid. The results are in Tables 14 and 15, below.

Table 14.

Catalyst 17 hour 23 hour Amount of solution 120 uL 240 uL 120 uL 240 uL added

Dow Corning-12 C C not tested not tested

Dow Corning-12 3 C C not tested

Table 15.

[0256] With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush group members. Each member of a Markush group may be relied upon individually and or in combination with one or more of the other members and provides adequate support for specific embodiments within the scope of the appended claims.

[0257] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. The enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and As just one example, a range of "300 to 700" may be further delineated into a lower t i.e., 300 to 433, a middle third, i.e., 434 to 566, and an upper third, i.e., 567 to 700, w...„.. individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific

embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 0.1 %" inherently includes a subrange from 0.1 % to 35%, a subrange from 10% to 25%, a subrange from 23% to 30%, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range of Ί to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[0258] The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is expressly contemplated but is not described in detail for the sake of brevity. The disclosure has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation.

Embodiments of the Invention

[0259] In one embodiment of the invention, a urethane composition comprises:

(A) a urethane catalyst, comprising a reaction product of ingredients comprising (i) a metal precursor and (ii) a ligand,

(B) an isocyanate-functional compound, and

(C) a hydroxy-functional compound; where one of conditions (I) to (VII) is satisfied; Where condition (I) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to and is distinct from A and

where D is a divaler hydrocarbon group of formula (CR⁸2)_X, where subscript x is 0, 1 or 2 and each R independently H, an alkyl group, or a haloalkyl group; and R⁵, R⁶, and R⁷ are each independently selected from a monovalent organic group, a heteroatom, and H;

OR

Where condition (II) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi and Fe; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the ligand is distinct from A and has general formula (iii), which is

, where Q is selected from O and S, R^{1 5} is selected from a monovalent organic group and H, each R^{1 6} is independently selected from a monovalent organic group, H, and a halogen, each R^{1 7}, R^{1 8}, R^{1 9}, and R²⁰ is independently selected from H, a monovalent organic group, and a halogen, with the proviso that alternatively A^{1 6} and A²⁰ may combine to form a fused ring structure;

OR

Where condition (III) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Fe and Zn; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the the ligand is distinct from A and has general formula (iv),

which is

, where R¹ and R² are each independently selected from H and a monovalent organic group, R³ and R⁴ are each independently a monovalent organic group;

OR

Where condition (IV) is that the metal precursor has general formula: M-A_a, where M metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the ligand is distinct from A and has general

O O formula (vi), where general formula (vi) is R R _> where R¹ and R² are each independently selected from H and a monovalent organic group, R³ and R⁴ are each independently a monovalent organic group, with the proviso that at least one of R³ and R⁴ has formula -CR²¹2-C(=0)OR²², where R²¹ is alkyl or haloalkyl; and where R²² is alkyl or haloalkyl;

OR Where condition (V) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the ligand is distinct from A and is has general

formula (v), where general formula (v) is

, where each and each R^{1 0} is independently selected from H and a monovalent hydrocarbon group, and each R^{1 1} , each R^{1 2}, and each R^{1 3} is independently selected from H, halogen, and a monovalent organic group;

OR

Where condition (VI) is that the metal precursor has general formula: Ti-A_a, where each A is independently a displaceable substituent; and subscript a has a value from 1 to 4; and

the ligand is distinct from A and has general formula (vii), which is

where R¹ and R² are each independently selected from H and a monovalent organic group, R³ is alkyl of 1 or 2 carbon atoms and R⁴ is alkoxy of 1 or 2 carbon atoms, with the proviso that when R³ has 2 carbon atoms then R⁴ has 1 carbon atom and when R⁴ has 2 carbon atoms then R³ has 1 carbon atom ;

OR

Where condition (VII) is that the metal precursor has general formula M-A_a, where M ._ selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the

; and the ligand is distinct from A and is has general formula (vii):

, where each dotted line represents that the bond may be a single bond or a double bond, subscript aa is 0 or 1 , subscript bb is 0 or 1 , subscript ee is 1 or 2,

R³² and R³³ are each independently a monovalent organic group, each R³⁰ and each R³¹ are each independently selected from H, a monovalent organic group and an inorganic group, each R³⁴ is independently selected from H and a monovalent organic group, with the provisos that alternatively R³¹ and R³² can combine to form a ring moiety, and/or alternatively R³⁰ and R³³ can combine to form a ring moiety, and/or alternatively

R³² and R³⁴ can combine to form a ring moiety, and/or alternatively, R³³ and R³⁴ can combine to form a ring moiety.

[0260] Alternatively, in the urethane composition, the ligand may be selected from the group consisting of 3,5-heptanedione, 8-hydroxyquinoline, 2-thiopheneacetic acid, ethylacetylacetonate, n-octylchloroacetoacetate, ethyl 3-oxopentanoate, and N,N'-dimethyl- 1 ,3-propanediamine.

[0261] Alternatively, the composition may be a polyorganosiloxane composition curable by a urethane reaction, where ingredient (B) may be an isocyanate-functional

polyorganosiloxane, and ingredient (C) may be a hydroxy-functional polyorganosiloxane. In the urethane composition and/or the polyorganosiloxane composition curable by a urethane reaction, the composition may further comprises an additional ingredient selected from the group consisting of (D) a blowing agent, (E) a surfactant, (F) a vehicle, (G) a filler, (H) a pigment, (I) a flame retardant, (J) a cell stabilizer, and a combination of two or more of (D), (E), (F), (G), (H), (l), and (J).

[0262] In an alternative embodiment of the invention, an ester composition comprises: (A) an ester catalyst, comprising a reaction product of ingredients comprising (i) a metal precursor and (ii) an ligand, where

(i) the metal precursor has general formula M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of metal selected for M; and

(ii) the ligand general formula (ii):

, where D is a divalent hydrocarbon group of formula (CR⁸2)_X, where subscript x is 0, 1 or 2 and each R⁸ is independently H, an alkyl group, or a haloalkyl group, and R⁵, R⁶, and R⁷ are each independently selected from a monovalent organic group, a heteroatom, and H;

(Β') a compound of formula R(C(=0)-OR")p, where R is an organic group, each R" is independently a hydrogen atom (H) or a monovalent hydrocarbon group, and subscript p is an integer representing the number of functional groups per molecule, and p > 1 ; and (C) a compound of formula R'(OR"')_m, where R' is an organic group, each R'" is independently a hydrogen atom or a monovalent hydrocarbon group, subscript m is an integer representing the number of functional groups per molecule, and m > 1 .

[0263] Alternatively, in the ester composition, M may be selected from Fe, Ti, and Zr; and alternatively Ti. Alternatively, in the ester composition, the ligand may be 2-thiophene acetic acid. Alternatively, the ester composition may further comprise an additional ingredient selected from a filler, a stabilizer, a flame retardant, an impact modifier, a pigment, a cobinder, a hardner, or a combination thereof.

[0264] In an alternative embodiment of the invention, a condensation readable polyorganosiloxane composition comprises:

(A) a condensation catalyst, comprising a reaction product of ingredients comprising (i) a metal precursor and (ii) an ligand,

(B") a silicon containing base polymer having an average, per molecule, of one or more hydrolyzable substituents; where one of conditions (I) to (III) is satisfied, where

Condition (I) is that (i) the metal precursor has the metal precursor has general formula: Fe-A_a, where M is Fe, and subscript a is 1 to 3, alternatively 2 to 3, alternatively 3;

and (ii) the ligand has general formula (iv)

, where R¹ and R² are each independently selected from H, and a monovalent organic group, and R³ and R⁴ are each independently a monovalent organic group; OR

Condition (II) is that (i) the metal precursor has general formula M-A_a, where M is selected from Fe and Ti, subscript a has a value from 1 to maximum valence of the n

selected for M, and (ii) the ligand has general formula (ii),

where D is a divalent hydrocarbon group of formula (CR⁸2)_X, where subscript x is 0, 1 or 2 and each R⁸ is independently H, an alkyl group, or a haloalkyl group, R⁵, R⁶, and R⁷ are each independently selected from a monovalent organic group, a heteroatom, and H; OR

Condition (III) is that (i) the metal precursor has general formula M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent, and subscript a has a value from 1 to maximum valence of the metal selected for M, and (ii) the ligand has general formula

general formula (vii)

, where each dotted line represents that the bond may be a single bond or a double bond, subscript aa is 0 or 1 , subscript bb is 0 or 1 , subscript ee is 1 or 2, each R³⁰ and each R³¹ are each independently selected from H, a monovalent organic group and an inorganic group, R³² and R³³ are each independently a monovalent organic group with the proviso that at least one of R³⁰ and/or R³¹ is an organosilane group of formula -R³⁵ _ccSi(R³⁶), where subscript cc is 0 or 1 , R³⁵ is a divalent hydrocarbon group, and each R³⁴ is independently selected from H and a monovalent organic group. Alternatively, condition (I) is met and the ligand is selected from ethyl 4-chloroacetoacetate and ethyl 3-oxopentanoate. Alternatively, condition (II) is met and the ligand is 2-thiophene acetic acid. Alternatively, condition (III) is met and the metal is Fe. Alternatively, condition (III) is met and the ligand is trimethylsilyloxy-3-penten- 2-one.

[0265] The condensation readable polyorganosiloxane composition may optionally further comprise one or more additional ingredients selected from (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;

tackifying agent; (U") a corrosion inhibitor; and a combination of two or more of (C"), (E"), (P), (G"), (H"), (J"), (K"), (L"), (M"), (N"), (O"), (P"), (Q"), (R"), (S"), (Γ), and (IT).

Claims

CLAIMS:

1. A method comprising:

(1 ) combining ingredients comprising a metal precursor and an organic ligand, where one of conditions (I) to (VI) is satisfied;

Where condition (I) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected organic ligand is distinct from

A and has general formula (ii), which is

, where D is a divalent hydrocarbon group of formula (CR⁸2)_X, where subscript x is 0, 1 or 2 and each

R⁸ is independently H, an alkyl group, or a haloalkyl group; and R⁵, R⁶, and R⁷ are each independently selected from a monovalent organic group, a heteroatom, and H;

OR

Where condition (II) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi and Fe; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selecte nd is distinct from A and has general formula

(iii), which is

where Q is selected from O and S, R¹ ^ is selected from a monovalent organic group and H, each R^{1 6} is independently selected from a monovalent organic group, H, and a halogen, R^{1 7}, R^{1 8}, R^{1 9}, and R²⁰ are each independently selected from H, a monovalent organic group, and a halogen, with the proviso that alternatively A^{1 6} and A²⁰ may combine to form a fused ring structure;

OR

Where condition (III) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the organic ligand is distinct from A and has general formula (vi), where general formula (vi) is

, where

R¹ and R² are each independently selected from H and a monovalent organic group, R³ and R⁴ are each independently a monovalent organic group, with the proviso that at least one of R³ and R⁴ has formula -CR²¹2-C(=0)OR²², where R²¹ is alkyl or haloalkyl; and where R²² is alkyl or haloalkyl;

OR

Where condition (IV) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the organic ligand is distinct from A

and is has general formula (v), where general formula (v)

where each R^ and each R¹ ^ is independently selected from H and a monovalent hydrocarbon group, and each R^{1 1} , each R^{1 2}, and each R^{1 3} is independently selected from H, halogen, and a monovalent organic group;

OR

Where condition (V) is that the metal precursor has general formula: Ti-A_a, where ea

is independently a displaceable substituent; and subscript a has a value from 1 tc and the organic ligand is distinct from A and has general formula

which is

, where R¹ and R² are each independently selected from H and a monovalent organic group, R³ is alkyl of 1 or 2 carbon atoms and R⁴ is alkoxy of 1 or 2 carbon atoms, with the proviso that when R³ has 2 carbon atoms then R⁴ has 1 carbon atom and when R⁴ has 2 carbon atoms then R³ has 1 carbon atom;

OR

Where condition (VI) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of r M; and the ligand is distinct from A and has

general formula (vii)

where each dotted line represents that the bond may be a single bond or a double bond, subscript aa is 0 or 1 , subscript bb is 0 or 1 , subscript ee is 1 or 2, each R³⁰ and each R³¹ are each independently selected from H, a monovalent organic group and an inorganic group, R³² and R³³ are each independently a monovalent organic group with the proviso that at least one of R³⁰ and/or R³¹ is an organosilane group of formula -R³⁵ _ccSi(R³⁶), where subscript cc is 0 or 1 , R³⁵ is a divalent hydrocarbon group, and each R³⁴ is independently selected from H and a monovalent organic group;

thereby preparing a reaction product and

optionally (2) recovering the reaction product.

2. The method of claim 1 , where the organic ligand is selected from the group consisting of 3,5-heptanedione, 8-hydroxyquinoline, 2-thiopheneacetic acid, ethylacetylacetonate, n- octylchloroacetoacetate, ethyl 3-oxopentanoate, N,N'-dimethyl-1 ,3-propanediamine, trimethylsilyloxy-3-penten-2-one, and ethyl-4-chloroacetoacetate.

3. The method of claim 1 , where one of conditions (a) to (f) is satisfied, where condit (a) to (f) are as follows:

(a) the ligand has general formula (ii), and M is Zr, Ti, or Fe; or

(b) the ligand has general formula (ii) and M is Zr.

(c) the ligand has general formula (vi) and M is Bi, Fe, Ti, Zn, or Zr; or

(d) the ligand has general formula (vi) and M is Fe, Ti, or Zn; or

(e) the ligand has general formula (vi) and M is Fe; or

(f) the ligand has general formula (v) and M is Fe

(g) the ligand has general formula (vii) and M is Fe.

4. The method of any one of claims 1 to 3, where one of conditions (h) to (q) is satisfied, where conditions (h) to (q) are as follows:

(h) the ligand is 2-thiophene acetic acid, and the metal precursor is a metal alkoxide; or (i) the ligand is 8-hydroxyquinoline and M is Bi; or

(j) the ligand is 3,5-heptanedione and M is Fe; or

(k) the ligand is 3,5-heptanedione and M is Zn; or

(I) the ligand is n-octylchloroacetoacetate and M is Fe; or

(m) the ligand is ethyl 3-oxopentanoate, and M is Fe; or

(n) the ligand is N,N'-dimethyl-1 ,3-propanediamine and M is Fe; or

(0) the ligand is ethylacetylacetonate; or

(p) the ligand is trimethylsilyloxy-3-penten-2-one and M is Fe; or

(q) the ligand is ethyl 4-chloroacetoacetate and M is Fe.

5. The method of claim 1 , where one of conditions (a) to (i) is satisfied, where

(a) M is Bi, A is a carboxylic acid ester, a is 3, and the ligand is selected from 3,5- heptanedione and 8-hydroxyquinolone; or

(b) M is Fe, A is a carboxylic acid ester, a is 3, and the ligand is selected from 3,5- heptandione, 8-hydroxyquinoline, 2-thiopheneacetic acid, ethylacetylacetonate, ethyl 3- oxopentanoate, n-Octyl-4-chloro-acetoacetate, and N,N'-Dimethyl-1 ,3-propanediamine; or

(c) M is Ti, A is an alkoxy, a is 4, and the ligand is selected from 3,5-heptandione, 2- thiopheneacetic acid, and ethylacetylacetonate; or

(d) M is Zn, A is a carboxylic acid ester, a is 2, and the ligand is selected from 3,5- heptandione and ethylacetylacetonate; or

(e) M is Zr, A is an alkoxy, a is 4, and the ligand is selected from 3,5-heptandione and 2- thiopheneacetic acid; or

(f) M is Fe, A is 2-ethylhexanoate, a is 3, and the ligand is 3,5-heptandione or Ν,Ν'- dimethyl-1 ,3-propanediamine; or

(g) M is Ti, A is ethoxy, a is 4, and the ligand is ethylacetyl acetonate; or

(h) M is Zn, A is 2-ethylhexanoate, a is 2, and the ligand is 3,5-heptandione; or

(1) M is Zr, A is iso-propoxy, a is 4, and the ligand is selected from 3,5-heptandione and 2- thiopheneacetic acid.

6. A catalyst comprising a reaction product prepared by the method of any one of claims 1 to 5.

7. A composition comprising:

(A) the catalyst of claim 6, and

(X) a reactive component.

8. The composition of claim 7, where ingredient (X) comprises

(B) an isocyanate-functional compound, and

(C) a hydroxy-functional compound.

9. The composition of claim 7, where ingredient (X) comprises

(B) a compound of formula R(C(=0)-OR")p, where R is an organic group, each R" is independently a hydrogen atom (H) or a monovalent hydrocarbon group, and subscript p is an integer representing the number of functional groups per molecule, and p > 1 , alternatively p > 2, and

(C) a hydroxy-functional compound.

10. The composition of claim 7, where ingredient (X) comprises

(B") a silanol functional base compound, and

optionally (C") a crosslinker and/or (L") a chain lengthener.

11 . A composition comprising:

(A) a urethane catalyst, comprising a reaction product of ingredients comprising (i) a metal precursor and (ii) an organic ligand,

(B) an isocyanate-functional compound, and

(C) a hydroxy-functional compound; where one of conditions (I) to (VI) is satisfied; Where condition (I) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected organic ligand is distinc

A and has general formula (ii), which is

OR

Where condition (II) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi and Fe; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the ligand is distinct from A and has general formula (iii),

where Q is selected from O and S, R^{1 5} is selected from a monovalent organic group and H, each R^{1 6} is independently selected from a monovalent organic group, H, and a halogen, each R^{1 7}, R^{1 8}, R^{1 9}, and R²⁰ is

independently selected from H, a monovalent organic group, and a halogen, with the proviso that alternatively A^{1 6} and A²⁰ may combine to form a fused ring structure;

OR

Where condition (III) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Fe and Zn; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the the organic ligand is distinct from A and has general formula

O O

(iv), which is R R _> where R¹ and R² are each independently selected from H and a monovalent organic group, R³ and R⁴ are each independently a monovalent organic group;

OR

Where condition (IV) is that the metal precursor has general formula: M-A_a, where M metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each . . .„ independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the organic ligand is distinct from A and has

O O general formula (vi), where general formula (vi) is R R _> where R¹ and R² are each independently selected from H and a monovalent organic group, R³ and R⁴ are each independently a monovalent organic group, with the proviso that at least one of R³ and R⁴ has formula -CR²¹2-C(=0)OR²², where R²¹ is alkyl or haloalkyi; and where R²² is alkyl or haloalkyi; OR

Where condition (V) is that the metal precursor has general formula: M-A_a, where M is one metal atom selected from the group consisting of Bi, Cu, Fe, Hf, Ti, Zn, and Zr; each A is independently a displaceable substituent; and subscript a has a value from 1 to maximum valence of the metal selected for M; and the organic ligand is distinct from A and is has

general formula (v), where general formula (v)

, where each

R⁹ and each R^{1 0} is independently selected from H and a monovalent hydrocarbon group, and each R^{1 1} , each R¹², and each R^{1 3} is independently selected from H, halogen, and a monovalent organic group;

OR

Where condition (VI) is that the metal precursor has general formula: Ti-A_a, where each A is independently a displaceable substituent; and subscript a has a value from 1 to 4; and the organic ligand is distinct from A and has general formula (vii), which is

, where R¹ and R² are each independently selected from H and a monovalent organic group, R³ is alkyl of 1 or 2 carbon atoms and R⁴ is alkoxy of 1 or 2 carbon atoms, with the proviso that when R³ has 2 carbon atoms then R⁴ has 1 carb™ atom and when R⁴ has 2 carbon atoms then R³ has 1 carbon atom.

12. The composition of claim 1 1 , where the organic ligand is selected from the group consisting of 3,5-heptanedione, 8-hydroxyquinoline, 2-thiopheneacetic acid,

ethylacetylacetonate, n-octylchloroacetoacetate, ethyl 3-oxopentanoate, and N,N'-dimethyl- 1 ,3-propanediamine.

13. The composition of claim 1 1 , where one of conditions (a) to (f) is satisfied, where conditions (a) to (f) are as follows:

(a) the ligand has general formula (ii), and M is Zr, Ti, or Fe; or

(b) the ligand has general formula (ii) and M is Zr.

(c) the ligand has general formula (vi) and M is Bi, Fe, Ti, Zn, or Zr; or

(d) the ligand has general formula (vi) and M is Fe, Ti, or Zn; or (e) the ligand has general formula (iv) or general formula (vi) and M is Fe; or

(f) the ligand has general formula (v) and M is Fe.

14. The composition of any one of claims 1 1 to 13, where one of conditions (g) to (n) is satisfied, where conditions (g) to (n) are as follows:

(g) the ligand is 2-thiophene acetic acid, and the metal precursor is a metal alkoxide; or

(h) the ligand is 8-hydroxyquinoline and M is Bi; or

(i) the ligand is 3,5-heptanedione and M is Fe; or

(j) the ligand is 3,5-heptanedione and M is Zn; or

(k) the ligand is n-octylchloroacetoacetate and M is Fe; or

(I) the ligand is ethyl 3-oxopentanoate, and M is Fe; or

(m) the ligand is N,N'-dimethyl-1 ,3-propanediamine and M is Fe; or

(n) the ligand is ethylacetylacetonate.

5. The composition of claim 1 , where one of conditions (a) to (i) is satisfied, where

(e) M is Zr, A is an alkoxy, a is 4, and the ligand is selected from 3,5-heptandione am thiopheneacetic acid; or

(g) M is Ti, A is ethoxy, a is 4, and the ligand is ethylacetyl acetonate; or

(i) M is Zr, A is iso-propoxy, a is 4, and the ligand is selected from 3,5-heptandione and 2- thiopheneacetic acid.

16. The composition of any one of claims 1 1 to 15, where ingredient (B) is an isocyanate- functional organic compound.

17. The composition of any one of claims 1 1 to 16, where ingredient (B) is selected from the group consisting of aromatic diisocyanates, methylene bis(phenyl isocyanate), meta- tetramethyl xylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate; aliphatic isocyanates, cycloaliphatic isocyanates, hexamethylene diisocyanate (HDI), 1 - isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate), 4,4'-diisocyanato dicyclohexylmethane, nonanetriisocyanate (TTI), vinylisocyanate;

polymeric isocyanates, isocyanurates, isocyanurate trimer, allophanate, biuret compounds, or a combination thereof.

18. The composition of any one of claims 1 1 to 15, where ingredient (B) is an isocyanate- functional polyorganosiloxane.

19. The composition of any one of claims 1 1 to 18, where ingredient (C) is a hydroxy- functional organic compound.

20. The composition of claim 19, where ingredient (C) is selected from the group consisting of: a polyether polyol, dipropylene glycol, a poly(tetramethylene ether) glycol; a polyester polyol; a polycarbonate polyol; a polycaprolactone polyol; a polybutadiene polyol; a polysulfide polyol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 ,3-propanediol, 1 ,3- butanediol, 1 ,4-butanediol, neopentyl glycol, 1 ,6-hexanediol, 1 ,4-cyclohexanedimethanol, glycerol, trimethylolpropane, 1 ,2,6-hexanetriol, glycerol propoxylate, and a combination thereof.

21 . The composition of any one of claims 1 1 to 18, where ingredient (C) is a hydroxy functional polyorganosiloxane.

22. The composition of any one of the preceding claims, where the composition further comprises an additional ingredients selected from the group consisting of (D) a blowing agent, (E) a surfactant, (F) a vehicle, (G) a filler, (H) a pigment, (I) a flame retardant, (J) a cell stabilizer, and a combination of two or more of (D), (E), (F), (G), (H), (I), and (J).

23. A method of forming the composition of any one of the preceding claims, where the method comprises:

(i) mixing ingredients comprising (A), (B), and (C) and optionally one or more of ingredients (D) to (J); or (ii) mixing Part A and Part S of a two part composition, where Part B comprises ingredient (B), and Part A comprises ingredients (A) and (C), and optionally one or more of ingredients (D) to (J).

24. The method of claim 23, where one of conditions (a) to (d) is satisfied, where

(a) 1 ppm to 10 wt% of ingredient (A) based on total weight of all ingredients in the composition is added; and/or

(b) 30 wt% to 50 wt% of ingredient (B) based on the total weight of all ingredients in the composition is added; and/or

(c) 40 wt% to 65 wt% of ingredient (C) based on the total weight of all ingredients in the composition is added; and/or

(d) ingredients (B) and (C) are added in sufficient amounts to provide a molar ratio of isocyanate groups on ingredient (B) : OH groups on ingredient (C) from 0.1 :1 to 10:1 .

25. The method of claim 23 or claim 24, further comprising adding an additional ingredient selected from the group consisting of (D) a blowing agent, (E) a surfactant, (F) a vehicle, (G) a filler, (H) a pigment, (I) a flame retardant, (J) a cell stabilizer and a combination of two or more of (D), (E), (F), (G), (H), (I), and (J).