WO2016106390A2 - Moisture curable compositions - Google Patents

Abstract

The present invention provides moisture-curable compositions comprising a cure agent that is the reaction product of a silicate and alkoxysilane and that comprising of at least one T (SiO_3/2) unit, and at least one Q (SiO_4/2) unit, wherein the silicon atom of at least one of the said T (SiO_3/2) and Q (SiO_4/2) units are bonded to an alkoxysilane with at least one free reactive group. The use of the cure agents provides a composition that exhibits good adhesion and storage stability. The cure agents may promote curing of compositions comprising a reactive silyl group without the need for additional cure catalysts, adhesion promoters, and or crosslinkers.

Description

TITLE

MOISTURE CURABLE COMPOSITIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to and the benefit of U.S. Provisional

Patent Application No. 62/095,801, filed December 23, 2014, the disclosure of which is incorporated herein by reference in its entirety.

FIELD

[0002] The present invention relates to moisture-curable compositions comprising a metal free curing system. In particular, the present invention provides curable compositions comprising a cure agent that may be a substitute for one or more components that are conventionally employed in such components including, for example, such as catalysts, cross- linkers, and/or adhesion promoters.

BACKGROUND

[0003] Polymers having reactive-silyl groups or compositions comprising such polymers can be hydrolyzed and condensed in the presence of water and metal catalysts. Suitable known catalysts for curable compositions include compounds employing metals such as Sn, Ti, Zn, or Ca. Organotin compounds such as, for example, dibutyltin dilaurate (DBTDL) are widely used as condensation cure catalysts to accelerate the moisture-assisted curing of a number of different polyorganosiloxanes and non-silicone polymers having reactive terminal silyl groups such as room temperature vulcanizing (RTV) formulations including RTV-1 and RTV-2 formulations. Environmental regulatory agencies and directives, however, have increased or are expected to increase restrictions on the use of organotin compounds in formulated products. For example, while formulations with greater than 0.5 wt. % dibutyltin presently require labeling as toxic with reproductive IB classification, dibutyltin-containing formulations are proposed to be completely phased out in consumer applications during the next two to three years.

[0004] The use of alternative organotin compounds such as dioctyltin compounds and dimethyltin compounds can only be considered as a short-term remedial plan, as these organotin compounds may also be regulated in the future. It would be beneficial to identify non-tin-based catalysts that accelerate the condensation curing of moisture-curable silicones and non-silicones. [0005] Substitutes for organotin catalysts should exhibit properties similar to organotin compounds in terms of curing, storage, and appearance. Non-tin catalysts would also desirably initiate the condensation reaction of the selected polymers and complete this reaction upon the surface and may be in the bulk in a desired time schedule. There are therefore many proposals for the replacement of organometallic tin compounds with other metal- and non-metal-based compounds. These new catalysts have specific advantages and disadvantages in view of replacing tin compounds perfectly. Therefore, there is still a need to address the weaknesses of possible non-tin compounds as suitable catalysts for condensation cure reactions. The physical properties of uncured and cured compositions also warrant examination, in particular to maintain the ability to adhere onto the surface of several substrates.

[0006] Prior replacement catalysts for organotin compounds generally cannot maintain their ability to cure when exposed to humidity or ambient air after storage over months in a sealed cartridge. It is always a specific requirement for moisture-curable compositions to achieve the shortest possible curing times, showing a tack-free surface as well as curing through the complete bulk in thick section for RTV-1 and RTV-2 compositions. Additionally, such compositions should provide a reasonable adhesion after cure onto a variety of substrates. Thus, there is still a need for altemative materials to replace tin as a core catalyst in moisture curable compositions.

SUMMARY

[0007] The present invention provides tin-free, curable compositions comprising silyl- terminated polymers and a cure agent. In one embodiment, the present invention provides curable compositions employing a cure agent that is metal free and a reaction product of a silicate and alkoxysilane having at least one free reactive group. The cure agents have been found to promote curing and may also function as a cross-linker and/or adhesion promoter.

[0008] In one embodiment, the curable composition comprises (A) a polymer having a reactive silicon-containing group, (B) a cure agent derived from the reaction product of a silicate and an alkoxysilane having a free reactive group, and (C) optionally a filler.

[0009] In one aspect, the invention provides a curable composition exhibiting a relatively short tack-free time, curing through the bulk, as well as long storage stability in the cartridge, i.e., in the absence of humidity. The cure agents described herein have been found to exhibit good curing behavior, including good tack free time and/or bulk curing. Thus, the cure agents can be suitable as replacements for organotin catalysts in compositions having a reactive, silyl- terminated polymer that can undergo condensation reactions, such as in RTV-1 and RTV-2 formulations. [0010] Curable compositions using the present cure agents may also exhibit certain storage stability of the uncured composition in the cartridge, adhesion onto several surfaces, and a cure rate in a predictable time scheme.

[0011] In one embodiment, the present invention provides a curable composition that is substantially free of tin. In one embodiment, the composition is substantially metal free.

[0012] In one aspect, the present invention provides (A) a polymer having at least a reactive silyl group; (B) a cure agent which is a reaction product of a silicate and alkoxysilane and that comprising of at least one T (S1O₃/2) unit, and at least one Q (S1O4/2) unit, wherein the silicon atom of at least one of the said T (S1O₃/2) and Q (S1O4/2) units are bonded to an alkoxysilane with at least one free reactive group, the alkoxysilane being chosen from a compound of the formulas:

A ⁹Si(OR²⁰)₃;

(R²¹0)₃-_qR²² _xSi-R² -A²-R² -SiR²² _q(OR²¹)₃-_q;

or a combination of two or more thereof, wherein R¹⁹ is independently selected from hydrocarbon group optionally substituted with heteroatom selected from N, S, P, and O; R²⁰ is independently a substituted or unsubstituted hydrocarbon group of 1 to 5 carbon atoms; A¹ is independently selected from a substituted or unsubstituted amine, epoxy, acryl, acetyl, or acidic group; R²¹ is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 5 carbon atoms; R²² and R²³ are independently chosen from a substituted or unsubstituted divalent hydrocarbon group; A² is independently selected from an amine, epoxy, acryl, acetyl, acidic derivatives; and q is independently an integer selected from 1 to 3; and (C) optionally, a filler component.

[0013] In one embodiment, the polymer (A) has the formula: [R¹ _aR²3-_aSi-Z-]_n- -Z-

SiR¹ _aR²3-_a. In another embodiment, X is chosen from a polyurethane; a polyester; a polyether; a polycarbonate; a poly olefin; a polyesterether; and a polyorganosiloxane having units of R₃S1O1/2, R2S1O, RS1O₃/2, and/or S1O2_, n is 0 to 100, a is 0 to 2, R, R¹, and R² can be identical or different at the same silicon atom and chosen from C1-C10 alkyl; C1-C10 alkyl substituted with one or more of CI, F, N, O, or S; a phenyl; C7-C1₆ alkylaryl; C7-C1₆ arylalkyl; C2-C2o-polyalkylene ether; or a combination of two or more thereof. In yet another aspect, R² is chosen from OH, Ci-Cg alkoxy, C2-C1₈ alkoxyalkyl, alkoxyaryl, oximoalkyl, oximoaryl, enoxyalkyl, enoxyaryl, aminoalkyl, aminoaryl, carboxyalkyl, carboxyaryl, amidoalkyl, amidoaryl, carbamatoalkyl, carbamatoaryl, or a combination of two or more thereof, and Z is a bond, a divalent unit selected from the group of a C1-C14 alkylene, or O.

[0014] In one embodiment, the composition may optionally comprise (D) a crosslinker or chain extender. In one embodiment, the crosslinker is chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkoxyaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof.

[0015] According to one embodiment, the polymer component (A) is chosen from a polyorganosiloxane comprising divalent units of the formula [R2S1O] in the backbone, wherein R is chosen from C1-C1₀ alkyl; C1-C1₀ alkyl substituted with one or more of CI, F, N, O, or S; phenyl; C7-C1₆ alkylaryl; C7-C1₆ arylalkyl; C2-C2₀ polyalkylene ether; or a combination of two or more thereof.

[0016] According to one embodiment, the crosslinker component (D) is chosen from tetraethylorthosilicate (TEOS); methyltrimethoxysilane (MTMS); vinyltrimethoxysilane; methylvinyldimethoxysilane; dimethyldimethoxysilane; dimethyldiethoxysilane; vinyltriethoxysilane; tetra(n-propyl)orthosilicate; tris(methylethylketoximo)vinylsilane; tris(methylethylketoximo)methylsilane; tris(acetamido)methylsilane; bis(acetamido)dimethylsilane; tris(N-methylacetamido)methylsilane; bis(N- methylacetamido)dimethylsilane; (N-methylacetamido)methyldialkoxysilane; tris(benzamido)methylsilane; tris(propenoxy)methylsilane; alkyldialkoxyamidosilanes; alkylalkoxybisamidosilanes; methylethoxybis(N-methylbenzamido)silane; methylethoxydibenzamidosilane; methyldimethoxy(ethylmethylketoximo)silane; bis(ethylmethylketoximo)methylmethoxysilane; (acetaldoximo)methyldimethoxysilane; (N- methylcarbamato)methyldimethoxysilane; (N-methylcarbamato) ethyldimethoxy silane; (isopropenoxy)methyldimethoxysilane; (isopropenoxy)trimethoxysilane; tris(isopropenoxy)methylsilane; (but-2-en-2-oxy)methyldimethoxysilane; (1 - phenylethenoxy)methyldimethoxysilane; 2-((l -carboethoxy)propenoxy) methyldimethoxysilane; bis(N-methylamino)methylmethoxysilane; (N-methylamino)vinyldimethoxysilane; tetrakis(N,N- diethylamino)silane; methyldimethoxy(N-methylamino)silane; methyltris(cyclohexylamino)silane; methyldimethoxy(N-ethylamino)silane; dimethylbis(N,N- dimethylamino)silane; methyldimethoxy(N-isopropylamino)silane dimethylbis(N,N- diethylamino)silane; ethyldimethoxy(N-ethylpropionamido)silane; methyldimethoxy(N- methylacetamido)silane; methyltris(N-methylacetamido)silane; ethyldimethoxy(N- methylacetamido)silane; methyltris(N-methylbenzamido)silane; methylmethoxybis(N- methylacetamido)silane; methyldimethoxy(8-caprolactamo)silane; trimethoxy(N- methylacetamido)silane; methyldimethoxy(0-ethylacetimidato)silane; methyldimethoxy(0- propylacetimidato)silane; methyldimethoxy(N,N'^V'-trimethylureido)silane; methyldimethoxy(N-allyl-N',N'-dimethylureido)silane; methyldimethoxy(N-phenyl-N',N'- dimethylureido)silane;

methyldimethoxy(isocyanato)silane; dimethoxydiisocyanatosilane; methyldimethoxy- isothiocyanatosilane; methylmethoxydiisothiocyanatosilane; methyltriacetoxysilane; methylmethoxydiacetoxysilane; methylethoxydiacetoxysilane; methylisopropoxydiacetoxysilane; methyl(n-propoxy)diacetoxysilane; methyldimethoxyacetoxysilane; methyldiethoxyacetoxysilane; methyldiisopropoxyacetoxysilane; methyldi(n-propoxy)acetoxysilane; or the condensates thereof; or a combination of two or more thereof.

[0017] In one embodiment, the curable composition is free of any adhesion promoters.

In another embodiment, the curable composition comprises an adhesion promoter.

[0018] In one embodiment, the composition may optionally comprise (E) at least one adhesion promoter chosen from a silane or siloxane other than the compounds listed under (D).

[0019] According to one embodiment, the adhesion promoter component (E) is chosen from an (aminoalkyl)trialkoxysilane, an (aminoalkyl)alkyldialkoxysilane, a bis(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)cyanuarate, a tris(trialkoxysilylalkyl)isocyanurate, an

(epoxyalkyl)trialkoxysilane, an (epoxyalkylether)trialkoxysilane, or a combination of two or more thereof.

[0020] According to one embodiment, the composition is provided as a one-part composition. In another embodiment, the composition is provided as a two-part composition.

DETAILED DESCRIPTION

[0021] The present invention provides a curable composition employing a metal-free curing agent. The curing agent comprises an oligomeric resin material that is the reaction product of a silicate and an alkoxysilane having a free reactive group. Without being bound to any particular theory, the curing agent may function within the composition as a cure catalyst, crosslinker, and/or an adhesion promoter. Thus, use of the present cure agent may provide a composition that is free of any additional catalyst, e.g., a tin or other metal or non-metal catalyst, crosslinker, or adhesion promoter. It will be appreciated, however, that other components such as, for example, crosslinkers, adhesion promoters, catalysts, etc., may be employed in the composition. Compositions comprising the present cure agents exhibit good curing properties and can even exhibit similar or superior curing properties compared to compositions employing organotin compounds, such as DBTDL, in terms of accelerating moisture-assisted condensation curing of silicones to result in cross-linked silicones that can be used as sealants and RTVs (Room-Temperature Vulcanized Rubber). Compositions employing the present cure agents may exhibit excellent properties with respect to deep section cure, surface cure, and/or adhesion. Further, the compositions comprising such cure agents also exhibit improved storage stability.

[0022] As used herein, "alkyl" includes straight, branched, and cyclic alkyl groups.

Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl, ethyl-hexyl, etc.

[0023] As used herein, "substituted alkyl" includes an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. As used herein, unsubstituted means the particular moiety carries hydrogen atoms on its constituent atoms, e.g. CH₃ for unsubstituted methyl. Substituted means that the group can carry typical functional groups known in organic chemistry.

[0024] As used herein, "aryl" includes a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups. Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl, naphthalenyl, etc.

[0025] As used herein, "substituted aryl" includes an aromatic group substituted as set forth in the above definition of "substituted alkyl." Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. In one embodiment, substituted aryl groups herein contain 1 to about 30 carbon atoms.

[0026] As used herein "aralkyl" include an alkyl group substituted by aryl groups.

[0027] As used herein, "alkenyl" includes any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group. Specific and non-limiting examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, etc.

[0028] As used herein, "alkynyl" includes any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carbon-carbon triple bond or elsewhere in the group.

[0029] As used herein, "unsaturated" refers to one or more double or triple bonds. In one embodiment, it refers to carbon-carbon double or triple bonds.

[0030] As used herein, the terms "alkylene," "cycloalkylene," "alkynylene,"

"alkenylene," and "arylene" alone or as part of another substituent refers to a divalent radical derived from an alkyl, cycloalkyl, heteroalkyl, alkynyl, alkenyl, or aryl group, respectively. The respective radicals can be substituted or unsubstituted, linear or branched.

[0031] As used herein, "silicon-containing alkyl," "silicon-containing aryl," etc., include compounds comprising the group -S1R3, where R may be the same or different and is chosen from the group containing an alkyl, a cycloalkyl, a heteroalkyl, a heterocycloalkyl, an aryl, a heteroaryl, an alkoxy, or a hydroxy.

[0032] As used herein, "heteroalkyl," "heteroaryl," etc. include compounds comprising a hetero atom such as O, N, P, S, etc.

[0033] In one embodiment, the present invention provides a curable composition comprising (A) a polymer having at least a reactive silyl group; (B) an oligomeric curing agent which is derived from the reaction product of an alkoxysilane and a silicate, the oligomer comprising at least one T (S1O3/2) unit, and at least one Q (S1O4/2) unit, wherein the silicon atom of at least one of the said T (S1O₃/2) and Q (S1O4/2) units are bonded to an alkoxysilane with at least one free reactive group; and (C) optionally, a filler component.

[0034] The polymer component (A) may be a liquid- or solid-based polymer having a reactive terminal silyl group. The polymer component (A) is not particularly limited and may be chosen from any cross-linkable polymer as may be desired for a particular purpose or intended use. Non-limiting examples of suitable polymers for the polymer component (A) include polyorganosiloxanes (Al) or organic polymers free of siloxane bonds (A2), wherein the polymers (Al) and (A2) comprise reactive terminal silyl groups. In one embodiment, the polymer component (A) may be present in an amount of from about 10 to about 90 wt. % of the curable composition. In one embodiment, the curable composition comprises about 100 pt. wt. of the polymer component (A).

[0035] As described above, the polymer component (A) may include a wide range of polyorganosiloxanes. In one embodiment, the polymer component may comprise one or more polysiloxanes and copolymers of formula (1):

R¹ may be chosen from linear or branched alkyl, linear or branched heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, linear or branched aralkyl, linear or branched heteroaralkyl, or a combination of two or more thereof. In one embodiment, R¹ may be chosen from C1-C1₀ alkyl; C1-C1₀ alkyl substituted with one or more of CI, F, N, O, or S; phenyl; C7-C1₆ alkylaryl; C7-C1₆ arylalkyl; C2-C2₀ polyalkylene ether; or a combination of two or more thereof. Exemplary groups are methyl, trifluoropropyl, and/or phenyl groups.

[0036] R² may be a group reactive to protic agents such as water. Exemplary groups for

R² include OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy, arylcarboxy, alkylamido, arylamido, or a combination of two or more thereof. In one embodiment, R² is chosen from OH, Ci-Cg alkoxy, C2-C 18 alkoxyalkyl, amino, alkenyloxy, alkyloximo, alkylamino, arylamino, alkylcarboxy, arylcarboxy, alkylamido, arylamido, alkylcarbamato, arylcarbamato, or a combination of two or more thereof.

[0037] Z may be a bond, a divalent linking unit selected from the group of O, hydrocarbons which can contain one or more O, S, or N atom, guanidine-containing, urethane, ether, ester, urea units or a combination of two or more thereof. If the linking group Z is a hydrocarbon group, then Z is linked to the silicon atom over a silicon-carbon bond. In one embodiment, Z is chosen from a C1-C 14 alkylene.

[0038] X is chosen from a polyurethane; a polyester; a polyether; a polycarbonate; a polyolefin; a polyesterether; and a polyorganosiloxane having units of

R^iC ^, and/or S1O2, where R¹ is defined as above. X may be a divalent or multivalent polymer unit selected from the group of siloxy units linked over oxygen or hydrocarbon groups to the terminal silyl group comprising the reactive group R² as described above, polyether, alkylene, isoalkylene, polyester, or polyurethane units linked over hydrocarbon groups to the silicon atom comprising one or more reactive groups R² as described above. The hydrocarbon group X can contain one or more heteroatoms such as N, S, O, or P forming guanidine-containings, esters, ethers, urethanes, esters, and/or ureas. In one embodiment, the average polymerization degree (P_n) of X should be more than 6, e.g. polyorganosiloxane units of

and/or S1O2. In formula (2), n is 0 to 100; desirably 1, and c is 0 to 2, desirably 0 to 1.

[0039] Non-limiting examples of the components for unit X include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyethylene- polyoxypropylene copolymer, polyoxytetramethylene, or polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, polychloroprene, polyisoprene, polybutadiene, copolymer of isobutylene and isoprene, copolymers of isoprene or butadiene and acrylonitrile and/or styrene, or hydrocarbon polymers such as hydrogenated polyolefin polymers produced by hydrogenating these polyolefin polymers; polyester polymer manufactured by a condensation of dibasic acid such as adipic acid or phthalic acid and glycol, or ring-opening polymerization of lactones; polyacrylic acid ester produced by radical polymerization of a monomer such as C2-Cg-alkyl acrylates, vinyl polymers, e.g., acrylic acid ester copolymer of acrylic acid ester such as ethyl acrylate or butyl acrylate and vinyl acetate, acrylonitrile, methyl methacrylate, acrylguanidine-containing, or styrene; graft polymer produced by polymerizing the above organic polymer with a vinyl monomer; polycarbonates; polysulfide polymer; polyguanidine-containing polymer such as Nylon 6 produced by ring-opening polymerization of ε-caprolactam, Nylon 6-6 produced by polycondensation of hexamethylenediamine and adipic acid, etc., Nylon 12 produced by ring-opening polymerization of ε-laurolactam, copolymeric polyguanidine-containings, polyurethanes, or poly ureas.

[0040] Particularly suitable polymers include, but are not limited to, polysiloxanes, polyoxyalkylenes, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polybutadiene and hydrogenated polyisoprene, or polyethylene, polypropylene, polyesters, polycarbonates, polyurethanes, polyurea polymers and the like. Furthermore, saturated hydrocarbon polymer, polyoxyalkylene polymer, and vinyl copolymer are particularly suitable due to their low glass transition temperature which provide a high flexibility at low temperatures, i.e., below 0 °C.

[0041] The reactive silyl groups in formula (1) can be introduced by employing silanes containing a functional group which has the ability to react by known methods with unsaturated hydrocarbons via hydrosilylation, or reaction of SiOH, aminoalkyl or -aryl, HOOC-alkyl or - aryl, HO-alkyl or -aryl, HS-alkyl or -aryl, Cl(0)C-alkyl or -aryl, epoxyalkyl or epoxycycloalkyl groups in the prepolymer to be linked to a reactive silyl group via condensation or ring-opening reactions. Examples of the main embodiments include the following: (i) siloxane prepolymers having a SiOH group that can undergo a condensation reaction with a silane (LG)SiR¹ _cR²3_-c whereby a siloxy bond≡Si-0-SiR¹ _cR²3-c is formed while the addition product of the leaving group (LG) and hydrogen is released (LG-H); (ii) silanes having an unsaturated group that is capable of reacting via hydrosilylation or radical reaction with a SiH group or radically activated groups of a silane such as SiH or an unsaturated group; and (iii) silanes including organic or inorganic prepolymers having OH, SH, amino, epoxy, -COCl, -COOH groups, which can react complementarily with epoxy, isocyanato, OH, SH, cyanato, carboxylic halogenides, reactive alkylhalogenides, lactones, lactams, or amines, that is to link the reactive prepolymer with the organofunctional silanes to yield a silyl functional polymer.

[0042] Silanes suitable for method (i) include alkoxysilanes, especially tetraalkoxysilanes, di- and trialkoxysilanes, di- and triacetoxysilanes, di- and triketoximosilanes, di- and trialkenyloxysilanes, di- and tricarbonamidosilanes, wherein the remaining residues at the silicon atom of the silane are substituted or unsubstituted hydrocarbons. Other non-limiting silanes for method (i) include alkyltrialkoxysilanes, such as vinyltrimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, aminoalkyltrimethoxysilane, ethyltriacetoxysilane, methyl- or propyltriacetoxysilane, methyltributanonoximosilane, methyltripropenyloxysilane, methyltribenzamidosilane, or methyltriacetamidosilane. Prepolymers suitable for reaction under method (i) are SiOH-terminated polyalkylsiloxanes, which can undergo a condensation reaction with a silane having hydrolyzable groups attached to the silicon atom. Exemplary SiOH-terminated polyalkyldisiloxanes include polydimethylsiloxanes.

[0043] Suitable silanes for method (ii) include alkoxysilanes, especially trialkoxysilanes

(HSi(OR)₃) such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Hydrogenchlorosilanes are in principle possible but are less desirable due to the additional replacement of the halogen through an alkoxy, acetoxy group, etc. Other suitable silanes include organofunctional silanes having unsaturated groups which can be activated by radicals, such as vinyl, allyl, mercaptoalkyl, or acrylic groups. Non-limiting examples include vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, and methacryloxypropyltrimethoxysilane. Prepolymers suitable for reaction under method (ii) include vinyl-terminated polyalkylsiloxanes, preferably polydimethylsiloxanes, hydrocarbons with unsaturated groups which can undergo hydrosilylation or can undergo radically induced grafting reactions with a corresponding organofunctional group of a silane comprising, for example, unsaturated hydrocarbon or a SiH group.

[0044] Another method for introducing silyl groups into hydrocarbon polymers can be the copolymerization of unsaturated hydrocarbon monomers with the unsaturated groups of silanes. The introduction of unsaturated groups into a hydrocarbon prepolymer may include, for example, the use of alkenyl halogenides as chain stopper after polymerization of the silicon free hydrocarbon moiety.

[0045] Desirable reaction products between the silanes and prepolymers include the following structures:

Suitable silanes for method (iii) include, but are not limited to, alkoxysilanes, especially silanes having organofunctional groups to be reactive to -OH, -SH, amino, epoxy, -COC1, or -COOH.

[0046] In one embodiment, these silanes have an isocyanatoalkyl group such as gamma- isocyanatopropyltrimethoxysilane, gamma-isocyanatopropylmethyldimethoxysilane, gamma- isocyanatopropyltriethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, epoxylimonyltrimethoxysilane, N-(2-arninoethyl)-aminopropyltrimethoxysilane, gamma- aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma- aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, etc.

[0047] In one embodiment, it is desirable to select either blocked amines or isocyanates

(Z^'-X)_n-Z' for carrying out first a complete mixing and then the following coupling reaction. Examples of blocking agents are disclosed in EP 0947531 and other blocking procedures that employ heterocyclic nitrogen compounds such as caprolactam or butanone oxime, or cyclic ketones referred to in U.S. Patent 6,827,875 both of which are incorporated herein by reference in their entirety.

[0048] Examples of suitable prepolymers for a reaction under method (iii) include, but are not limited to, polyalkylene oxides having OH groups, in one embodiment with a high molecular weight (M_w, weight-average molecular weight > 6000 g/mol) and a polydispersity M_w/M_n of less than 1.6; urethanes having remaining NCO groups, such as NCO functionalized polyalkylene oxides, especially blocked isocyanates. Prepolymers selected from the group of hydrocarbons having -OH, -COOH, amino, epoxy groups, which can react complementarily with an epoxy, isocyanato, amino, carboxyhalogenide or halogenalkyl group of the corresponding silane having further reactive groups useful for the final cure.

[0049] Suitable isocyanates for the introduction of a NCO group into a polyether may include toluene diisocyanate, diphenylmethane diisocyanate, or xylene diisocyanate, or aliphatic polyisocyanate such as isophorone diisocyanate, or hexamethylene diisocyanate.

[0050] The polymerization degree of the unit X depends on the requirements of viscosity and mechanical properties of the cured product. If X is a polydimethylsiloxane unit, the average polymerization degree based on the number average molecular weight M_n is preferably 7 to 5000 siloxy units, preferably 200 to2000 units. In order to achieve a sufficient tensile strength of > 5 MPa, an average polymerization degree P_n of > 250 is suitable whereby the polydimethylsiloxanes have a viscosity of more than 300 mPa.s at 25 °C. If X is a hydrocarbon unit other than a polysiloxane unit, the viscosity with respect to the polymerization degree is much higher.

[0051] Examples of the method for synthesizing a polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a metal-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound, a polymerization method using a composite metal cyanide complex catalyst disclosed, e.g., in U.S. Patent Nos. 3,427,256; 3,427,334; 3,278,457; 3,278,458; 3,278,459; 3,427,335; 6,696,383; and 6,919,293.

[0052] If the group X is selected from hydrocarbon polymers, then polymers or copolymers having isobutylene units are particularly desirable due to its physical properties such as excellent weatherability, excellent heat resistance, and low gas and moisture permeability.

[0053] Examples of the monomers include olefins having 4 to 12 carbon atoms, vinyl ether, aromatic vinyl compound, vinylsilanes, and allylsilanes. Examples of the copolymer component include 1-butene, 2-butene, 2-methyl-l-butene, 3-methyl-l-butene, pentene, 4- methyl-l-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, alpha-methylstyrene, dimethylst rene, beta-pinene, indene, and for example, but not limited to, vinyltrialkoxysilanes, e.g. vinyltrimethoxysilane, vinylmethyldichlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, gamma-methacryloyloxypropyltrimethoxysilane, and gamma- methacryloyloxypropylmethyldimethoxysilane.

[0054] Examples of suitable siloxane-free organic polymers include, but are not limited to, silylated polyurethane (SPUR), silylated polyester, silylated polyether, silylated polycarbonate, silylated polyolefins like polyethylene, polypropylene, silylated polyesterether and combinations of two or more thereof. The siloxane-free organic polymer may be present in an amount of from about 10 to about 90 wt. % of the composition or about 100 pt. wt.

[0055] In one embodiment, the polymer component (A) may be silylated polyurethane

(SPUR). Such moisture curable compounds are known in the art in general and can be obtained by various methods including (i) reacting an isocyanate-terminated polyurethane (PUR) prepolymer with a suitable silane, e.g., one possessing both hydrolyzable functionality at the silicon atom, such as, alkoxy, etc., and secondly active hydrogen-containing functionality such as mercaptan, primary or secondary amine, preferably the latter, etc., or by (ii) reacting a hydroxyl- terminated PUR (polyurethane) prepolymer with a suitable isocyanate-terminated silane, e.g., one possessing one to three alkoxy groups. The details of these reactions, and those for preparing the isocyanate-terminated and hydroxyl-terminated PUR prepolymers employed therein can be found in, amongst others: U.S. Pat. Nos. 4,985,491; 5,919,888; 6,207,794; 6,303,731 ; 6,359,101 ; and 6,515,164, and published U.S. Patent Publication Nos. 2004/0122253 and US 2005/0020706 (isocyanate-terminated PUR prepolymers); U.S. Pat. Nos. 3,786,081 and 4,481,367 (hydroxyl- terminated PUR prepolymers); U.S. Pat. Nos. 3,627,722; 3,632,557; 3,971,751; 5,623,044; 5,852,137; 6,197,912; and 6,310,170 (moisture-curable SPUR (silane modified/terminated polyurethane) obtained from reaction of isocyanate-terminated PUR prepolymer and reactive silane, e.g., aminoalkoxysilane); and, U.S. Pat. Nos. 4,345,053; 4,625,012; 6,833,423; and published U.S. Patent Publication 2002/0198352 (moisture-curable SPUR obtained from reaction of hydroxyl-terminated PUR prepolymer and isocyanatosilane). The entire contents of the foregoing U.S. patent documents are incorporated by reference herein. Other examples of moisture-curable SPUR materials include those described in U.S. Pat. No. 7,569,653, the disclosure of which is incorporated by reference in its entirety.

[0056] In one embodiment, the polymer component (A) may be a polymer of formula (2):

(2) where R¹, R², Z, and c are defined as above with respect to formula (2); R is C1-C6 alkyl (an exemplary alkyl being methyl); x is 0 to about 10,000, in one embodiment from 11 to about 2500; and y is 0 to about 10,000; preferably 0 to 500. In one embodiment, Z in a compound of formula (2) is a bond or a divalent C1-C14 alkylene group, especially preferred is -C2H4-.

[0057] In one embodiment, the polymer component (A) may be a polyorganosiloxane of the formula (3):

R²3-_c-_dSiR _cR⁴ _d-[OSiR R⁴]_x-[OSiR R⁴]_y-OSiR _eR⁴ _fR²3_-e-f (3) R³ and R⁴ can be identical or different on the same silicon atom and are chosen from hydrogen; C1-C1₀ alkyl; C1-C1₀ heteroalkyl, C3-C12 cycloalkyl; C2-C₃₀ heterocycloalkyl; C6-C1₃ aryl; C7-C30 alkylaryl; C7-C30 arylalkyl; C4-C12 heteroaryl; C5-C30 heteroarylalkyl; C5-C30 heteroalkylaryl; C2- C1₀₀ poly alkylene ether; or a combination of two or more thereof. R², c, x, and y are as defined above; d is 0, 1, or 2; e is 0, 1, or 2; and f is 0, 1, or 2.

[0058] Non-limiting examples of suitable polysiloxane-containing polymers (Al) include, for example, silanol-stopped polydimethylsiloxane, silanol or alkoxy-stopped polyorganosiloxanes, e.g., methoxystopped polydimethylsiloxane, alkoxy-stopped polydimethylsiloxane-polydiphenylsiloxane copolymer, and silanol or alkoxy-stopped fluoroalkyl-substituted siloxanes such as poly(methyl 3,3,3-trifluoropropyl)siloxane and poly(methyl 3,3,3-trifluoropropyl)siloxane-polydimethyl siloxane copolymer. The polyorganosiloxane component (Al) may be present in an amount of about 10 to about 90 wt. % of the composition or 100 pt. wt. In one preferred embodiment, the polyorganosiloxane component has an average chain length in the range of about 10 to about 2500 siloxy units, and the viscosity is in the range of about 10 to about 500,000 mPa.s at 25 °C.

[0059] Alternatively, the composition may include silyl-terminated organic polymers

(A2) that are free of siloxane units, and which undergo curing by a condensation reaction comparable to that of siloxane containing polymers (Al). Similar to the polyorganosiloxane polymer (Al), the organic polymers (A2) that are suitable as the polymer component (A) include a terminal silyl group. In one embodiment, the terminal silyl group may be of the formula (4):

where R¹, R², and d are as defined above.

[0060] The cure agent (B) comprises an oligomeric curing agent. The oligomeric curing agent is derived from the reaction product of a silicate an alkoxysilane having a free reactive group, which product comprises at least one T (S1O₃/2) unit, and at least one Q (S1O4/2) unit, wherein the silicon atom of at least one of the said T (S1O₃/2) and Q (S1O4/2) units are bonded to an alkoxysilane with at least one free reactive group. [0061] The silicate, which provides the Q unit, is not particularly limited and can be chosen from any suitable silicate. In one embodiment, the silicate may be chosen from a compound of the formulas:

Si(OR¹⁷)₄ (5)

(R¹⁸0)₃SiO[SiO(OR¹⁸)₂]_pSi(OR¹⁸)₃ (6)

in which the groups R¹⁷ and R¹⁸ are independently chosen from a hydrogen, a CI -CIO alkyl, a C1-C10 alkoxyalkyl, and p is 0-50. Examples of suitable groups for R¹⁷ and R¹⁸ included, but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-amyl, 1 -methoxy ethyl, 2-methoxy ethyl, 1 -methoxypropyl, 2-methoxypropyl, alkyl poly ether group, especially corresponding esters of ethyl glycol, butyl glycol, etc. It will be appreciated that a combination of silicates may be employed.

[0062] Examples of suitable silicates include, but are not limited to, tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, etc.

[0063] The alkoxysilane may be chosen from a compound of formula (7), formula (8):

A¹R¹⁹Si(OR²⁰)₃ (7)

(R²¹0)_3-qR²² _qSi-R² -A²-R² -SiR²² _q(OR²¹)_3-q (8) or a combination thereof, wherein R¹⁹ is independently selected from hydrocarbon group optionally substituted with heteroatom selected from N, S, P, and O; R²⁰ is independently a substituted or unsubstituted hydrocarbon group of 1 to 5 carbon atoms, A¹ is independently selected from substituted or unsubstituted amine, epoxy, acryl, acetyl, acidic group; R²¹ is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 5 carbon

22 23 2 atoms, R , R are independently a substituted or unsubstituted divalent hydrocarbon group, A is independently selected from amine, epoxy, acryl, acetyl, acidic derivatives and q is independently an integer selected from 1 to 3.

[0064] In one embodiment, A¹ and/or A² are chosen from an amine. The amine may be a primary, secondary, or tertiary amine. In one embodiment, A¹ and/or A² are chosen from an amine of the formula -NR²⁴2, where R²⁴ is independently chosen from hydrogen, or a CI -CIO alkyl group. In on embodiment A 1 and/or A 2 are chosen from NH₂, NHR 24 , or NR 24₂.

[0065] In one embodiment, the alkoxysilane for forming the cure agent is chosen from a compound of the formulas:

E²- [(CR³ ₂ )_r-W-(CH₂ )_r-SiR¹ ₅(R²)_3-5] ₃ ( 10) where s is 2 to 3; r is 0-8; E may be selected from either a group E¹ or E². E¹ may be selected from a monovalent group comprising amine, -NH₂, -NHR²⁴, -(NHC₂H₅)_aNHR²⁴, NHC₆H₅, halogen, pseudohalogen, unsaturated aliphatic group with up to 14 carbon atoms, epoxy-group- containing aliphatic group with up to 14 carbon atoms, cyanurate-containing group, and an isocyanurate-containing group; E² may be selected from a group comprising a di- or multivalent group consisting of amine, polyamine, cyanurate-containing, and an isocyanurate-containing group, sulfide, sulfate, phosphate, phosphite, and a polyorganosiloxane group, which can contain R⁵ and R² groups; W is selected from a single bond, a heteroatomic group selected from -COO-, -0-, epoxy, -S-, -CONH-, -HN-CO-NH- units; R³ is as defined above, R¹ may be identical or different as defined above, R² is defined as above and may be identical or different; and R⁵ is E- (CR ₂)r-w-(CH²)_r-.

[0066] Examples of other suitable for the alkoxysilane include, but are not limited to, N-

(2-aminoethyl)aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- aminopropyltrimethoxysilane, bis(3-trimethoxysilypropyl)amine, N-phenyl-gamma- aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, gamma- aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, gamma- glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- glycidoxyethyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma- glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta- (3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, beta-(3,4- epoxycyclohexyl)ethyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, beta- cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma- methacryloxypropylmethyldimethoxysilane, alpha, omega- bis(aminoalkyldiethoxysilyl)polydimethylsiloxanes (Pn =1 -7), alpha, omega- bis(aminoalkyldiethoxysilyl)octamethyltetrasiloxane, 4-amino-3,3- dimethylbutyltrimethoxysilane, and N-ethyl-3-trimethoxysilyl-2-methylpropanamine, 3-(N,N- diethylaminopropyl) trimethoxysilane combinations of two or more thereof, etc.

[0067] In one embodiment, more than one "arm" of the alkoxysilane may be reacted such that the alkoxysilane is bonded to other Q units. For example, a single arm may be bonded to a Q unit, two arms may be bonded to separate Q units, or three arms may be bonded to separate Q units.

[0068] For example, a simple illustration of a possible oligomer structure may be represented by the structure:

where G represents OR¹⁷, and T represents a T_1; T₂, or T₃ unit comprising the reactive group A¹. T¹ represents a T unit that is bonded to one Si atom:

T represents a T unit that is bonded to two Si atoms:

^>vwww S i wwwv

J 9 . 1

-Si-

.20

OR ; and

T³ represents a T unit that is bonded to three Si atoms.

I 19 1

-O Si R A

S ί This example illustrates how the T units may provide a oligomeric network. It will be appreciated that the alkoxysilane of Formula (9) may also provide linkages between siloxane oligomers.

[0069] The molar equivalent ratio of alkoxysilane to silicate in the cure agent may be from about 150: 1 to about 700: 1 ; from about 200: 1 to about 500: 1 , from about 250: 1 to about

450: 1 ; even from about 300: 1 to about 400: 1. Here as elsewhere in the specification and claims, numerical values may be combined to form new and non-disclosed ranges.

[0070] The cure agent may have a weight average molecular weight of about 750 to about 3000; from about 1000 to about 2500; even from about 1500 to about 2000.

[0071] The cure agents may be made by reacting the silicate and the alkoxysilane. The reaction may be one step reaction and may be carried out in the absence of a solvent. The reaction may be carried out a temperature of from about 40 °C to about 99 °C for a period of from about 65 to about 150 hours.

[0072] The cure agent may be added to the curable composition in an amount of from about 0.01 to about 15 parts per weight per 100 parts of the polymer (A); from about 0.1 to about 10 parts per weight per 100 parts of the polymer (A); from about 0.5 to about 8 parts per weight per 100 parts of the polymer (A); from about 1 to about 7 parts per weight per 100 parts of the polymer (A); even from about 2 to about 5 parts per weight per 100 parts of the polymer (A). Here as elsewhere in the specification and claims, numerical values may be combined to form new and non-disclosed ranges.

[0073] The present compositions may further include a filler component (C). The filler component(s) (C) may have different functions, such as to be used as reinforcing or semi- reinforcing filler, i.e., to achieve higher tensile strength after curing. The filler component may also have the ability to increase viscosity, establish pseudoplasticity/shear thinning, and demonstrate thixotropic behavior. Non-reinforcing fillers may act as volume extenders. The reinforcing fillers are characterized by having a specific surface area of more than 50 m²/g related BET-surface, whereby the semi-reinforcing fillers have a specific surface area in the range of 10-50 m²/g. So-called extending fillers have preferably a specific surface area of less than 10 m²/g according to the BET-method and an average particle diameter below 100 μιη. In one embodiment, the semi-reinforcing filler is a calcium carbonate filler, a silica filler, or a mixture thereof. Examples of suitable reinforcing fillers include, but are not limited to, fumed silicas or precipitated silicas, which can be partially or completely treated with organosilanes or siloxanes to make them less hydrophilic and decrease the water content or control the viscosity and storage stability of the composition. These fillers are named hydrophobic fillers. Tradenames are Aerosil®, HDK®, Cab-O-Sil® etc. [0074] Examples of suitable extending fillers include, but are not limited to, ground silicas (Celite™), precipitated and colloidal calcium carbonates (which are optionally treated with compounds such as stearate or stearic acid); reinforcing silicas such as fumed silicas, precipitated silicas, silica gels and hydrophobized silicas and silica gels; crushed and ground quartz, cristobalite, alumina, aluminum hydroxide, titanium dioxide, zinc oxide, diatomaceous earth, iron oxide, carbon black, powdered thermoplastics such as acrylonitrile, polyethylene, polypropylene, polytetrafluoroethylene and graphite or clays such as kaolin, bentonite or montmorillonite (treated/untreated), and the like.

[0075] The type and amount of filler added depends upon the desired physical properties for the cured silicone/non-silicone composition. As such, the filler may be a single species or a mixture of two or more species. The extending fillers can be present from about 0 to about 300 wt. % of the composition related to 100 parts of component (A). The reinforcing fillers can be present from about 5 to about 60 wt. % of the composition related to 100 parts of component (A), preferably 5 to 30 wt. %.

[0076] The polysiloxane composition may optionally include a crosslinker or a chain extender component (D). In one embodiment, the crosslinker is of the formula (11):

wherein R¹, R², and d are as defined above. Alternatively, the crosslinker component may be a condensation product of formula (5) wherein one or more but not all R² groups are hydrolyzed and released in the presence of water and then intermediate silanols undergo a condensation reaction to give a Si-O-Si bond and water. The average polymerization degree can result in a compound having 2 to 10 Si units. In one embodiment, the composition may comprise a crosslinker. In one embodiment, the crosslinker is an alkoxysilane having a formula (12):

R _d(R¹0)_4-dSi, (12)

wherein R¹, R³, and d are defined as above.

[0077] In another embodiment, the crosslinker is an acetoxysilane having a formula (13):

(R _d(R¹C0₂)₄-_dSi, (13)

wherein R¹, R³, and d are defined as above.

[0078] In still another embodiment, the crosslinker is an oximosilane having a formula (14)

R _d(R¹R⁴C=N-0)₄-_dSi,(14)

where R¹, R³, R⁴, and d are defined as above.

[0079] In one embodiment, the crosslinker is of the formula (15):

wherein R²⁵ may be chosen from saturated Ci- C₁₂ alkyl (which can be substituted with one or more of a halogen (e.g., CI, F, O, S or N atom), C5-C1₆ cycloalkyl, C2-C12 alkenyl, C7-C1₆ arylalkyl, C7-C1₆ alkylaryl, phenyl, C2-C4 polyalkylene ether, or a combination of two or more thereof. Exemplary preferred groups are methyl, trifluoropropyl and/or phenyl groups; R²⁶ may be a group reactive to protonated agents such as water and may be chosen from OH, Ci-Cg- alkoxy, C2-Ci₈-alkoxyalkyl, amino, alkenyloxy, oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl, carbamatoalkyl or a combination of two or more thereof. Exemplary groups for R²⁶ include OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy, alkylamido, arylamido, or a combination of two or more thereof; and t is 0-3. Alternatively, the cross-linker component may be a condensation product of formula (15) wherein one or more but not all R²⁶ groups are hydrolyzed and released in the presence of water and then intermediate silanols undergo a condensation reaction to give a Si-O-Si bond and water. The average polymerization degree can result in a compound having 2-10 Si units.

[0080] As used herein, the term crosslinker includes a compound including an additional reactive component having at least two hydrolysable groups and less than three silicon atoms per molecule not defined under (A). In one embodiment, the crosslinker or chain extender may be chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkylarylaminosiloxane, an alkoxy carbamatosilane, an alkoxycarbamatosiloxane, an imidatosilane, a ureidosilane, an isocyanatosilane, a isothiocyanatosilane, the condensates thereof, a hydridosilane, a hydridosiloxane (organosiloxane monomer, oligomer and/or polymer having, per molecule, at least one reactive ≡SiH unit), and combinations of two or more thereof. Examples of suitable cross-linkers include, but are not limited to, tetraethylorthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltripropionoxysilane; methyltris(methylethylketoximo)silane; vinyltris(methylethylketoximo)silane; 3,3,3-trifluoropropyltris(methylethylketoximo)silane; methyltris(isopropenoxy)silane; vinyltris(isopropenoxy)silane; ethylpolysilicate; dimethyltetraacetoxydisiloxane; tetra-n-propylorthosilicate; methyldimethoxy(ethylmethylketoximo)silane; methylmethoxybis(ethylmethylketoximo)silane; methyldimethoxy(acetaldoximo)silane; methyldimethoxy(N-methylcarbamato)silane; ethyldimethoxy(N-methylcarbamato)silane; methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyltriisopropenoxysilane; methyldimethoxy(but-2-en-2- oxy)silane; methyldimethoxy(l-phenylethenoxy)silane; methyldimethoxy-2-(l - carboethoxypropenoxy)silane; methylmethoxydi(N-methylamino)silane; vinyldimethoxy(methylamino)silane; tetra-N,N-diethylaminosilane; methyldimethoxy(methylamino)silane; methyltri(cyclohexylamino)silane; methyldimethoxy(ethylamino)silane; dimethyldi(N,N-dimethylamino)silane; methyldimethoxy(isopropylamino)silane; dimethyldi(N,N-diethylamino)silane; ethyldimethoxy(N-ethylpropionamido)silane; methyldimethoxy(N-methylacetamido)silane; methyltris(N-methylacetamido)silane; ethyldimethoxy(N-methylacetamido)silane; methyltris(N- methylbenzamido)silane; methylmethoxybis(N-methylacetamido)silane; methyldimethoxy(caprolactamo)silane; trimethoxy(N-methylacetamido)silane; methyldimethoxy(ethylacetimidato)silane; methyldimethoxy(propylacetimidato)silane; methyldimethoxy(N,N',N'-trimethylureido)silane; methyldimethoxy(N-allyl-N',N'- dimethylureido)silane; methyldimethoxy(N-phenyl-N'^V'-dimethylureido)silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxyisothiocyanatosilane; methylmethoxydiisothiocyanatosilane, the condensates thereof, or combinations of two or more thereof.

[0081] In one embodiment, the crosslinker may be present in an amount from about 1 to about 10 wt. % of the composition or from about 0.1 to about 10 pt. wt. per 100 pt. wt. of the polymer component (A). In another embodiment, the crosslinker may be present in an amount from about 0.1 to about 5 pt. wt. per 100 pt. wt. of the polymer component (A). In still another embodiment, the crosslinker may be present in an amount from about 0.5 to about 3 pt. wt. per 100 pt. wt. of the polymer component (A). Here as elsewhere in the specification and claims, numerical values may be combined to form new or undisclosed ranges.

[0082] The composition can include a chain extender. The chain extenders can be reactive or non-reactive and can be chosen from a variety of compounds including, but not limited to, organo-functional silicon compounds, (e.g., hydroxyl, carboxylic acid, ester, polyether, amide, amine, alkyl, and/or aromatic grafted/capped siloxane), an alkyl stopped siloxone such as, for example, methyl stopped PDMS, nonreactive organic polymers, or a combination of two or more thereof. The organo-functional silicon compounds can be referred to as organosilicon compounds. The organosilicon compounds can be linear or branched. Examples of suitable organo-functional silicon compounds include, but are not limited to hydride terminated, vinyl terminated, hydroxyl terminated, and/or amino terminated siloxane. In one embodiment, the extender is a organo-functional polydimethylsiloxane such as, for example, hydride terminated polydimethylsiloxane, silanol terminated polydimethylsiloxane, vinyl terminated polydimethylsiloxane, and/or amino terminated poly dimethyl siloxane. [0083] In one embodiment, the chain extender is an organosilicon compound having hydrolyzable groups. Examples of suitable hydrolyzable groups include, but are not limited to an alkoxy group, an alkoxyalkoxy group, or a combination of two or more thereof. Non-limiting examples of suitable hydrolyzable groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxyethoxy, etc., and combinations of two or more thereof. Still further examples of suitable organosilicon compounds include, but are not limited to, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, vintlytrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, ethylorthosilicate, propylyorthosilicate, partial hydrosylates of such compounds, etc., and combinations of two or more thereof.

[0084] The composition optionally includes an adhesion promoter component (E) that is different from component (A) or (B). In another embodiment, the curable compositions comprise an adhesion promoter.

[0085] In one embodiment, the adhesion promoter (E) may be an organofunctional silane comprising the group R⁵, e.g., aminosilanes, and other silanes that are not identical to the silanes of component (D), or are present in an amount that exceeds the amount of silanes necessary for endcapping the polymer (A). The amount of non-reacted silane (D) or (E) in the reaction for making (A) can be defined in that after the endcapping reaction the free silanes are evaporated at a higher temperature up to 200 °C and vacuum up to 1 mbar to be more than 0.1 wt.% of (A).

[0086] Thus, some selected amines can advantageously be added to fine tune the rate of the cure agent -catalyzed condensation curing of silicone/non-silicone polymer containing reactive silyl groups, as desired.

[0087] In one embodiment, the composition comprises an adhesion promoter (E) comprising a group R⁵ as described by the general formula (16):

R⁵ _gR¹ _dSi(R²)₄-d-g (16)

where R⁵ is E-(CR ₂)r-W-(CH₂)_r-; R¹, R², and d are as described above; g is 1 or 2; d + g = 1 to 2; and r is 0 to 8, and may be identical or different.

[0088] Non-limiting examples of suitable compounds include:

E²-[(CR³2 )_r-W-(CH₂ y S-R'SCR S] 5

where s is 2 to 3.

[0089] The group E may be selected from either a group El or E2. El may be selected from a monovalent group comprising amine, -NH2, -NHR, -(NHC2H5)aNHR, NHC6H5, halogen, pseudohalogen, unsaturated aliphatic group with up to 14 carbon atoms, epoxy-group- containing aliphatic group with up to 14 carbon atoms, cyanurate-containing group, and an isocyanurate-containing group. [0090] E² may be selected from a group comprising a di- or multivalent group consisting of amine, polyamine, cyanurate-containing, and an isocyanurate-containing group, sulfide, sulfate, phosphate, phosphite, and a polyorganosiloxane group, which can contain R⁵ and R² groups; W is selected from the group consisting of a single bond, a heteroatomic group selected from -COO-, -0-, epoxy, -S-, -CONH-, -HN-CO-NH- units; R³ is as defined above, R¹ may be identical or different as defined above, R² is defined as above and may be identical or different.

[0091] Non-limiting examples of component (E) include:

wherein R¹, R², and d are as defined above. Examples of component (E) include compounds of the formulas (16a-161). Furthermore the formula (16b) of compounds (E) shall comprise compounds of the formula (16m): (R²)s-d— Si— o- -SiO- -SiO- "Si— (R )₃-_d

R R^" (16m)

wherein: R, R², R⁵, and d are as defined above; k is 0 to 6 (and in one embodiment desirably 0); b is as described above (in one embodiment desirably 0 to 5); and 1 + b < 10. In one embodiment, R is selected from:

E^CR^_h-W- -

[0092] An exemplary group of adhesion promoters are selected from amino-group- containing silane coupling agents. The amino-group-containing silane adhesion promoter agent (E) is an compound having a group containing a silicon atom bonded to a hydrolyzable group (hereinafter referred to as a hydrolyzable group attached to the silicon atom) and an amino group. Specific examples thereof include the same silyl groups with hydrolyzable groups described above. Among these groups, the methoxy group and ethoxy group are particularly suitable. The number of the hydrolyzable groups may be 2 or more, and particularly suitable are compounds having 3 or more hydrolyzable groups.

[0093] Examples of other suitable adhesion promoter (E) include, but are not limited to

N-(2-aminoethyl)aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- aminopropyltrimethoxysilane, bis(3-trimethoxysilypropyl)amine, N-phenyl-gamma- aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, gamma- aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, gamma- glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- glycidoxyethyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma- glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta- (3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, beta-(3,4- epoxycyclohexyl)ethyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, beta- cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma- methacryloxypropylmethyldimethoxysilane, alpha, omega- bis(aminoalkyldiethoxysilyl)polydimethylsiloxanes (Pn =1-7), alpha, omega- bis(aminoalkyldiethoxysilyl)octamethyltetrasiloxane, 4-amino-3,3- dimethylbutyltrimethoxysilane, and N-ethyl-3-trimethoxysilyl-2-methylpropanamine, 3-(N,N- diethylaminopropyl) trimethoxysilane combinations of two or more thereof, and the like. Particularly suitable adhesion promoters include bis(alkyltrialkoxysilyl)amines and tris(alkyltrialkoxysilyl)amines including, but not limited to, bis(3-trimethoxysilylpropyl)amine and tris(3-trimethoxysilylpropyl)amine.

[0094] Also it is possible to use derivatives obtained by modifying them, for example, amino-modified silyl polymer, silylated amino polymer, unsaturated aminosilane complex, phenylamino long-chain alkyl silane and aminosilylated silicone. These amino-group-containing silane coupling agents may be used alone, or two or more kinds of them may be used in combination.

[0095] The adhesion promoter (E) may be present in an amount of from about 0.1 to about 5.0 wt. % based on 100 parts of the polymer component (A). In one embodiment, the adhesion promoter may be present in an amount of from about 0.15 to about 2.0 wt. % based on 100 parts of the polymer component (A). In another embodiment, the adhesion promoter may be present in an amount of from about 0.5 to about 1.5 wt. % of the polymer component (A). This defines the amount of (E) in composition of (A) wherein the content of free silanes coming from the endcapping of polymer (A) is smaller than 0.1 wt.%.

[0096] In one embodiment, the composition can further include (F) an organo-functional silicon compound, a low-molecular-weight organic polymer, a high-boiling-point solvent, or a combination of two or more thereof. Organo-functional silicon compounds include, but are not limited to, an organo-functional silane and/or an organo-functional siloxane. The use of organo- functional silanes, organo-functional siloxanes, and/or low-molecular-weight organic polymers with the cure agent may enhance the properties of the composition. The compositions still exhibit good curability and adhesion as well as retaining stability under storage and not exhibiting phase separation. [0097] The low-molecular-weight organic polymers, high-boiling-point solvents, and organo-functional silicon compounds may also be referred to herein as extenders.

[0098] Low-molecular-weight organic polymers suitable as the extender include compounds or materials having a boiling point greater than 150 °C; in one embodiment from 150 °C to 450 °C. Examples of suitable low-molecular-weight compounds as the extender include, but are not limited to, polyether polyols containing repeating ether linkage -R-O-R- and have two or more hydroxyl groups as terminal functional groups, or combinations of two or more thereof. In one embodiment, polyethylene glycol can be employed as an extender.

[0099] High-boiling molecules suitable as extenders include high-boiling-point solvents having a boiling point of at least 150 °C. For example, a boiling point between 150 °C and 450 °C, between 225 °C and 375 °C, even between 275 °C and 325 °C. Examples of high- boiling-point solvents as extenders include, but are not limited to DMF, DMSO, carbitols or combinations of two or more thereof.

[00100] The organo-functional silicon compound can be chosen from a variety of compounds, including, but not limited to, carboxylic acid, ester, polyether, amide, amine, alkyl, aryl, aromatic grafted or endcapped siloxanes, organic polymers, or a combination of two or more thereof. For example, the organo-functional silicon can be an alkyl-stopped siloxane such as, for example, methyl-stopped PDMS. The organo-functional silicon compounds can be referred to as organosilicon compounds. The organosilicon compounds can be linear or branched. Examples of suitable organo-functional silicon compounds include, but are not limited to, hydrido-functional siloxanes, vinyl- functional siloxanes, hydroxyl- functional siloxanes, and amino-functional siloxanes. In one embodiment, the extender is an organo-functional polydimethylsiloxane compound such as, for example, hydride-terminated polydimethylsiloxane, silanol-terminated polydimethylsiloxane, vinyl-terminated polydimethylsiloxane, or amino- terminated polydimethylsiloxane.

[00I0I] In one embodiment, the composition comprises an organo-functional siloxane of the formula (17):

M D D'_fc T_z T'_j M (17) where M represents R⁶ ₃SiOi/₂; D is R⁷ ₂Si0₂/2; D' is R⁸ ₂Si0₂/2, T is R⁹Si0_3/2; T' is R¹⁰SiO_3/2; R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently chosen from a hydrogen and a monovalent organic group, such as an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, a cycloalkyl group, a heterocycloalkyl, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a heteroaralkyl group, an alkylaryl group, a heteroalkylaryl group, an epoxy group, an amino group, a mercapto group, a trifluoropropyl group, a polyalkylene oxide group, a silicon-containing alkyl group, a silicon-containing aryl group, an alkyl, aryl, alkylaryl, or aralkyl bridge formed by at least two R⁶, two R⁷, or two R⁸ groups. The values of h, k, z, and j may vary greatly depending upon the desired end viscosity of the polymers of the present invention. In one embodiment, the viscosity of the organo-functional silicon compound is between the range of about 1 centiStokes (cSt) at 25 °C to about 2,000,000 centiStokes (cSt) at 25 °C. In another embodiment, the viscosity of the organo-functional silicon compound is between the range of about 1 cSt at 25 °C to about 200,000 cSt at 25 °C. In yet another embodiment, the viscosity of the organo-functional silicon compound is between the range of about 1 cSt at 25 °C to about 10,000 cSt at 25 °C. In yet another embodiment, the viscosity of the organo-functional silicon compound is between the range of about 1 cSt at 25 °C to about 3,000 cSt at 25 °C. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges. The organo-functional silicon compound comprises at least one organic group. In one embodiment, R⁶, R⁷, and R⁸ are independently chosen from a CI -CI 3 alkyl group, a CI -CI 3 alkoxy group, a C2-C13 alkenyl group, a C2-C13 alkenyloxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, a C6-C14 aryl group, a C6-C10 aryloxy group, a C7-C13 aralkyl group, a C7-C13 aralkoxy group, a C7-C13 alkylaryl group, a C7-C13 alkylaryloxy group, and a C2-C8 ether group. In one embodiment, at least one of R⁶, R⁷, R⁸, R⁹, and/or R¹⁰ group is a hydrogen.

[00102] In one embodiment, the organo-functional siloxane compound comprises an alkoxy group, an alkylaryl group, an ether group, or a combination of two or more thereof. Examples of suitable alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc. Examples of suitable alkylaryl groups include, but are not limited to, alkyl phenols. Examples of suitable ether groups include alkyl ethers such as, but not limited to, methyl ether groups, ethyl ether groups, propyl ether groups, butyl ether groups, etc., and combinations of two or more thereof.

[00103] In one embodiment, the organo-functional siloxane can be of the formula (18):

where R⁶, R , R , h, and k are described above. In one embodiment, the viscosity of the organo- functional silicon compound is from about 1 cSt at 25 °C to about 2,000 cSt at 25 °C. In one embodiment, at least one of R is chosen from an alkyl, an aryl, alkoxy, an ether group, or combinations of two or more thereof.

[00104] In one embodiment, the organo-functional silicon compound is of the formula (19):

wherein h and k are described above and at least one R⁶, R⁷, or R⁸ is chosen from a group of the formula (20):

where R¹¹ is a divalent hydrocarbon and R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently chosen from hydrogen, a hydroxy, an alkyl, a heteroalkyl, an alkoxy, an alkenyl, a heteroalkenyl, an alkenyloxy, a cycloalkyl, a heterocycloalkyl, a cycloalkoxy, an aryl, a heteroaryl, an aryloxy, an aralkyl, a heteroaralkyl, an alkylaryl, a heteroalkylaryl, an alkylaryloxy, an alkyl, aralkyl, alkylalkoxy, dialkoxy, heteroalkyl, heteroaryl, heteroaralkyl, or heteroalkylaryl bridge formed by one or more of R¹²-R¹³, R¹ -R¹⁴, R¹⁴-R¹⁵, and R¹⁵-R¹⁶, or a combination of two or more thereof. In one embodiment, the organo-functional siloxane is alkyl-stopped. In one embodiment, the organo-functional siloxane is methyl-stopped. In one embodiment, the organo-functional siloxane is of the formula (21):

where R⁶, R⁷, R⁸,R⁹, h, and k are described above.

[00105] embodiment, the organo-functional siloxane is of the formula (22):

where v = 0 or 1, b= 0 or 1, G represents an oxygen atom or an unsubstituted bivalent hydrocarbon group, and R⁶, R⁷, R⁸, R⁹, h, and k are described above.

[00106] In one embodiment, the organo-functional siloxane comprises an alkylaryl group such as, for example an alkyl phenol group. In one embodiment, the organo-functional siloxane is of

where R⁶, R⁷, R⁸, k, and k are described above.

[00107] In one embodiment, the organo-functional silicon compound is an organosilicon compound having hydrolyzable groups. Examples of suitable hydrolyzable groups include, but are not limited to an alkoxy group, an alkoxyalkoxy group, or a combination of two or more thereof. Non-limiting examples of suitable hydrolyzable groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxy ethoxy, etc., and combinations of two or more thereof. Still further examples of suitable organosilicon compounds include, but are not limited to, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, ethylorthosilicate, propylorthosilicate, partial hydrolysates of such compounds, and combinations of two or more thereof.

[00108] In one embodiment, at least one of the organo-functional silicon compound, a low-molecular-weight organic polymer, a high-boiling-point solvent, or a combination of two or more thereof has at least one hydridosilyl group, and the composition can be used to prepare a polymer by the dehydrogenative condensation reaction between a Si-OH group and a Si-H group to form Si-O-Si bonds and the release of hydrogen gas. [00109] The organo-functional silicon material can be provided in an amount of from about 0.0001 to about 20 parts per weight per 100 parts per weight of the polymer component; 0.001 to 15 parts per weight; 0.01 to 10 parts per weight; even 0.1 to 5 parts per weight per 100 parts per weight of the polymer. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges.

[00110] Additionally, the crosslinker and/or chain extender can be provided as part of a composition such as that disclosed in U. S. Patent Application Publication No. 2013/0303676, which is incorporated herein by reference in its entirety.

[00111] The extender can be provided in an amount of from about 0.0001 to about 20 parts per weight of the extender per 100 parts per weight of the polymer component; 0.001 to 15 parts per weight; 0.01 to 10 parts per weight; even 0.1 to 5 parts per weight per 100 parts per weight of the polymer. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges.

[00112] Additional alkoxysilane adhesion promoters in an amount greater than 0.1 wt.% of component (A) that are not consumed by the reaction between the prepolymer Z^'-X-Z^' and which comprise additional functional groups selected from R⁵ can also work as an adhesion promoter and are defined and counted under component (E).

[00113] While the present cure agents may suitably function to catalyze or accelerate curing of the composition, the curable composition may optionally comprise other catalyst materials (G). These materials may be metal based or metal-free materials that may function as catalysts to cure compositions having a polymer with a reactive silyl group. Such catalyst materials may include, but are not limited to, complexes or salts of metals including but not limited to titanium, zirconium, zinc, aluminum, iron, and bismuth; carboxylic acids including but not limited to acetic acid, lauric acid, stearic acid, and versatic acid; alkyl- and arylsulfonic acids including but not limited to p-toluenesulfonic acid and methanesulfonic acid; inorganic acids including but not limited to hydrochloric acid, phosphoric acid, and boric acid; amines including but not limited to trioctylamine; guanidines including but not limited to tetramethylguanidine; amidines including but not limited to 1 ,8- diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5- diazabicyclo[4.3.0]non-5-ene (DBN); and inorganic bases including but not limited to lithium hydroxide and sodium methoxide. The catalyst (G), however, is desirably chosen such that the system is substantially free of fluorine and tin.

[00114] The catalyst component (G) can be present in an amount of from 0.0001 to about 10 parts per weight (wt. pt.) based on 100 parts off the polymer (A); 0.005 to about 7.5 wt. pt. based on 100 parts of the polymer (A); about 0.01 to about 5.0 wt. pt. based on 100 parts of the polymer component (A); from about 0.15 to about 2.0 wt. pt. based on 100 parts of the polymer component (A); even from about 0.5 to about 1.5 wt. pt. of the polymer component (A). In one embodiment, the catalyst (G) is present in an amount of from about 0.01 to about 1 wt. pt. based on 100 parts of the polymer (A); from about 0.025 to about 0.8 wt. pt. based on 100 parts of the polymer (A); even from about 0.05 to about 0.5 wt. pt. based on 100 parts of the polymer (A).

[00115] The inventive compositions optionally comprise an acidic compound (H), which may accelerate curing (as compared to curing in the absence of such compounds). The component (H) may be present in an amount of from about 0.01 to about 5 wt. % of the composition. In another embodiment 0.01 to about 8 parts per weight (pt. wt.) per 100 pt. wt. of component (A) are used, more preferably 0.02 to 3 pt. wt. per 100 pt. wt. of component (A) and most preferably 0.02 to 1 pt. wt. per 100 pt. wt. of component (A) are used.

[00116] The acidic compounds (H) may be chosen from various phosphate esters, phosphonates, phosphites, phosphonites, sulfites, sulfates, pseudohalogenides, branched alkyl carboxylic acids, combinations of two or more thereof, and the like. Without being bound to any particular theory, the acidic compounds (F) may, in one embodiment, be useful as stabilizers in order to ensure a longer storage time when sealed in a cartridge before use in contact with ambient air. Alkoxy -terminated polysiloxanes can lose the ability to cure after storage in a cartridge and show decreased hardness under curing conditions. It may, therefore be useful to add compounds of the formula (24), which can extend storage time or ability to cure over months.

0=P(OR²⁷)_3-c(OH)_c (24)

whereby c is as defined above; and R²⁷ is selected from the group of linear or branched and optionally substituted C1-C30 alkyl groups, linear or branched C5-C14 cycloalkyl groups, C6-C14 aryl groups, C6-C₃1 alkylaryl groups, linear or branched C2-C₃₀ alkenyl groups or linear or branched C1-C30 alkoxy alkyl groups, C4-C300 polyalkenylene oxide groups (poly ethers), such as Marlophor® N5 acid, triorganylsilyl- and diorganyl (Ci-C8)-alkoxysilyl groups. The phosphates can include also mixtures of primary and secondary esters. Non-limiting examples of suitable phosphonates include l-hydroxyethane-(l,l-diphosphonic acid) (HEDP), aminotris(methylene phosphonic acid) (ATMP), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), 1,2- diaminoethane-tetra(methylene phosphonic acid) (EDTMP), and phosphonobutanetricarboxylic acid (PBTC).

[00117] In another embodiment, a compound of the formula

may be present or added where g is 1 or 2, and R²⁸ is defined as R²⁷ or di- or mulitvalent hydrocarbons with one or more amino group.

[00118] Another type are phosphonic acid compounds of the formula R⁶P(0)(OH)2 such as alkyl phosphonic acids preferably hexyl or octyl phosphonic acid. [00119] In one embodiment, the acidic compound may be chosen from a mono ester of phosphoric acid of the formula (R²⁹0)PO(OH)₂; a phosphonic acid of the formula R P(0)(OH)₂; or a monoester of phosphorous acid of the formula (R 0)P(OH)₂ where R is a C1-C18 alkyl, a C2-C20 alkoxyalkyl, phenyl, a C7-C12 alkylaryl, a C2-C4 polyalkylene oxide ester or its mixtures with diesters, etc.

[00120] In another embodiment, the acidic compound is a carboxylic acid, including, for example, a C4-C30 carboxylic acid, a branched C4-C30 alkyl carboxylic acids, including C5-C 19 acids with an alpha tertiary carbon, or a combination of two or more thereof. Examples of such suitable compounds include, but are not limited to, Versatic™ Acid, lauric acid, and stearic acid. In one embodiment, the acidic compound may be a mixture comprising branched alkyl carboxylic acids. In one embodiment, the acidic compound is a mixture of mainly tertiary aliphatic C10 carboxylic acids.

[00121] Generally, the acidic component (H) is added in a molar ratio of less than or equal to 1 with respect to cure agent (B). In embodiments, the acidic component (H) is added in a molar ratio of (H) : (B) of 1 : 15 to 1 : 1.

[00122] The curable composition may also include auxiliary substances (I) such as plastizers, pigments, stabilizers, anti-microbial agents, fungicides, biocides, and/or solvents. Preferred plastizers for reactive polyorganosiloxanes (A) are selected from the group of polyorganosiloxanes having chain lengths of 10 to 300 siloxy units. Preferred are trimethylsilyl terminated polydimethylsiloxanes having a viscosity of 100 to 1000 mPa.s at 25 °C. The choice of optional solvents (dispersion media or extenders) may have a role in assuring uniform dispersion of the accelerator, thereby altering curing speed. Such solvents include polar and non- polar solvents such as toluene, hexane, chloroform, methanol, ethanol, isopropyl alcohol, acetone, methylethyl ketone, dimethylformguanidine-containing (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidinone (ΝΜΡ), and propylene carbonate. Water can be an additional component (I) to accelerate fast curing 2-part compositions RTV-2, whereby the water can be in one part of the 2 compositions. Particularly suitable non-polar solvents include, but are not limited to, toluene, hexane, and the like if the solvents should evaporate after cure and application. In another embodiment, the solvents include high-boiling hydrocarbons such as alkylbenzenes, phthalic acid esters, arylsulfonic acid esters, trialkyl- or triarylphosphate esters, which have a low vapor pressure and can extend the volume providing lower costs. Examples cited by reference may be those of U.S. 6,599,633; U.S. 4,312,801. The solvent can be present in an amount of from about 20 to about 99 wt. % of the catalyst composition. [00123] Applicants have found that the present cure agents may provide a curable composition that yields a cured polymer exhibiting suitable tack-free time, hardness, and/or cure time, and may even be comparable to compositions made using tin catalysts.

[00124] In one embodiment, a composition in accordance with the present invention comprises: 100 pt. wt. polymer component (A); about 0.1 to about 10 pt. wt. of the cure agent (B); and optionally one or more of components (C) - (I).

[00125] It will be appreciated that the curable compositions may be provided as either a one-part composition or a two-part composition. A one-part composition refers to a composition comprising a mixture of the various components described above. A two-part composition may comprise a first portion and a second portion that are separately stored and subsequently mixed together just prior to application for curing. In one embodiment, a two-part composition comprises a first portion (i) comprising a polymer component (A), optionally filler (C), and optionally a crosslinker component (D), and a second portion (ii) comprising the cure agent (B), optionally a crosslinker (D), optionally an adhesion promoter (E), and optionally a cure catalyst (G), where portions (i) and (ii) are stored separately until applied for curing by mixing of the components (i) and (ii).

[00126] All these polymerization/crosslinking routes result in more or less polymerized and more or less crosslinked silicone products which can constitute products that can be used in multiple applications. The curable compositions may be used in a wide range of applications including as materials for sealing, mold making, glazing, prototyping; as adhesives; as coatings in sanitary rooms; as joint seal between different materials, e.g., sealants between ceramic or mineral surfaces and thermoplastics; as paper release; as impregnation materials; weather strip coatings, release coatings, adhesives, adhesion finishes, leak tight products, pointing products, foams, etc. A curable composition comprising the present cure agents may be suitable for a wide variety of applications such as, for example, a general purpose and industrial sealant, potting compound, caulk, adhesive or coating for construction use, insulated glass, structural glazing, where glass sheets are fixed and sealed in metal frame; caulks, adhesives for metal plates, car bodies, vehicles, electronic devices, and the like. Furthermore, the present composition may be used either as a one-part RTV-1 or as a two-part RTV-2 formulation that can adhere onto broad variety of metal, mineral, ceramic, rubber, or plastic surfaces.

[00127] Curable compositions comprising the present cure agents may be further understood with reference to the following Examples. EXAMPLES

Preparation of Curing Agents

[00128] Cure agents comprising the reaction product of a silicate and an alkoxysilane with a free reactive group were prepared by mixing the silicate and alkoxysilane and reacting the mixture at temperature of 70 °C for a period of 6 hours to 120 hours. The reaction mixture is provided as a neat solution of the components without any additional solvent. The silicate is an ethylpoly silicate, and alkoxysilanes are chosen from gamma-Aminopropyl triethoxysilane; bis- [gamma-(Trimethoxysilyl)propyl]amine (Al); N-(beta-aminoethyl)-gamma-Aminopropyl trimethoxysilane (A2); and a trialkoxysilane with a secondary amino functionality .

[00129] Tables 1-3 show the formulations for oligomers OL1-OL16.

Table 1

Table 2

Table 3

General Experimental Procedure

[00130] Preparation of component A: The component A is prepared by mixing about 60 -

70 % of hydroxyl terminated PDMS and about 30 -40 % of filler such as CaC03 and or silica fillers at room temperature. The resultant uniformly mixed mixture is component A.

[00131] The Component A [premixed mixture of hydroxy terminated PDMS and fillers (CaC03 and silica)] was mixed with the various concentrations of oligomers using a Hauschild mixer for 1.5 min. The mixed formulation was poured into a Teflon mold (L x W x D = 10 cm x 10 cm x 1 cm) and placed inside a fume hood. The surface curing (TFT) and bulk curing was monitored as a function of time (maximum of 3 days). Heat Ageing Method

[00132] The Oligomeric curing agent is further heat aged to study the shelf life stability of the curing agent with or without additional cross linker and adhesion promoters by keeping in an oven for (1) 4 hours at 50 °C, or (2) 5 days at 70 °C. After the specified period, the oligomeric curing agent was removed from the oven and allowed to return to ambient temperature. This mixture was then combined with component A and mixed on a Hauschild mixer for 1.5 min. The mixed formulation was poured into a Teflon mold (L x W x D = 10 cm x 10 cm x 2 cm) and placed inside a fume hood. These heat-ageing procedures should simulate the storage effect at room temperature over longer time periods.

Tack-Free Time (TFT) Measurement Method A

[00133] In a typical TFT measurement, the premixed composition of component A and the oligomer is poured into a Teflon mold (L x W x D = 50mm x 30mm x 20 mm) and spread evenly using a stainless steel spatula. A 10-gram, stainless steel weight/ stainless steel spatula was placed on the surface of the formulation to determine the tackiness of the surface. TFT is defined as the time taken for getting a non-tacky surface. This time is recorded to the nearest minute.

Tack-Free Time Measurement Method B

[00134] Tack-free time was determined using finger soft touch method wherein the dried finger is softly placed on the surface of formulation and checked for non-sticky surface and recorded.

Shore A Hardness Measurement Method

[00135] Shore A hardness values were determined by preparing three samples of dimension (50mniX30mniX10mm/20mm). The sample specimens were taken out of the mold after the interval of 24 hrs. (samples-1), 48 hrs. (sample-2) & 72 hrs. (sample-3). The shore A measurement was performed both on top and bottom immediately after taking it out from the mold. This measurement method was used as a measure of time required for bulk cure of the sample. Bulk cure time is the time required for complete curing of formulation throughout the thickness (i.e. top to bottom).

Substrate Adhesion Test Method

[00136] Cohesive failure to glass, metal, and plastic substrates was determined in the following manner. The premixed composition of component A and component B was applied as thick lines on the pre-cleaned and dried standard plastic, glass and metal substrates. The substrates were kept at room temperature for three days. After three days, the adhered and cured materials were removed from substrates to check the cohesive or adhesive failure.

[00137] Tables 4-8 show the properties of curable compositions employing various curing agents.

Table 4

Table 5

Table 6

Table 7

Table 8

[00138] Embodiments of the invention have been described above and modifications and alterations may occur to others upon the reading and understanding of this specification. The claims as follows are intended to include all modifications and alterations insofar as they come within the scope of the claims or the equivalent thereof.

Claims

CLAIMS What is claimed is:

1. A composition for forming a cured polymer composition comprising:

(A) a polymer having at least a reactive silyl group;

(B) a cure agent of oliogomeric resin which is a reaction product of a silicate and alkoxysilane and comprising at least one T (S1O₃/2) unit, and at least one Q (S1O4/2) unit, wherein the silicon atom of at least one of the said T (S1O₃/2) and Q (S1O4/2) units are bonded to an alkoxysilane with at least one free reactive group, the alkoxysilane being chosen from a compound of the formulas:

A^SKOR²⁰^;

(R²¹0)_3-qR²² _xSi-R² -A²-R² -SiR²² _q(OR²¹)_3-q;

or a combination of two or more thereof, wherein R¹⁹ is independently selected from hydrocarbon group optionally substituted with heteroatom selected from N, S, P, and O; R²⁰ is independently a substituted or unsubstituted hydrocarbon group of 1 to 5 carbon atoms; A¹ is independently selected from a substituted or unsubstituted amine, epoxy, acryl, acetyl, or acidic group;

R²¹ is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 5 carbon atoms; R²² and R²³ are independently chosen from a substituted or unsubstituted divalent hydrocarbon group; A² is independently selected from an amine, epoxy, acryl, acetyl, acidic derivatives; and q is independently an integer selected from 1 to 3; and

(C) optionally, a filler component.

2. The composition of claim 1, wherein the silicate is chosen from a compound of the formula:

Si(OR¹⁷)₄;

(R¹⁸0)₃SiO[SiO(OR¹⁸)₂]_nSi(OR¹⁸)₃;

or a combination of two or more thereof, wherein R¹⁷ and R¹⁸ are independently chosen from a hydrogen, a CI -CIO alkyl, a CI -CIO alkoxyalkyl, , and p is 0-50.

3. The composition of claim 1 or 2, wherein A¹, A², or both A¹ and A² are chosen from an amine.

4. The composition of any one of claims 1-3, wherein the alkoxysilane for forming the cure agent is chosen from a compound of the formula: E¹-(CR ₂)_r-W-(CH₂)_r-SiR¹ ₅(R²)_3-5;

E²-[(CR ₂)_r-W-(CH₂)_r-SiR¹ ₅(R²)_3-5]₃;

or a combination thereof; where s is 2 to 3; r is 0-8; E¹ is chosen from a monovalent group comprising amine, -NH₂, -NHR²⁴, -(NHC₂H₅)_aNHR²⁴, NHC₆H₅, halogen, pseudohalogen, unsaturated aliphatic group with up to 14 carbon atoms, epoxy-group-containing aliphatic group with up to 14 carbon atoms, cyanurate-containing group, and an isocyanurate-containing group; E² is chosen from a group comprising a di- or multivalent group consisting of amine, polyamine, cyanurate-containing, and an isocyanurate-containing group, sulfide, sulfate, phosphate, phosphite, and a polyorganosiloxane group, which can contain R⁵ and R² groups; R⁵ is E-(CR ₂)_r- W-(CH₂)_r-; W is chosen from a single bond, a heteroatomic group selected from -COO-, -0-, epoxy, -S-, -CONH-, -HN-CO-NH- units; R²⁴ is independently hydrogen, or a C1-C10 alkyl; R³ is chosen from hydrogen; Ci-Cio alkyl; Ci-Cio heteroalkyl, C₃-Ci₂ cycloalkyl; C₂-C₃o heterocycloalkyl; C6-Ci₃ aryl; C7-C₃o alkylaryl; C7-C₃o arylalkyl; C₄-C₁₂ heteroaryl; C5-C₃o heteroarylalkyl; C5-C₃o heteroalkylaryl; C₂-Cioo polyalkylene ether; or a combination of two or more thereof, R¹ is independently chosen from linear or branched alkyl, linear or branched heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, linear or branched aralkyl, linear or branched heteroaralkyl, or a combination of two or more thereof. In one embodiment, R¹ may be chosen from Ci-Cio alkyl; Ci-Cio alkyl substituted with one or more of CI, F, N, O, or S; phenyl; C7-C1₆ alkylaryl; C7-C1₆ arylalkyl; C₂-C₂o polyalkylene ether; or a combination of two or more thereof, R² is independently chosen from OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy, arylcarboxy, alkylamido, arylamido, or a combination of two or more thereof.

5. The composition of claim 4, wherein the alkoxy silane of the cure agent is chosen from N-(2-aminoethyl)aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis(3-trimethoxysilypropyl)amine, N-phenyl-gamma- aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, gamma- aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, gamma- glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- glycidoxyethyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma- glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta- (3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, beta-(3,4- epoxycyclohexyl)ethyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, beta- cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma- methacryloxypropylmethyldimethoxysilane, alpha, omega- bis(aminoalkyldiethoxysilyl)polydimethylsiloxanes (Pn =1-7), alpha, omega- bis(aminoalkyldiethoxysilyl)octamethyltetrasiloxane, 4-amino-3,3- dimethylbutyltrimethoxysilane, and N-ethyl-3-trimethoxysilyl-2-methylpropanamine, 3-(N,N- diethylaminopropyl) trimethoxysilane, or a combination of two or more thereof.

6. The composition of any one of claims 1-5, wherein the cure agent has a molar equivalent ratio of alkoxysilane to silicate of from about 150: 1 to about 700: 1.

7. The composition of any one of claims 1-6, wherein the cure agent has a molar equivalent ratio of alkoxysilane to silicate of from about 250: 1 to about 450: 1.

8. The composition of any one of claims 1-7, wherein the cure agent has a weight average molecular weight of from about 750 to about 3000.

9. The composition of any one of claims 1-8, wherein the curing compound (B) is an oligomer with independent Q, T_1; and T₂ units, wherein at least one of Ti and T₂ units are bonded with a silyl functionality, the Ti and T₂ units comprising at least one free reactive amine group, wherein Ti is a S1O₃/2 unit with one arm reacted unit and T₂ is a S1O₃/2 unit two arms reacted unit.

10. The composition of any one of claims 1-9, wherein the composition comprises the cure agent in an amount of from about 0.01 to about 15 parts per weight per 100 parts per weight of the polymer (A).

11. The composition of any one of claims 1-10, wherein the composition further comprises a crosslinker (D) chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof.

12. The composition of claim 11, wherein the crosslinker component (D) is chosen from tetraethylorthosilicate (TEOS), a polycondensate of TEOS; methyltrimethoxysilane (MTMS); vinyl-triniethoxysilane; methy 1 v i ny 1 di methoxv si I ane; dimethyldiethoxysilane; vinyltriethoxysilane; tetra-n-propylorthosilicate; vinyltris(methylethylketoxime)silane; methy1tris(methylethylketoxime)silane; trisacetamidomethylsilane; bisacetamidodimethylsilane; tris(N-methyl-acetamido)methylsilane; bis(N-methylacetamido)dimethylsilane; ( -methy 1- acetamido)methy ldi alkoxy silane; trisbenzaraidomethylsilane; trispropenoxymethylsilane; alkyldialkoxyamidosilanes; alkylalkoxybisamidosilanes; CH₃Si(OC₂Hs)i.₂(NHCOR)₂-i. (CH₃Si(OC₂H₅)(NCH₃COC₆H₅)_2; ΟΗ₃8ι(Οθ₂Η₅)-(ΝΗ€Ό€₆Η₅)₂

methy 1 methoxv bi s-( ethy 1 methy 1 ketox i mo )s i 1 ane methyldimethoxy(acetaldoximo)silane; methy 1 di methoxv ( N -methy 1 carbamalo )s i 1 ane; ethyldimethoxy( -methylcarba.mato)silane; methy 1 di methoxv i sopropenoxy sil ane; trimethoxyisopropenoxysilane; methyltri-iso-propenoxysilane; methy Idimethoxy (but-2-ene-2- oxy )silane; methy ldi methoxy( l -phenylethenoxy )silane; methy ldi methoxv -2 ( 1 - carboelhoxypropenoxy )silane; methylmethoxydi-N-methylaminosilane; v i ny 1 d i meth oxy methy 1 am inosil an e; tetra-N\N-diethy laminosilane; methy 1 di methoxv methy lami nos i 1 ane; methx 1 tri cy cl ohexy 1 ami nosi 1 ane; melhyldimethoxy ethy laminosilane; di methy ldi- .N-di methy laminosilane; methy ldimethoxyisopropy laminosilane di methy Idi- .N-diethy laminosilane. ethyldimethoxy(N- ethylpropionamido)silane; methyldimethoxy(N-methylacetamido)silane; methyltris(N- methylacetamido)silane;

methy ltris( N- methylben/amido)silane; methy lmethoxybis(N-methylacetamido)silane; methy ldi methoxy(caprolactamo)sikuie; trimethoxy(N-methylacetamido)silane; methy ldi methoxv ethy lacetimidatosilane; methyldimethoxypropylacetimidatosilane; methyldimethoxy(N,N',N'-trimethylureido)silane; methy 1 di methoxv (N -al ly 1 - ^" .N^" - dimethylureido)silane; methyldimethoxy(TV-phenyl-N',N'-dimethylureido)silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methy ldimethoxythioisocyanatosilane; methylmethoxydithioisocyanatosilane, or a combination of two or more thereof.

13. The composition of claim 11, wherein the crosslinker component (D) is chosen from a silane or a siloxane, the silane or siloxane having two or more reactive groups that can undergo hydrolysis and/or condensation reaction with polymer (A) or on its own in the presence of water and component (B).

14. The composition of claim 11, comprising about 1 to about 10 wt. % of the crosslinker component (D) based on 100 wt.% of the polymer component (A).

15. The composition of any one of claims 1-14 further comprising an adhesion promoter (E).

16. The composition of any one of claims 1-15 further comprising a cure catalyst (G) chosen from a metal, metal chelate, an amine, an acid, a base, or a combination of two or more thereof.

17. The composition of any one of claims 1-16 further comprising a solvent chosen from an alkylbenzene, a trialkyphosphophate, a triarylphosphate, a phthalic acid ester, an arylsul Ionic acid ester having a viscosity-density constant (VDC) of at least 0.86 that is miscible with a polyorganosiloxanes and catalyst component (C), a polyorganosiloxane devoid of reactive groups and having a viscosity of less than 2000 mPa.s at 25 °C, or a combination of two or more thereof.

18. The composition of any one of claims 1-17, wherein the composition is provided as a one part composition.

19. The composition of any one of claims 1-18 comprising:

100 pt. wt of component (A),

0.1 to about 10 pt. wt of at least one curing compound (B); and

optionally the filler compound (C), a crosslinker component (D), an adhesion promoter (E), a curing catalyst (F), or a combination of two or more thereof; whereby this composition can be stored in the absence of humidity and is curable in the presence of humidity upon exposure to ambient air.

20. The composition of any one of claims 1-17, wherein the composition is a two-part composition comprising:

(i) a first portion comprising the polymer having at least a reactive silyl group (A), optionally the filler component (C), and optionally a crosslinker compound (D),

(ii) a second portion comprising the cure agent (B), optionally a crosslinker (D), optionally an adhesion promoter (E), and optionally a cure catalyst (F),

whereby (i) and (ii) are stored separately until applied for curing by mixing of the components (i) and (ii).

21. The two-part composition of claim 20 where:

portion (i) comprises 100 pt. wt of component (A), and at least one cure agent (B).

22. A method of providing a cured material comprising exposing the composition of any one of claims 1-21 to ambient air.

23. A method of providing a cured material comprising combining the first portion and the second portion of claim 20 and curing the mixture.

24. The method of claim 23 whereby the composition is stored in a sealed cartridge or flexible bag having outlet nozzles for extrusion and or shapin of the uncured composition prior to cure.

25. A cured polymer material formed from the composition of any one of claims I -

21.

26. The cured polymer material of claim 25 in the form of an elastomeric or duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, and an impression material.

27. A composition for forming a cured polymer composition comprising:

(A) a siloxane polymer having at least a reactive silyl group, the polymer being of the formula

whereby

x is O to 10000;

y is 0 to 1000;

a is 0 to 2;

R is methyl;

R¹ is chosen from a Ci-Cio-alkyl; a Ci-Cio alkyl substituted with one or more of CI, F, N, O or S; a phenyl; a C₇-C₁₆ alkylaryl; a C₇-C₁₆ arylalkyl; a (^' _.>-(^' i polyalkyiene ether; or a combination of two or more thereof, and other siloxane units may be present in amounts less than 10 mol.% preferably meth l, vinyl, phenyl;

R is chosen from OH, a G-CValkoxy. a C^Ge-alkoxy alkyl, an oximoalkyl, an enoxyalkyl, an aminoalkyl, a carboxvalkyl, an amidoalkyl, an amidoaiyl, a carbamatoalkyl, or a combination of two or more thereof, and

Z is -O- , bond, or -C2H4-;

(B) a curing compound which is a oligomeric resin having at least one T and Q units with at least one reactive silyl group consists of at least one free amine group; and

(C) a filler component.

28. A cured composition formed from the composition of claim 27, wherein the polymer is formed by crosslinking via a condensation reaction and/or a dehydrogenative condensation reaction.