Stabile silane modified polymer composition and method

Abstract

To provide a stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition that is useful as a component in the preparation of coatings, adhesives, sealants, consumer goods and industrial products.SOLUTION: An alkoxysilyl-containing polyurethane polymer composition is prepared using a urethane-forming organometallic catalyst, and then stabilized against moisture exposure by addition of a mercapto-containing compound. The stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition is activated for moisture curing by addition of hydrolysis and condensation catalysts.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to the field of alkoxysilyl-containing polymer compositions, particularly alkoxysilyl-containing polyurethane polymer compositions, and methods for more stably producing such alkoxysilyl-containing polymers.

Background Art

[0002] Alkoxysilyl-containing polymers have desirable properties provided by crosslinking of the polymers by hydrolysis and condensation reactions of alkoxysilyl groups. Moisture-curable compositions based on alkoxysilyl-containing polymers are known. Such polymers usually undergo hydrolysis and condensation when contacted with moisture in the presence of a curing catalyst. Conventional catalysts for curing alkoxysilyl-containing polymers include organometallic compounds containing metals such as tin, nickel, cobalt, aluminum, iron or bismuth. For example, organotin compounds such as dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dibutyltin diacetate (DBTDA) and dibutyltin (II) oxide (DBTO) are commonly used as catalysts to promote the curing of many different moisture-curable compositions such as alkoxysilyl-containing silicones and non-silicone resins, and coatings, sealants, adhesives formulated with such resins.

[0003] When modifying a hydroxyl-functional polymer using an aliphatic isocyanato-functional alkoxysilane, or chain-extending a polyol using a polyisocyanate, or end-blocking a polyol with an isocyanate-containing intermediate and then silylating, a metal urethane-forming catalyst is used to facilitate the reaction between the isocyanate and the hydroxyl groups. These urethane-forming metal catalysts include organometallic compounds such as metal salts or metal complexes. These metal urethane-forming catalysts often remain in the polymer matrix after the silylation reaction is complete. These same catalysts can then catalyze both the hydrolysis reaction and the condensation reaction of the alkoxysilyl functional groups. The hydrolysis and condensation reactions can lead to insufficient storage stability and / or premature hardening during the processing of the alkoxysilyl-containing polymer.

[0004] One approach to stabilizing these polymers was to incorporate low molecular weight silane additives such as vinyltrimethoxysilane or methyltrimethoxysilane to enhance moisture stability. Water typically reacts faster with these silane additives than with the alkoxysilyl functional groups of the polymer. Thus, these silane additives may remove water from the system before water can participate in early hydrolysis and condensation reactions. However, since these silane additives require relatively high additions to be effective, it can result in a long tack-free time, affect the curing characteristics, and raise safety concerns. Therefore, for these and other reasons, they have not proven to be entirely satisfactory.

[0005] Another approach is to use sulfur or other sulfur-containing compounds to poison the catalyst. However, this poisoning can inhibit or completely deactivate the hydrolysis and condensation catalysts, which can result in a reduced curing rate.

[0006] Therefore, there remains a need for methods and compositions for preventing premature curing of alkoxysilyl-containing polymer compositions that use organometallic urethane-forming catalysts in the preparation of polymers during the handling and compounding of coatings, adhesives, sealants, and other products, and also for providing rapid curing of the compounded products after exposure to moisture. SUMMARY OF THE INVENTION

[0007] According to one aspect of the present invention, an alkoxysilyl-containing polyurethane polymer composition is prepared using an organometallic compound such as a metal salt or metal complex as a urethane-forming catalyst when the organometallic compound is added to the composition as a hydrolysis and condensation catalyst, and is then stabilized by adding a mercapto-containing compound, particularly a mercapto-containing alkoxysilane, to the composition. The curing rate of the present invention is compared to a composition that does not contain a mercapto-containing compound.

[0008] Alkoxysilyl-containing polyurethanes are prepared from the reaction of a polyol with an isocyanato-containing alkoxysilane, or the reaction of an isocyanato-containing polymer with an amino-containing or ureido-containing alkoxysilane.

[0009] The polyol can be a polyester polyol, a polyether polyol, a polycarbonate polyol, a polybutadiene polyol, a polybutylene polyol, a polyol derived from a polystyrene / butadiene copolymer, a polyisoprene polyol, a poly(meth)acrylate polyol, a polyisocyanate-extended polyester polyol, a polyisocyanate-extended polyether polyol, a polyisocyanate-extended polycarbonate polyol, a polyisocyanate-extended polyol derived from a polystyrene / butadiene copolymer, a polyisocyanate-extended polyisoprene polyol, a polyisocyanate-extended poly(meth)acrylate polyol, a polyisocyanate-extended polybutadiene polyol, a polyisocyanate-extended polybutylene polyol, and mixtures thereof.

[0010] The isocyanato-containing polymer intermediate is prepared from the reaction of a polyisocyanate and a polyol and includes a polyester polyol, a polyol derived from a styrene / butadiene copolymer, a polyether polyol, a polycarbonate polyol, a poly(meth)acrylate polyol, a polyisoprene polyol, a polybutadiene polyol or a polybutylene polyol. The reaction of the polyol with an isocyanato-containing alkoxysilane or the reaction of the polyol with a polyisocyanate is carried out in the presence of at least one metal salt or metal complex that is a urethane-forming catalyst. The urethane-forming catalyst increases the reaction rate, thereby providing the advantages of a shorter reaction time and a lower reaction temperature for the preparation of an alkoxysilyl-containing polymer or an intermediate polyisocyanate-extended polyol or a polyisocyanate-containing polymer.

[0011] In the present invention, the urethane-forming catalyst is not limited to an organometallic catalyst. The amount of the urethane-forming catalyst used in the preparation of the alkoxysilyl-containing polyurethane polymer composition is about 1 to about 100 ppm, preferably about 5 to about 50 ppm, most preferably about 10 to about 25 ppm, based on the weight of the metal added to the polyol. The stabilizing amount of the mercapto-containing compound depends on the amount of the urethane-forming catalyst used and is about 4 to about 100 equivalents of mercapto (-SH) per equivalent of metal in the catalyst, more preferably about 8 to about 50 equivalents of mercapto (-SH) per equivalent of metal in the catalyst, and most preferably about 12 to about 25 equivalents of mercapto (-SH) per equivalent of metal in the catalyst.

[0012] An alkoxysilyl-containing polyurethane polymer composition stabilized with a mercapto compound can be activated for moisture curing by the addition of a hydrolysis and condensation catalyst. The amount of the hydrolysis and condensation catalyst added to the alkoxysilyl-containing polyurethane polymer composition is about 0.02 to about 1.0 weight percent, preferably about 0.05 to about 0.5 weight percent, and even more preferably about 0.1 to about 0.3 weight percent of metal, based on the weight of the alkoxysilyl-containing polyurethane polymer.

[0013] The alkoxysilyl-containing polyurethane polymer composition can be combined with other components to form coatings, adhesives, sealants, or other consumer or industrial products.

DETAILED DESCRIPTION OF THE INVENTION

[0014] In the specification and claims herein, the following terms and expressions should be understood to have the meanings indicated below.

[0015] The singular forms "a", "an", and "the" include the plural forms.

[0016] Unless otherwise indicated in the examples or otherwise shown, all numerical values representing amounts of materials, reaction conditions, durations, quantitatively defined properties of materials, etc. described in the specification and claims should be understood to be modified by the term "about".

[0017] All methods described herein can be performed in any suitable order unless otherwise indicated or clearly excluded by the context. The use of any examples or exemplary language provided herein (e.g., "such as" or "including") is merely intended to better illuminate the invention and does not limit the scope of the invention unless such is clearly intended.

[0018] No language in the specification should be construed to indicate that an element not claimed is essential to the practice of the invention.

[0019] As used herein, the terms "comprising", "including", "containing", "characterized by", and terms of similar meaning are to be understood as being inclusive or open-ended and not excluding additional, unrecited elements or method steps, and further, such terms are to be understood to include more limiting terms such as "consisting of" and "consisting essentially of".

[0020] Compositional percentages are given in weight percentages unless otherwise specified.

[0021] Unless the context clearly indicates otherwise, a particular numerical value includes at least that value, and any range of numerical values is understood to include all sub-ranges within that range and any combination of various combinations of the endpoints of such range or sub-ranges.

[0022] Compounds, materials or substances disclosed in the specification and / or recited in the claims, whether expressly or implicitly, as belonging to a group of structurally, compositionally and / or functionally related compounds, materials or substances, include individual representatives of that group and all combinations thereof.

[0023] The expression "alkoxysilyl-containing polyurethane polymer" as used herein is to be understood to apply to any polymer containing one or more terminal and / or pendant alkoxysilyl groups and at least one urethane (carbamate) functional group, preferably at least two urethane (carbamate) functional groups.

[0024] The terms "silylation" and "silylated" are to be understood herein as applying to any conventional or other known method by which an alkoxysilyl group is introduced into or becomes part of a silicone or non-silicone polymer, thereby rendering the curable polymer moisture-curable. Accordingly, the terms "silylation" and "silylated" should be regarded as including "hydrosilylation" and "hydrosilylated", respectively.

[0025] The term "organometallic compound" is to be understood herein as referring to a compound containing at least one metal atom and at least one carbon atom.

[0026] The term "metal complex" is to be understood herein as referring to an organometallic compound formed by the combination of a metal with another organic compound containing a coordination covalent bond and which is convertible back to the original metal and the original organic compound.

[0027] The term "metal salt" is to be understood herein as referring to an organometallic compound containing a metal ion and at least one anion having at least one lone pair of electrons and at least one carbon atom, where the metal ion and the anion are bonded via an ionic bond.

[0028] The term "cure" is to be understood herein as referring to a series of chemical changes in which the alkoxysilyl groups of an alkoxysilyl-containing polymer first undergo hydrolysis in the presence of moisture to form hydrolysis products (silanol-containing polymers), which then condense with themselves, other hydrolyzed products and / or the unhydrolyzed alkoxysilyl-containing polymer.

[0029] The term "polymer" as used herein is understood to be synonymous with "resin" and vice versa.

[0030] The term "moisture" as related to the hydrolysis of the alkoxysilyl-containing polymer should be understood herein to include liquid water, vapor, and steam.

[0031] As used herein, the term "monovalent" with respect to a group means that the group can form one covalent bond per group, and "divalent" means that the group can form two covalent bonds per group. As used herein, the term "polyvalent" with respect to a group means that the group can form two or more covalent bonds per group.

[0032] As used herein, the term "hydrocarbon group" is a group consisting of carbon atoms and hydrogen atoms, and includes acyclic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0033] The term "heteroatom" means an element selected from oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

[0034] As used herein, the term "acyclic hydrocarbon group" preferably means any straight-chain or branched hydrocarbon group containing from 1 to about 60 carbon atoms and which can be saturated or unsaturated. Suitable monovalent acyclic hydrocarbon groups include alkyl, alkenyl, and alkynyl groups. Representative and non-limiting examples of acyclic hydrocarbon groups are methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl, propenyl, and butynyl.

[0035] As used herein, the term "alkyl" means any saturated straight-chain or branched hydrocarbon group. In preferred embodiments, the monovalent alkyl group is selected from straight-chain or branched alkyl groups containing from 1 to about 60 carbons per group, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, and dodecyl. The term "monovalent alkyl" group is, for example, -CH2 CH 2 CH 3 means any saturated hydrocarbon group having one open valence, such as. The term "divalent alkyl" refers to, for example, -CH 2 CH 2 CH 2 -, a saturated straight-chain or branched hydrocarbon group having two open valences, such as. The term "polyvalent alkyl" means, for example, any saturated straight-chain or branched hydrocarbon group having two or more open valences, such as when the number of open valences is 3 (-CH 2 ) 2 CH-.

[0036] As used herein, the term "cycloalkyl" means an alicyclic hydrocarbon group that does not contain unsaturation.

[0037] As used herein, the term "alkenyl" means any straight-chain or branched monovalent hydrocarbon group that contains at least one carbon-carbon double bond and preferably contains from 2 to about 10 carbon atoms, such as ethenyl, 2-propenyl, 3-butenyl, 5-hexenyl, and 7-octenyl.

[0038] As used herein, the term "alicyclic hydrocarbon group" means a group containing one or more hydrocarbon rings, preferably containing from 3 to 12 carbon atoms, which may optionally be substituted on one or more of the rings with one or more monovalent or divalent acyclic groups preferably containing from 1 to about 6 carbon atoms. In the case of an alicyclic hydrocarbon group containing two or more rings, the rings may be fused rings in which two rings share two or more carbon atoms, or rings that are linked to each other via a covalent bond or a divalent acyclic group. Suitable monovalent alicyclic hydrocarbon groups include, for example, cycloalkyl groups such as cyclohexyl and cyclooctyl, or cycloalkenyl groups such as cyclohexenyl. Suitable divalent hydrocarbon groups include, for example, saturated or unsaturated divalent monocyclic hydrocarbon groups, such as 1,4-cyclohexyl, where the numbers 1 and 4 indicate where the open valences are located on the cyclohexyl group. The divalent alicyclic hydrocarbon is sometimes referred to as a 1,4-cyclohexylene group. Suitable trivalent alicyclic hydrocarbon groups include cycloalkanetriyl groups such as 1,2,6-cyclohexyl, where the numbers represent the positions of the open valences on the ring.

[0039] As used herein, the term "aromatic hydrocarbon group" means a hydrocarbon group containing one or more aromatic rings, which may optionally be substituted on the aromatic rings with one or more monovalent or divalent acyclic groups preferably containing from 1 to about 6 carbon atoms. In the case of an aromatic hydrocarbon group containing two or more rings, the rings may be fused rings in which the rings share two or more carbon atoms, or rings that are linked to each other via a covalent bond or a divalent acyclic group. Suitable monovalent aromatic hydrocarbon groups include, for example, phenyl, tolyl, 2,4,6-trimethylphenyl, naphthyl and anthryl, and aralkyl groups such as 2-phenylethyl.

[0040] The present invention involves adding a mercapto-containing compound to an alkoxysilyl-containing polyurethane polymer or urethane prepolymer containing a urethane-forming organometallic catalyst. The mercapto-containing compound renders the urethane-forming organometallic catalyst remaining in the resulting polymer inert or less active in its ability to catalyze the hydrolysis and / or condensation reaction of the alkoxysilyl groups with moisture. With an inert or less active catalyst, the alkoxysilyl-containing polyurethane polymer can be handled in an environment containing low levels of moisture without undergoing premature curing of the alkoxysilyl-containing polyurethane polymer, thereby rendering the alkoxysilyl-containing polyurethane polymer more stable. The addition of the mercapto-containing compound can result in better moisture stability of the composition containing the alkoxysilyl-containing polyurethane polymer and the urethane-forming organometallic catalyst.

[0041] Accordingly, by adding a suitable mercapto-containing compound, particularly a mercaptosilane, preferably towards the end of the alkoxysilyl-containing polyurethane polymer synthesis process, a stabilized alkoxysilyl-containing polyurethane polymer composition can be produced. The urethane-forming organometallic catalyst can be added to a mixture of polyol, polyisocyanate and / or silylating agent, thereby catalyzing the urethane-forming reaction to form an alkoxysilyl-containing polyurethane polymer and / or urethane prepolymer, and the final product exhibits effectively enhanced moisture stability after the addition of the mercapto-containing compound. Thus, an alkoxysilyl-containing polyurethane polymer is prepared and a mercapto-containing compound, particularly a mercaptosilane, is added to stabilize the composition from reaction with moisture, thereby avoiding premature curing during handling, processing, and compounding of the composition into coatings, adhesives, sealants or other products, and then a hydrolyzing and condensing organometallic catalyst is added to the alkoxysilyl-containing polyurethane polymer composition to activate the moisture curing reaction.

[0042] The amount of the mercapto-containing compound, particularly mercaptosilane, can be small, yet it can still inactivate or further reduce the activity of the urethane-forming organometallic catalyst.

[0043] In one embodiment, the alkoxysilyl-containing polymer composition of the present invention can be used in the production of moisture-curable compositions such as moisture-curable coatings, adhesives, sealants, consumer products, or industrial products.

[0044] Preparation of the alkoxysilyl-containing polyurethane polymer composition

[0045] The alkoxysilyl-containing polyurethane polymer has the general chemical formula (I),

Chemical formula

Chemical formula

[0046] In one embodiment, G is a polyvalent organic group derived from a polyol or a monool and formed by removing the hydroxyl groups of the polyol.

[0047] The polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, polybutylene polyols, polyols derived from polystyrene / butadiene copolymers, polyisoprene polyols, poly(meth)acrylate polyols, polyisocyanate-extended polyester polyols, polyisocyanate-extended polyether polyols, polyisocyanate-extended polycarbonate polyols, polyisocyanate-extended polyols derived from polystyrene / butadiene copolymers, polyisocyanate-extended polyisoprene polyols, polyisocyanate-extended poly(meth)acrylate polyols, polyisocyanate-extended polybutadiene polyols, polyisocyanate-extended polybutylene polyols, and mixtures thereof.

[0048] Polyisocyanate-extended polyester polyol, polyisocyanate-extended polyether polyol, polyisocyanate-extended polycarbonate polyol, polyisocyanate-extended polyol derived from polystyrene / butadiene copolymer, polyisocyanate-extended polyisoprene polyol, polyisocyanate-extended poly(meth)acrylate polyol, polyisocyanate-extended polybutadiene polyol, polyisocyanate-extended polybutylene polyol are hydroxyl-containing polyurethanes.

[0049] The hydroxyl-containing polyurethane polymer is prepared by reacting an excess of polyol with polyisocyanate in the presence of a urethane-forming organometallic catalyst.

[0050] The alkoxysilyl-containing polyurethane polymer can be prepared by a batch process, a semi-continuous process, or a continuous process.

[0051] In one embodiment, the polyol can react with an isocyanate-containing alkoxysilane in the presence of a urethane-forming organometallic catalyst to produce an alkoxysilyl-containing polyurethane polymer composition, and subsequently, a mercapto-containing compound, particularly mercaptosilane, is added to the reaction product. The alkoxysilyl-containing polyurethane polymer has the general formula (I) where b is 0.

[0052] In another embodiment, the polyol can react with an excess of polyisocyanate in the presence of a urethane-forming organometallic catalyst to form an isocyanate-containing prepolymer composition, which reacts with an amine-containing alkoxysilane to produce an alkoxysilyl-containing polyurethane polymer composition. The addition mode can include adding the amino-containing alkoxysilane to the polyisocyanate to form an isocyanate-containing alkoxysilane, which is subsequently reacted with the polyol, adding the amino-containing alkoxysilane during the reaction of the polyisocyanate and the polyol, or adding the amino-containing alkoxysilane to the already formed isocyanate-containing prepolymer. A mercapto-containing compound, particularly mercaptosilane, is usually added after the urethane-forming reaction is completed. The addition of the mercapto-containing compound can be to the isocyanato-containing prepolymer composition or the alkoxysilyl-containing polyurethane polymer composition. The alkoxysilyl-containing polyurethane polymer in this reaction sequence has the general formula (I) where b is 1.

[0053] Hydroxyl-containing polyurethanes and isocyanate-containing polyurethanes

[0054] An alkoxysilyl-containing polymer composition can be prepared using hydroxyl-containing polyurethanes and isocyanate-containing polyurethanes. The hydroxyl-containing polyurethanes and isocyanato-containing urethanes are obtained by reacting at least one of the above polyols with at least one organic polyisocyanate in the presence of a catalytically effective amount of a urethane-forming organometallic catalyst under urethane-forming reaction conditions such as any well-known in the art.

[0055] Suitable organic polyisocyanates can be represented by formula (III), G 1 (NCO) z (III) Here, z is 2 or 3, more specifically 2, or a blend of polyisocyanates having at least one diisocyanate of structure (III) where z is 2 and at least one triisocyanate of structure (III) where z is 3, and G 1 is a z-valent organic group, preferably a divalent or trivalent hydrocarbon group such as an aliphatic or alicyclic group containing from 1 to 30 carbon atoms, preferably from 6 to 24 carbon atoms, or a divalent or trivalent organic group derived from a hydrocarbon and containing at least one isocyanurate ring, at least one urethane group and / or at least one oxygen atom. Polyisocyanates containing a hydrocarbon and at least one urethane group can be prepared from the reaction of a diisocyanate or triisocyanate with a trihydroxyalkane having from 3 to 10 carbon atoms.

[0056] Organic polyisocyanates suitable for use in the preparation of hydroxyl-terminated polyurethanes and isocyanate-terminated polyurethanes include, but are not limited to, diisocyanates, triisocyanates, dimers, trimers, and mixtures thereof. Specific examples of useful polyisocyanates include hydrogenated 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, isophorone diisocyanate dimer, isophorone diisocyanate trimer, the reaction product of isophorone diisocyanate and a triol, and equivalents thereof, and mixtures thereof, but are not limited thereto. Isophorone diisocyanate, its dimer and trimer and mixtures thereof are preferred for use herein.

[0057] In one embodiment, the organic polyisocyanate (III) is a mixture comprising an organic polyisocyanate containing two isocyanate groups and an organic polyisocyanate containing three isocyanate groups. The molar ratio of the organic polyisocyanate containing two isocyanate groups to the organic polyisocyanate containing three isocyanate groups is from about 10:1 to about 1:10, preferably from about 2:1 to about 1:2, more preferably from about 1.5:1 to about 1:1.5.

[0058] The chain extension reaction can be carried out in various ways depending on the desired properties of the chain extended polyol. For example, the polyisocyanate (III) is very suitable as a chain extender. In one embodiment, when it is desired to have at least one chain extended polyol, the at least one chain extended polyol can be produced by continuously mixing a molar excess of polyol with the polyisocyanate (III) to produce a hydroxyl-terminated polyurethane. The molar excess of polyol in the chain extension reaction produces an OH:NCO molar ratio greater than about 1:1. In a more specific embodiment, the molar ratio of OH:NCO ranges from about 1.1:1 to about 10:1, even more specifically from about 1.5:1 to about 3:1, even more specifically from about 1.8:1 to about 2.2:1, to provide a hydroxyl-terminated polyurethane.

[0059] In one embodiment where it is desired to have an isocyanate-containing polyurethane prepolymer in which the reactive functional group is an isocyanate group, the isocyanate-containing polyurethane prepolymer can be produced by continuously mixing a molar excess of the polyisocyanate (III) with the polyol to provide the isocyanate-containing polyurethane prepolymer. The molar excess of the polyisocyanate (III) in the urethane-forming reaction produces an OH:NCO molar ratio less than about 1:1. In a more specific embodiment, the molar ratio of OH:NCO ranges from about 0.1:1 to about 0.9:1, even more specifically from about 0.3:1 to about 0.7:1, even more specifically from about 0.45:1 to about 0.55:1, to provide an isocyanate-terminated polyurethane prepolymer.

[0060] The conditions for the polyurethane-forming reaction can include a reaction temperature of from about 20 to about 180 °C, preferably from about 60 to about 130 °C, a pressure of from about 10 to about 300 kilopascals, preferably from about 50 to about 150 kilopascals, more preferably about 100 kilopascals, and a reaction time of from about 0.50 to about 24 hours, preferably from about 2 to about 8 hours. The chain extension reaction can be carried out in the presence of a urethane-forming organometallic catalyst used in the urethane-forming reaction.

[0061] Known and conventional urethane-forming organometallic catalysts for the urethane-forming reaction are contemplated. Suitable urethane-forming catalysts include organometallic salts or organometallic complexes. Examples of the metal moiety of the urethane-forming organometallic catalysts useful in the present invention include tin, zirconium, iron, cobalt, manganese, nickel, bismuth, and zinc, more preferably tin, bismuth, and zinc, and even more preferably tin. Urethane-forming organometallic catalysts include metal complexes, such as chelates of various metals having acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, salicylaldehydeimine, etc., obtained from various metals such as Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn; and organometallic salts, such as alcoholates and phenolates of various metals, such as Zr(OR 8 ) 2 , Sn(OR 8 ) 4 , Sn(OR 8 ) 2 , Bi(OR 8 ) 3 etc., where R 8 is a monovalent alkyl or aryl of 1 to 18 carbon atoms, or carboxylates of various metals, such as Zr(O(C=O)R 8 ) 2 , Sn(O(C=O)R 8 ) 4 , Sn(O(C=O)R 8 )2 , Bi(O(C=O)R 8 ) 3 , R 9 2 Sn(O(C=O)R 8 ) 2 , where R 8 is a monovalent alkyl or aryl of 1 to 18 carbon atoms, and R 9 is a monovalent alkyl or aryl of 1 to 18 carbon atoms; and reaction products of alcoholates of various metals with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino)alkanols are included.

[0062] In one particular embodiment, the organotin compound that is a dialkyltin salt of a carboxylic acid can include non-limiting examples such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-bis(6-methylaminocaproate), and combinations thereof.

[0063] Similarly, in another particular embodiment, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride and combinations thereof can be used. Non-limiting examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and equivalents, and combinations thereof.

[0064] The amount of the urethane-forming catalyst used in the preparation of the alkoxysilyl-containing polyurethane polymer composition is about 1 to about 100 ppm, preferably about 5 to about 50 ppm, and most preferably about 10 to about 25 ppm based on the weight of the metal added to the polyol.

[0065] Silylation reaction for forming an alkoxysilyl-containing polyurethane polymer

[0066] In one embodiment, the alkoxysilyl-containing polyurethane polymer can be prepared from the reaction of a polyol and an isocyanato-containing alkoxysilane in the presence of a urethane-forming organometallic catalyst. The polyol includes a polyisocyanate-extended polyol, also referred to as a hydroxyl-containing polyurethane. The polyol is a compound having the general formula (IV). G(O-H) c+1 (IV)

[0067] Here, G is an organic group, and the subscript c is an integer from 0 to 5, preferably 1, 2, or 3. The organic group G is derived from a polyester polymer, a polyether polymer, a polycarbonate polymer, a polybutadiene polymer, a polybutylene polymer, a polystyrene / butadiene copolymer, a polyisoprene polymer, a poly(meth)acrylate polymer, a polyisocyanate-extended polyester polymer, a polyisocyanate-extended polyether polymer, a polyisocyanate-extended polycarbonate polymer, a polyisocyanate-extended polystyrene / butadiene copolymer, a polyisocyanate-extended polyisoprene polymer, a polyisocyanate-extended poly(meth)acrylate polymer, a polyisocyanate-extended polybutadiene polymer, a polyisocyanate-extended polybutylene polymer, and mixtures thereof.

[0068] The polyol is selected from the group consisting of polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polybutylene polyol, polyol derived from polystyrene / butadiene copolymer, polyisoprene polyol, poly(meth)acrylate polyol, polyisocyanate-extended polyester polyol, polyisocyanate-extended polyether polyol, polyisocyanate-extended polycarbonate polyol, polyisocyanate-extended polyol derived from polystyrene / butadiene copolymer, polyisocyanate-extended polyisoprene polyol, polyisocyanate-extended poly(meth)acrylate polyol, polyisocyanate-extended polybutadiene polyol, polyisocyanate-extended polybutylene polyol, and mixtures thereof.

[0069] The isocyanate-containing alkoxysilane useful for silylating the polyol has the general formula (V), O=C=N-R 3 -SiR 2 (3-a) (OR 1 ) a (V) where each R 1 is independently a monovalent alkyl group of 1 to 6 carbon atoms; each R 2 is independently a monovalent alkyl group or phenyl group of 1 to 4 carbon atoms; each R 3 is independently a divalent alkyl group of 1 to 12 carbon atoms; and the subscript a is an integer, where a is 1, 2, or 3.

[0070] In one embodiment, R 3 is -(CH 2 ) n -, where n is 1, 2 or 3, each R 1 is independently methyl, ethyl, propyl, or isopropyl, and a is 3.

[0071] Specific isocyanato-containing alkoxysilanes (V) that can be used here to react with the aforementioned polyols and hydroxyl-containing polyurethanes to provide an alkoxysilyl-containing polyurethane polymer (I) include isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, isocyanato-t-butyltrimethoxysilane, isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, isocyanatoisopropyltriethoxysilane, 4-isocyanato-n-butyltriethoxysilane, isocyanato-t-butyltriethoxysilane, and the like.

[0072] Urethane-forming organometallic catalysts useful for the silylation of the aforementioned polyols, including hydroxyl-containing polyurethanes, include those indicated above as being suitable for use in the preparation of hydroxyl-containing polyurethanes.

[0073] Known and conventional urethane-forming organometallic catalysts for the urethane-forming reaction are contemplated. Suitable urethane-forming catalysts include organometallic salts or organometallic complexes. Examples of the metal moieties of urethane-forming organometallic catalysts useful in the present invention include tin, zirconium, iron, cobalt, manganese, nickel, bismuth, and zinc, more preferably tin, bismuth, and zinc, and even more preferably tin. Urethane-forming organometallic catalysts include metal complexes, such as chelates of various metals obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, salicylaldehydeimine, etc., having various metals such as Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn; and organometallic salts, such as alcoholates and phenolates of various metals, such as Zr(OR 7 ) 2 , Sn(OR7 ) 4 , Sn(OR 7 ) 2 , Bi(OR 7 ) 3 etc., where R 7 is a monovalent alkyl or aryl having 1 to 18 carbon atoms, or carboxylates of various metals, for example, Zr(O(C=O)R 7 ) 2 , Sn(O(C=O)R 7 ) 4 , Sn(O(C=O)R 7 ) 2 , Bi(O(C=O)R 7 ) 3 , R 8 2 Sn(O(C=O)R 7 ) 2 , where R 8 is a monovalent alkyl or aryl having 1 to 18 carbon atoms; and reaction products of various metal alcoholates with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino)alkanols are included.

[0074] In one particular embodiment, the organotin compound that is a dialkyltin salt of a carboxylic acid can include non-limiting examples such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-bis(6-methylaminocaproate), and combinations thereof.

[0075] Similarly, in another specific embodiment, trialkyltin hydroxides, dialkyltin oxides, dialkyltin dialkoxides, or dialkyltin dichlorides and combinations thereof can be used. Non-limiting examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, etc., and combinations thereof.

[0076] The amount of the urethane-forming catalyst used in the preparation of the alkoxysilyl-containing polyurethane polymer composition is from about 1 to about 100 ppm, preferably from about 5 to about 50 ppm, and most preferably from about 10 to about 25 ppm, based on the weight of the metal added to the polyol.

[0077] The isocyanato-containing alkoxysilane used in the silylation reaction can be used in a slight molar excess or a slight molar deficiency of the hydroxyl equivalent (OH groups) of the polyol relative to the isocyanate equivalent (NCO groups) of the isocyanatosilane. Advantageously, the molar ratio of NCO to OH is from about 0.7 to about 1.5, more preferably from about 0.9 to about 1.1, and more specifically from about 0.98 to about 1.02.

[0078] Particularly useful alkoxysilyl-containing polyurethane polymers having formula (I) are prepared from polypropylene diol, an aliphatic diisocyanate and 3-isocyanatopropyltrialkoxysilane. The polypropylene diol advantageously has a level of terminal ethylenic unsaturation of less than about 0.02 milliequivalents per gram (meq / g) of polyol, more advantageously less than about 0.008 meq / g, and a number average molecular weight of from about 5,000 to about 15,000 grams per mole as determined by hydroxyl end group analysis. The molar ratio of the isocyanate (NCO) of the isocyanatosilane to the hydroxyl of the hydroxyl-terminated polyurethane resin can range from about 0.9 to about 1.05, more specifically from about 1.0 to about 1.5.

[0079] The conditions of the silylation reaction can include a reaction temperature of from about 20 to about 180 °C, preferably from about 60 to about 130 °C, a pressure of from about 10 to about 300 kilopascals, preferably from about 50 to about 150 kilopascals, preferably about 100 kilopascals, and a reaction time of from about 0.50 to about 24 hours, preferably from about 2 to about 8 hours.

[0080] The silylation of the polyol is completed when there are no hydroxyl groups after silylation when an isocyanato-containing alkoxysilane is used in excess, or when there are no isocyanate groups after silylation when an excess of polyol is used. When an excess of polyol is used, when more than about 90 mole percent, preferably more than about 95 mole percent, most preferably more than about 98 mole percent of the isocyanato-containing alkoxysilane has reacted with the hydroxyl groups of the polyol, the silylation reaction is substantially complete. When an excess of isocyanato-containing silane is used, when more than about 80 mole percent, preferably more than about 90 mole percent, most preferably more than about 95 mole percent of the isocyanato-containing alkoxysilane has reacted with the hydroxyl groups of the polyol, the silylation reaction is substantially complete. The amount of residual isocyanato-containing silane is determined by measuring the amount of isocyanate groups. The amount of isocyanate groups can be determined using ASTM D2572-97(2010), Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers.

[0081] In another embodiment, the alkoxysilyl-containing polyurethane polymer can be prepared from the reaction of an isocyanato-containing polyurethane prepolymer and an amino-containing alkoxysilane in the presence or absence of a urethane-forming organometallic catalyst. When no urethane-forming organometallic catalyst is present, the reaction proceeds at a sufficient rate such that a urethane-forming organometallic catalyst is not required for these silylation reactions. However, a urethane-forming organometallic catalyst may be present from the preparation of the isocyanato-containing polyurethane prepolymer and need not be removed prior to the silylation reaction.

[0082] The isocyanato-containing polyurethane prepolymer can include a chain-extended isocyanato-containing polyurethane prepolymer in which two or more polyols react with a polyisocyanate to form a hydroxyl-containing polyurethane, followed by reaction with more polyisocyanate. The isocyanato-containing polyurethane prepolymer is a compound having the general formula (VI), G[O-(C=O)NHR10 N=C=O] c+1 (VI) Here G is a polyvalent organic group derived from a polyol or a monovalent organic group derived from a monool; Each R 10 is independently a divalent alkyl group having 1 to 16 carbon atoms, a divalent cycloalkyl group having 5 to 16 carbon atoms, and a group X having the general formula (VII) 2 and is a divalent organic group selected from the group consisting of; [Chemical formula] Here each R 6 is independently an alkylene group having 1 to 12 carbon atoms or a cycloalkylene group having 5 to 16 carbon atoms; each R 7 is independently a divalent organic group selected from the group consisting of a divalent alkyl group having 1 to 16 carbon atoms and a divalent cycloalkyl group having 5 to 16 carbon atoms; and the subscript c is an integer, where c is 0 to 5, preferably 1, 2, or 3.

[0083] The organic group G is derivable from a polyol from which a hydroxyl group has been removed. The polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, polybutylene polyols, polyols derived from polystyrene / butadiene copolymers, polyisoprene polyols, poly(meth)acrylate polyols, polyisocyanate-extended polyester polyols, polyisocyanate-extended polyether polyols, polyisocyanate-extended polycarbonate polyols, polyisocyanate-extended polyols derived from polystyrene / butadiene copolymers, polyisocyanate-extended polyisoprene polyols, polyisocyanate-extended poly(meth)acrylate polyols, polyisocyanate-extended polybutadiene polyols, polyisocyanate-extended polybutylene polyols, and mixtures thereof.

[0084] Amino-containing alkoxysilanes useful for silylating polyols have the general formula (VIII): HN(R 4 )-R 3 -SiR 2 (3-a) (OR 1 ) a (VIII) where each R 1 is independently a monovalent alkyl group of 1 to 6 carbon atoms; each R 2 is independently a monovalent alkyl group of 1 to 4 carbon atoms or a phenyl group; each R 3 is independently a divalent alkyl group of 1 to 12 carbon atoms; each R 4 is independently a monovalent alkyl group of 1 to 6 carbon atoms, a phenyl group, hydrogen, or a -R 3 SiR 2 3-a (OR 1 ) a group; and the subscript a is an integer, where a is 1, 2, or 3.

[0085] In one embodiment, R 3 is -(CH 2 ) n -, where n is 1, 2, or 3, each R 1 is independently methyl, ethyl, propyl, or isopropyl, and a is 3.

[0086] Specific amino-containing alkoxysilanes (VIII) that can be used herein to react with the aforementioned isocyanato-containing polyurethane prepolymer to provide an alkoxysilyl-containing polyurethane polymer (I) include amino-containing alkoxysilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropyl-methyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3-(N-methyl-2-amino-1-methyl-1-ethoxy)-propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethyl-butyl-dimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane, N-(cyclohexyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, bis-(3-trimethoxysilyl-2-methylpropyl)amine, N-(3'-trimethoxysilylpropyl)-3-amino-2-methylpropyltrimethoxysilane or combinations thereof.

[0087] The amino-containing alkoxysilane used in the silylation reaction can be used in a slight molar excess or slight molar deficiency of the isocyanate equivalent of the isocyanato-containing polyurethane prepolymer with respect to the amino equivalent of the amino-containing alkoxysilane (NH groups). Advantageously, the molar ratio of NH to NCO is from about 0.7 to about 1.5, more preferably from about 0.9 to about 1.1, and more specifically still from about 0.98 to about 1.02.

[0088] Particularly useful alkoxysilyl-containing polyurethane polymers having formula (I) are prepared from polypropylene diol, an aliphatic diisocyanate, and a secondary amino-containing trialkoxysilane. The polypropylene diol advantageously has a level of terminal ethylenic unsaturation of less than about 0.02 meq / g, more advantageously less than about 0.008 meq / g, per gram of polyol, and a number average molecular weight determined by hydroxyl end group analysis of from about 5,000 to about 15,000 grams per mole. The molar ratio of the amino groups (NH) of the amino-containing alkoxysilane to the isocyanate groups (NCO) of the isocyanato-containing polyurethane prepolymer can range from about 0.9 to about 1.05, more specifically from about 0.98 to about 1.02.

[0089] The conditions of the silylation reaction can have a reaction temperature of from about 20 to about 180 °C, preferably from about 60 to about 130 °C, a pressure of from about 10 to about 300 kilopascals, preferably from about 50 to about 150 kilopascals, more preferably about 100 kilopascals, and a reaction time of from about 0.50 to about 24 hours, preferably from about 2 to about 8 hours.

[0090] The silylation of the isocyanato-containing polyurethane prepolymer is completed when no isocyanate groups are present after silylation when an excess of amino-containing alkoxysilane is used, or when no amino groups are present after silylation when an excess of isocyanato-containing polyurethane prepolymer is used. When an excess of isocyanato-containing polyurethane prepolymer is used and more than about 90 mole percent, preferably more than about 95 mole percent, most preferably more than about 98 mole percent of the amino-containing alkoxysilane has reacted with the isocyanate groups of the isocyanato-containing polyurethane prepolymer, the silylation reaction is substantially complete. When an excess of amino-containing silane is used and more than about 80 mole percent, preferably more than about 90 mole percent, most preferably more than about 95 mole percent of the amino-containing alkoxysilane has reacted with the isocyanate groups of the isocyanato-containing polyurethane prepolymer, the silylation reaction is substantially complete. The amount of residual isocyanato-containing polyurethane prepolymer is determined by measuring the amount of isocyanate groups. The amount of isocyanate groups can be determined using ASTM D2572-97(2010), Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers.

[0091] In the production of an alkoxysilyl-containing polyurethane polymer composition, residual isocyanate may remain in the composition due to an imbalance or incomplete reaction of the silylating agent. Residual isocyanate can be removed from the composition by reacting the isocyanate groups with a reactive hydrogen quenching agent such as, for example, a monoalcohol, a secondary amine, or a lactam. The quenching reaction is preferably carried out in the presence of a urethane-forming organometallic catalyst.

[0092] A mercapto-containing compound is added to an alkoxysilyl-containing polyurethane polymer composition to form a moisture-stable alkoxysilyl-containing polyurethane polymer composition. The moisture-stable alkoxysilyl-containing polyurethane polymer composition can be removed from the reaction apparatus for storage or for further incorporation into coatings, adhesives, sealants or other good products for consumers or industry.

[0093] The process for making the moisture-stable alkoxysilyl-containing polyurethane polymer composition can be a batch, semi-continuous, or continuous process, but the process is preferably a continuous process. The advantages of a continuous process include, for example, easy application to mass production and scale-up operations. Furthermore, the efficiency of the process can be improved. In a continuous process, reaction chambers can be provided as needed for the chain extension reaction of the polyol and polyisocyanate and for the silylation step.

[0094] Mercapto-containing compound as stabilizer

[0095] The mercapto-containing compound can render the urethane-forming organometallic catalyst inactive or less active for catalyzing the hydrolysis and condensation reactions of the alkoxysilyl groups in the alkoxysilyl-containing polyurethane polymer composition. The mercapto-containing compound can have the general formula (IX), (HS) o R 11 X 2 p (IX) where each R 11 is independently a divalent or polyvalent hydrocarbon containing 1 to 20 carbon atoms, or a divalent or polyvalent hydrocarbon containing 1 to 20 carbon atoms and at least one oxygen atom; each X 2 is independently hydroxyl (-OH), carboxyl (-C(=O)OH), ester (-C(=O)OR 17 , where R 17is a divalent alkyl group having 1 to 10 carbon atoms or a divalent alkyl group having 1 to 10 carbon atoms and substituted with at least one hydroxyl group), carboxylate (-C(=O)O-HN + (R 12 )(R 13 ) 2 , where R 12 is a chemical bond to R 11 , hydrogen, or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and each R 13 is independently hydrogen or a monovalent hydrocarbon group having 1 to 12 carbon atoms), amino - NR 13 2 , where each R 13 is independently hydrogen or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and alkoxysilyl group (-Si(OR 14 ) e (R 15 ) 3-e , each R 14 is independently a monovalent alkyl group having 1 to 10 carbon atoms, a monovalent alkyl group having 1 to 10 carbon atoms and substituted with at least one hydroxyl group, a monovalent alkyl group containing 3 to 30 carbon atoms and at least one oxygen atom, or -R 16 O[Si(R 11 (SH) o )(OR 17 ) f (R 15 ) 1-f q OR 18 group, where each R 15 is independently methyl or phenyl, each R 16 is independently a divalent alkyl group having 1 to 10 carbon atoms or a divalent alkyl group having 1 to 10 carbon atoms and substituted with at least one hydroxyl group, each R 17 is independently a divalent alkyl group having 1 to 10 carbon atoms or a divalent alkyl group having 1 to 10 carbon atoms and substituted with at least one hydroxyl group, each R 18 ​is, independently, a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, and the subscripts f and q are integers, where f is 0 or 1, and q is from 1 to about 5, provided that (i) when R 13 is a monovalent hydrocarbon group of 1 to 12 carbon atoms, two R 13 groups are bonded by a covalent bond to form a divalent group -R 13 -R 13 - that contains a nitrogen atom and forms a ring; (ii) when f is 1, R 17 and R 18 are bonded by a covalent bond to form a divalent group -R 17 -R 18 - that contains a silicon atom and two oxygen atoms and forms a ring; and (iii) when R 14 is an alkyl group of 1 to 10 carbon atoms and e is 2 or 3, two R 14 groups are bonded by a covalent bond to form a divalent -R 14 -R 14 - group that contains a silicon atom and two oxygen atoms and forms a ring; provided that, is a functional group selected from the group consisting of, and the subscripts o and p are integers, where o is 1, 2, or 3, and p is 0, 1, or 2.

[0096] In one embodiment, R 11 is a divalent alkyl group of 1 to 20 carbons, X 2 is -OH, -C(=O)OR 17 where R 17 is, independently, a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, or C(=O)OH, and o is 1, and p is 1.

[0097] In another embodiment, R 11is a divalent alkyl group having 1 to 20 carbon atoms, and X 2 is Si(OR 14 ) e (R 15 ) 3-e where each R 14 is independently a monovalent alkyl group having 1 to 6 carbon atoms, a monovalent alkyl group having 1 to 6 carbon atoms substituted with one hydroxyl group, or a monovalent alkyl group containing 3 to 30 carbon atoms and 1 to 13 oxygen atoms, provided that the oxygen atoms are separated from each other by at least two carbon atoms, R 15 is methyl, e is 2 or 3, o is 1, and p is 1.

[0098] In yet another embodiment, R 11 is a divalent alkyl group having 1 to 20 carbon atoms, and X 2 is Si(OR 14 ) e (R 15 ) 3-e where each R 14 is a monovalent alkyl group having 1 to 10 carbon atoms substituted with one hydroxyl group, or one R 14 , each R 14 is a monovalent alkyl group having 1 to 10 carbon atoms substituted with one hydroxyl group, and the other two R 14 groups are monovalent alkyl groups having 1 to 10 carbon atoms that are bonded via a covalent bond to form a divalent group -R 14 -R 14 - containing a silicon atom and two oxygen atoms to form a ring, e is 3, o is 1, and p is 1.

[0099] In yet another embodiment, R 11 is a divalent alkyl group having 1 to 20 carbon atoms, and X 2 is Si(OR 14 ) e (R 15 ) 3-e where each R 14is a monovalent alkyl group having from 1 to 10 carbon atoms and substituted with one hydroxyl group, or -R 16 O[Si(R 11 (SH) o )(OR 17 ) f (R 15 ) 1-f q OR 18 group, where each R 15 is methyl, each R 16 is, independently, a divalent alkyl group having from 1 to 10 carbon atoms, each R 17 is, independently, a divalent alkyl group having from 1 to 10 carbon atoms or a divalent alkyl group having from 1 to 10 carbon atoms and substituted with at least one hydroxyl group, each R 18 is, independently, a divalent alkyl group having from 1 to 10 carbon atoms or a divalent alkyl group having from 1 to 10 carbon atoms and substituted with at least one hydroxyl group, and the subscripts e, f, and q are integers, where e is 2 or 3, f is 0 or 1, and q is from 1 to about 5, provided that when f is 1, R 17 and R 18 are bonded by a covalent bond to form a divalent group -R 17 -R 18 -, which forms a ring containing a silicon atom and two oxygen atoms, provided that this is the case.

[0100] ​Representative and non-limiting specific examples of the mercapto-containing compounds include 1-mercaptododecane, 1-mercapto-2-hydroxyethane, 1-mercapto-3-hydroxypropane, 2-mercaptoacetic acid, methyl 3-mercaptopropionate, cysteine, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltri-sec-butoxysilane, 3-mercaptopropyltri-t-butoxysilane, 3-mercaptopropyltriisopropoxysilane, 2-mercaptoethyldimethoxyethoxysilane, 3-mercaptopropylmethoxyethoxypropoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropylethoxydimethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropylcyclohexoxydimethylsilane, 4-mercaptobutyltrimethoxysilane, 3-mercapto-3-methylpropyltrimethoxysilane, 3-mercapto-3-methylpropyl-tripropoxysilane, 3-mercapto-3-ethylpropyl-dimethoxymethylsilane, 3-mercapto-2-methylpropyltrimethoxysilane, 3-mercapto-2-methylpropyldimethoxyphenylsilane, 3-mercaptocyclohexyl-trimethoxysilane, 12-mercaptododecyltrimethoxysilane, 12-mercaptododecyltriethoxysilane, 2-mercapto-2-methylethyl-tripropoxysilane, 2-mercaptophenyltrimethoxysilane, 2-mercaptophenyltriethoxysilane, 2-mercaptotolyltrimethoxysilane, 2-mercaptotolyltriethoxysilane, 1-mercaptomethyltolyltrimethoxysilane, 1-mercaptomethyltolyltriethoxysilane, 2-mercaptoethylphenyltrimethoxysilane, 2-mercaptoethylphenyltriethoxysilane, 2-mercaptoethyltolyltrimethoxysilane, 2-mercaptoethyltolyltriethoxysilane, 3-mercaptopropylphenyltrimethoxysilane, 3-mercaptopropylphenyltriethoxysilane;3-(2-{3-[2-(3-Mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; 3-(2-{3-[2-(3-Mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-thiol; 3-(2-{3-[2-(3-Mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; 3-({3-[2-Mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanilyl)-propane-1-thiol; 3-[{3-[{3-Bis-(3-hydroxy-2-methyl-propyl)-(3-mercapto-propyl)-silanilyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanilyloxy]-2-methyl-propan-1-ol; 3-[[3-((3-Hydroxy-3-methyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanilyloxy)-2-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-3-mercapto-propyl)-silanilyl]-2-methylpropan-1-ol; 3-(2-{3-[2-(3-Mercapto-butyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-[1,3,2]dioxasilinan-2-yl)-butane-1-thiol; 3-(2-{3-[2-(3-Mercapto-phenyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-3-benzene-thiol;3-(2-{3-[2-(3-Mercapto-cyclohexyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-cyclohexane-1-thiol; 3-({3-[2-Mercapto-methyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-diethoxy]-silanil)-methane-1-thiol; 3-[{3-[{3-Bis-(3-hydroxy-2,2-dimethyl-propyl)-(3-mercapto-propyl)-silanilyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy)-(3-mercapto-propyl)-silanilyloxy]-2,2-dimethyl-propan-1-ol; 3-[[3-((3-Hydroxy-3-phenyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-phenyl-[1,3,2]dioxasilinan-2-yloxy]-2-phenyl-1-propoxy}-silanilyloxy)-2-phenyl-propoxy-(3-hydroxy-2-phenyl-propoxy)-3-mercapto-propyl)-silanil]-2-phenylpropan-1-ol; 3-[{3-[(Methyl)-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanilyloxy]-2-methyl-propoxy}-methyl)-(3-mercapto-propyl)-silanilyloxy]-2-methyl-propan-1-ol, and combinations thereof are included.;

[0101] In one embodiment, the stabilizing amount of the mercapto-containing compound depends on the amount of urethane-forming catalyst used and is from 4 to 100 equivalents of mercapto (-SH) per equivalent of metal in the catalyst, more preferably from 8 to 50 equivalents of mercapto (-SH) per equivalent of metal, and most preferably from 12 to 25 equivalents of mercapto (-SH) per equivalent of metal.

[0102] In one embodiment, the amount of metal in the urethane-forming organometallic catalyst can be determined using the Inductively Coupled Plasma (ICP) method (EPA / SW-846 method 3015 / 3050B.6010B) dated March 17, 2006, which can be obtained from the following. https: / / clu-in.org / download / ert / 1811-r30.pdf

[0103] In one embodiment, the amount of -SH in the mercapto-containing compound can be determined by titration with a silver nitrate solution. This method is outlined in the standard method (potentiometric method) for (thiomercaptan) sulfur in gasoline, kerosene, aviation turbine, and distillate fuels, ASTM D3227-16.

[0104] In one embodiment, the amount of the mercapto-containing compound is from about 10 to about 20,000 ppm, more specifically from about 100 to about 5000 ppm, and even more specifically from about 500 to about 2000 ppm, based on the weight of the alkoxysilyl-containing polyurethane polymer.

[0105] In one embodiment, the mercapto-containing compound can be added to the reaction mixture after the formation of the isocyanate-containing polyurethane prepolymer or after the formation of the alkoxysilyl-containing polyurethane polymer composition. The addition includes simply mixing the mercapto-containing compound with the isocyanate-containing polyurethane prepolymer composition or the alkoxysilyl-containing polyurethane polymer composition.

[0106] Hydrolysis and condensation catalyst

[0107] The alkoxysilyl-containing polyurethane polymer composition stabilized with the mercapto compound can be activated for moisture curing by the addition of a hydrolysis and condensation catalyst.

[0108] Hydrolysis and condensation catalysts are organometallic compounds known to catalyze the rates of hydrolysis and condensation. Suitable hydrolysis and condensation catalysts include organometallic salts or organometallic complexes. Examples of the metal portions of urethane-forming organometallic catalysts useful in the present invention include titanium, aluminum, tin, zirconium, iron, cobalt, manganese, nickel, bismuth, and zinc, more preferably tin, bismuth, and zinc, and even more preferably tin. Urethane-forming organometallic catalysts include metal complexes, such as chelates of various metals, such as acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, salicylaldehydeimine having various metals such as Ti, Al, Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn; and organometallic salts, such as alcoholates and phenolates of various metals, such as Ti(OR 8 ) 4 , Al(OR 8 ) 3 , Zr(OR 8 ) 2 , Sn(OR 8 ) 4 , Sn(OR 8 ) 2 , Bi(OR 8 ) 3 , etc., where R 8 is a monovalent alkyl or aryl of 1 to 18 carbon atoms, or carboxylates of various metals, such as Zr(O(C=O)R 8 ) 2 , Sn(O(C=O)R 8 ) 4 , Sn(O(C=O)R 8 ) 2 , Bi(O(C=O)R 8 ) 3 , R 9 2 Sn(O(C=O)R 8 ) 2 , where R 8is a monovalent alkyl or aryl of 1 to 18 carbon atoms, and R 9 is a monovalent alkyl or aryl of 1 to 18 carbon atoms; and reaction products of various metal alcoholates with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino)alkanols are included.

[0109] In one particular embodiment, the organotin compound that is a dialkyltin salt of a carboxylic acid includes non-limiting examples such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin bis(4-methylaminobenzoate), dibutyltin bis(6-methylaminocaproate), and combinations thereof.

[0110] Similarly, in another particular embodiment, trialkyltin hydroxides, dialkyltin oxides, dialkyltin dialkoxides, or dialkyltin dichlorides and combinations thereof can be used. Non-limiting examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and combinations thereof.

[0111] The amount of the hydrolysis and condensation catalyst added to the alkoxysilyl-containing polyurethane polymer composition is about 0.02 to about 1.0 weight percent, preferably about 0.05 to about 0.5 weight percent, and even more preferably about 0.1 to about 0.3 weight percent of metal, based on the weight of the alkoxysilyl-containing polyurethane polymer.

[0112] Other optional components

[0113] The moisture-curable composition of the present invention comprises an alkoxysilyl-containing polyurethane polymer (a), and a urethane-forming organometallic catalyst (b), a mercapto-containing compound (c), and, when curing is desired, in addition to a hydrolysis and condensation catalyst (d), one or more optional components, for example, optional materials commonly included in known and conventional amounts in moisture-curable coatings, sealants, adhesives, and consumer and industrial products.

[0114] For example, such optional components can include organic and inorganic compounds that contribute to the handling and flexibility of uncured and cured alkoxysilyl-containing polyurethane polymer compositions. Optional components include organic solvents, polysiloxanes, isocyanate-reactive scavenging agents, water scavenging agents, desiccants, surfactants, colorants, plasticizers, extenders, fillers, adhesion promoters, organic resin modifiers, UV stabilizers, color stabilizers, wetting agents, flow and leveling additives, thixotropes, defoamers, and the like.

[0115] Solvent

[0116] One or more organic solvents can be used to reduce the viscosity and improve the flow characteristics of the uncured composition, which is particularly useful when the composition is used as a coating. Various solvents such as alcohols, glycols, triols, polyols, glycol ethers, esters, ketones, hydrocarbons, etc. may be mentioned by way of example.

[0117] Representative and non-limiting examples of specific solvents include monoalcohols such as methanol, ethanol, 1-propanol, 2-propanol (i-propanol), 2-methyl-1-propanol (i-butanol), 2-methyl-2-propanol (tert-butanol), 1-butanol, 2-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol; glycols such as propylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol (hexylene glycol), diethylene glycol, triethylene glycol, tetraethylene glycol, poly(ethylene glycol), dipropylene glycol, tripropylene glycol, poly(propylene glycol), 1,5-pentanediol, estradiol 204, 2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, glycerol, glycerol ethoxylate, glycerol ethoxylate-co-propoxylate triol, glycerol propoxylate, pentaerythritol;Glycol ethers, such as 1-methoxy-2-propanol (propylene glycol methyl ether), 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxyl)ethanol, 2-(2-ethoxyethoxyl)ethanol, 2-(2-propoxyethoxyl)ethanol, 2-(2-butoxyethoxyl)ethanol (butyl carbitol), di(propylene glycol) butyl ether, tri(ethylene glycol) monomethyl ether, tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutyl ether, poly(ethylene glycol) methyl ether, poly(ethylene glycol) dimethyl ether, poly(ethylene glycol-co-propylene glycol), poly(ethylene glycol-co-propylene glycol) monobutyl ether, poly(propylene glycol) monobutyl ether, di(propylene glycol) dimethyl ether; esters including methyl acetate, ethyl acetate, ethyl lactate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-(2-methoxyethoxyl)ethyl acetate, 2-(2-ethoxyethoxyl)ethyl acetate, 2-(2-butoxyethoxyl)ethyl acetate, glycol diacetate, triethylene glycol diacetate, propylene glycol methyl ether acetate (1-methoxy-2-propanol acetate), propylene glycol ethyl ether acetate, ketones including acetone, methyl ethyl ketone, 2,4-pentanedione, diacetone alcohol, and hydrocarbons including toluene, xylene, naphtha, mineral spirit, hexane, heptane, cyclohexane, and mixtures thereof are included.;

[0118] In certain embodiments, the solvent can be present in the moisture-curable composition in an amount in the range of from 1 to about 80 weight percent, preferably from about 10 to about 30 weight percent, and in some embodiments from about 10 to about 25 weight percent, based on the total weight of the composition.

[0119] Surfactant

[0120] When the composition is used as a coating, in particular, one or more surfactants can be used to assist in wetting and leveling of the moisture-curable alkoxysilyl-containing polyurethane polymer composition of the present invention. Useful surfactants include nonionic, cationic, anionic, amphoteric and / or zwitterionic surfactants. Surfactants are typically hydrocarbon-based, silicone-based, or fluorocarbon-based. Some useful surfactants have short-chain hydrophobic substances. Other useful surfactants include alkoxylates, especially ethoxylates, including block copolymers containing copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylaryl alkoxylates, especially ethoxylates or propoxylates and their derivatives, including alkylphenol ethoxylates; arylaryl alkoxylates, especially ethoxylates or propoxylates, and their derivatives; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkyl naphthalene sulfonates; sulfated fatty alcohols, amines or acid amides; acidic esters of sodium isethionate; esters of sodium sulfosuccinate; sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and mixtures thereof.

[0121] Representative non-limiting examples of surfactants include alkyl acetylene diols sold under the trade name Surfonyl® by Air Products, pyrrolidone-based surfactants sold under the trade name Surfadone-LP® 100 by ISP, 2-ethylhexyl sulfate, isodecyl alcohol ethoxylate sold under the trade name Rhodasurf® 530 by Rhodia, ethylenediamine alkoxylate sold under the trade name Tetronics® by BASF, ethylene oxide / propylene oxide copolymers sold under the trade name Pluronics® by BASF, and diphenyl ether gemini-type surfactants sold under the trade name Dowfax® by Dow Chemical Corporation.

[0122] Generally, the moisture-curable composition of the present specification can optionally contain a surfactant in an amount of about 0.01 to about 5 weight percent, preferably about 0.05 to about 2 weight percent, and in certain embodiments about 0.1 to about 1 weight percent, based on the total weight of the composition.

[0123] Colorant

[0124] The moisture-curable alkoxysilyl-containing polyurethane polymer composition of the present invention can contain a colorant. As used herein, the term "colorant" means any substance that imparts color and / or other opacity and / or other visual effects to the polymer. The colorant can be added to the silylated polyurethane polymer composition in any suitable form such as discrete particles, dispersions, solutions, flakes, etc. A single colorant or a mixture of two or more colorants can be used in the moisture-curable composition of the present invention.

[0125] Useful colorants include pigments, dyes, and colorants such as those used in the paint industry and / or listed by the Dry Color Manufacturers Association (DCMA), as well as special effect materials. Useful types of colorants can be finely divided solid powders that are insoluble but wettable under the conditions of use. Colorants can be organic or inorganic and can be aggregated or non-aggregated. Colorants can be added to the moisture-curing compositions herein by using grinding vehicles such as acrylic grinding vehicles well known to those skilled in the art.

[0126] Exemplary useful pigments and pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, disazo, naphthol AS, salt types (lakes), benzimidazolone, condensed, metal complexes, isoindolinone, isoindoline, and polycyclic phthalocyanines, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthantrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrolopyrrole red, titanium dioxide, carbon black, and mixtures thereof. The terms "pigment" and "coloring filler" can be used interchangeably.

[0127] Useful dyes include, but are not limited to, solvent and / or water-based ones such as phthalocyanine green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum, and quinacridone.

[0128] Useful colorants include pigments dispersed in aqueous or water-miscible carriers such as Aqua-Chem® 896 commercially available from Degussa, Inc., Charisma Colorants® and Maxitoner Industrial Colorants® commercially available from the Accurate Dispersions Division of Eastman Chemical, Inc., but are not limited thereto.

[0129] Generally, the colorant can be present in the moisture-curable composition of the present specification in any amount sufficient to provide the desired visual and / or color effect. The colorant can comprise, for example, from about 1 to about 65 weight percent, such as from about 3 to about 40 weight percent or from about 5 to about 35 weight percent, based on the total weight of the composition, of the silylated polyurethane polymer composition.

[0130] Filler

[0131] The moisture-curable alkoxysilyl-containing polyurethane polymer composition of the present invention can include one or more fillers. The filler can be any inorganic or organic filler that strengthens and / or extends the composition. Useful fillers include, for example, reinforcing fillers such as carbon black, fumed silica, precipitated silica, clay, talc, aluminum silicate, metal oxides and hydroxides, and extending fillers such as treated and untreated calcium carbonate. The filler can be in the form of powder, particles, aggregates, agglomerates, platelets, fibers, etc. In one embodiment, one or more fillers are combined with a silane coupling agent.

[0132] To further improve the physical strength of the cured moisture-curable alkoxysilyl-containing polyurethane polymer composition herein, reinforcing carbon black can be used as the main filler to obtain a black or dark-colored silylated polyurethane polymer composition. Several commercially available grades of carbon black useful in the present invention are commercially available, such as products of Corax® from Degussa. To obtain a colorless / transparent moisture-curable composition, higher levels of fumed silica or precipitated silica can be used as the main filler, excluding carbon black. The surface area of the filler can exceed 20 square meters 2 / gram.

[0133] Processed calcium carbonates having an average particle size from 0.07 microns to 4 microns, such as those having an average particle size from 0.07 microns to 4 microns, are preferred fillers and are available under several trade names such as UltraPflex® and HiPflex® from Specialty Minerals; Winnofil® SPM and Winnofil® SPT from Zeneca Resin; Hubercarb® Qt, Hubercarb® 3Qt, and Hubercarb® W from Huber, and Kotomite® from ECC; Omyabond® 520, Omyacarb® 3, Omyacarb® 5, etc. from Omya. These fillers can be used alone or in combination.

[0134] Optional fillers can be included in the moisture-curable composition herein in an amount up to about 80 weight percent, advantageously in an amount from about 0.1 weight percent to about 50 weight percent, based on the total weight of the composition, and in certain embodiments, in an amount from about 20 to about 50 weight percent.

[0135] Plasticizers and Thixotropy

[0136] The moisture-curable alkoxysilyl-containing polyurethane polymer composition of this specification can optionally contain one or more plasticizers. Exemplary plasticizers include phthalates, dipropylene and diethylene glycol dibenzoate and mixtures thereof, epoxidized soybean oil, and the like. Useful commercially available dioctyl and diisodecyl phthalates include Jayflex® DOP and Jayflex® DIDP from Exxon Chemical. The dibenzoate plasticizers are available as Benzoflex® 9-88, Benzoflex® 50, Benzoflex® 400 from Velsicol Chemical Corporation, and Mesamoll® from Lanxess. The optional plasticizer can represent up to about 100 parts by weight per 100 parts of the moisture-curable composition, and preferably up to 40 parts by weight per 100 parts of the composition.

[0137] Optional thixotropes that can be incorporated into the moisture-curable composition of the present invention include various castor waxes, fumed silica, treated clays, and polyamides. Commercially available thixotropies include, for example, Aerosil from Degussa, Cabo-Sil TS 720 from Cabot, Castorwax from CasChem, Thixatrol and Thixcin from Rheox, Crayvallac from Crayvalley Corp., and Dislon from King Industries.

[0138] Isocyanate-reactive quenching agent

[0139] In the moisture-curable alkoxysilyl-containing polyurethane polymer composition, as described above, an optional isocyanate-reactive quenching agent can be added. The quenching agent has at least one active hydrogen and reacts with the isocyanate at a faster rate than unwanted reactions that cause an increase in viscosity, such as the further reaction of the isocyanate with the hydroxyl-terminated polymer when hydroxyl is still present, the reaction of the isocyanate with the urethane to form allophanate, and the reaction of the isocyanate with the urea to form biuret.

[0140] The isocyanate-reactive quenching agent can be added to the reaction mixture at the desired point at or near the end of the silylation reaction. In the case of diisocyanate or polyisocyanate-extended polyol, it is understood that the hydroxyl-terminated polyurethane polymer can contain residual isocyanate from either the partially reacted diisocyanate or polyisocyanate, or the unreacted diisocyanate or polyisocyanate. The residual isocyanate present in the silylated polyurethane polymer composition can be derived from the diisocyanate or polyisocyanate used to chain-extend the polyol (ii), or the isocyanato-containing alkoxysilane used to react with the hydroxyl-terminated polymer. The desired point of addition of the isocyanate reactant can be determined by the viscosity of the reaction mixture, or by some other means. Thus, the isocyanate-reactive scavenging agent is added to the reaction mixture at a specific viscosity, depending on the desired properties of the formulation and the final product.

[0141] In one embodiment of the present invention, the isocyanate-reactive scavenging agent is added to the reaction mixture in a viscosity range of from about 1,000 cP to about 150,000 cP when measured at a temperature of 25°C, and in another embodiment of the present invention, in a viscosity range of from about 30,000 cP to about 75,000 cP when measured at a temperature of 25°C. In this way, the isocyanate-reactive scavenging agent minimizes the variation between batches of the final viscosity of the silylated polyurethane polymer composition and reduces or eliminates the exposure of practitioners and consumers to reactive isocyanates.

[0142] Antioxidant

[0143] Optional antioxidants and stabilizers can be added to the moisture-curable alkoxysilyl-containing polyurethane polymer composition of the present invention to provide protection against oxidative changes. The amount of antioxidant that can be used varies within a wide range, for example, from about 0.01 to about 10 weight percent, more specifically from about 0.01 to about 3 weight percent, based on the weight of the composition.

[0144] Water scavenging agent

[0145] A water scavenging agent can be optionally added to the moisture-curable alkoxysilyl-containing polyurethane polymer composition herein to improve the stability of its package and prevent premature curing. Useful water scavenging agents include alkoxysilanes such as vinyltrimethoxysilane, methyltrimethoxysilane, and the like. The concentration of the water scavenging agent can range from about 0 to about 5 weight percent, more preferably from about 0.5 to about 5 weight percent, and even more preferably from about 1 to about 4 weight percent, based on the weight of the composition.

[0146] As an alternative to, or in addition to, the optional water scavenging agent, a desiccant can be optionally added to the moisture-curable composition herein to improve the stability of its package and prevent premature curing. Any known or conventional desiccant, such as silica gel, can be utilized for this purpose.

[0147] Color stabilizer

[0148] According to one embodiment of the present invention, a color stabilizer can be added to the moisture-curable composition to reduce its yellowing over time. Representative non-limiting examples of color stabilizers include, for example, triphenyl phosphite, diphenyl-alkyl phosphite, phenyl-dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)-pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-ethyl phosphite, 2,2’,2’’-nitrilo-[triethyl tris(3,3’,5,5’-tetra-tert-butyl-1,1’-biphenyl-2,2’-diyl) phosphite] and 2-ethylhexyl(3,3’,5,5’-tetra-tert-butyl-1,1’-biphenyl-2,2’-diyl) phosphite.

[0149] In one embodiment, the amount of color stabilizer used can vary from about 0.01 to about 3 weight percent, preferably from about 0.5 to about 2 weight percent, based on the weight of the moisture-curable composition.

[0150] All references cited in this specification are hereby incorporated by reference in their entirety into this specification.

[0151] The present invention can be better understood by reference to the following examples, in which parts and percentages are by weight, unless otherwise indicated.

Examples

[0152] The following materials are used in the following examples and / or are very suitable for inclusion in the stabilized polymers according to the present invention. The examples are to be construed as illustrative only and not as limiting the scope of the invention.

[0153] The reagents used in the following experiments include Silquest * A-171 with the structure vinyltrimethoxysilane, Silquest * A-1120 silane with the structure N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Silquest * A-1891 silane with the structure gamma-mercaptopropyltriethoxysilane, Silquest * A-1891 silane contains Mercaptan Y with the structure gamma-mercaptopropyltrimethoxysilane. All of these reagents are available from Momentive Performance Materials Inc. ( * denotes trademarks of Momentive Performance Materials Inc. and / or its affiliates).

[0154] Example 1 Preparation of an alkoxysilyl-containing polyurethane polymer composition Into a 2-liter resin kettle, 864 grams of dry hydroxyl-terminated polypropylene oxide (available from Covestro as Acclaim 18200 N, 0.046 mol), 4.3 grams of Irganox 1135, benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester processing stabilizer (available from BASF), and 12 ppm of a urethane-forming organometallic catalyst, dibutyltin dilaurate were added, and then the mixture was heated to 60 °C with stirring under a nitrogen atmosphere. After 10 minutes, 24.33 grams of 3-isocyanatopropyltrimethoxysilane (available from Momentive Performance Materials, Inc. as Silquest * A-Link * 35, 0.106 mol) was added. The mixture was heated to a temperature of about 78 °C and held at that temperature until the NCO content reached (by titration) approximately zero. The reaction mixture was allowed to cool, and then 7.2 grams of methanol was added to quench any remaining isocyanate.

[0155] Example 2 Preparation of a moisture-stabilized alkoxysilyl-containing polyurethane polymer composition A resin kettle was charged with 250 grams of the alkoxysilyl-containing polyurethane polymer composition of Example 1 and 0.125 grams of mercaptan Y, 3-mercaptopropyltrimethoxysilane (available from Momentive Performance Materials, Inc.). The mixture was blended twice at room temperature in a speed mixer for 2 minutes. The mixture was stored at room temperature.

[0156] Example 3 Moisture-stabilized alkoxysilyl-containing polyurethane polymer composition Into a resin kettle, 250 grams of the alkoxysilyl-containing polyurethane polymer composition of Example 1 and 0.250 grams of Silquest T-cure (a proprietary mercapto-functional silane available from Momentive Performance Materials Inc.) were placed. The mixture was blended twice at room temperature for 2 minutes in a speed mixer. The mixture was stored at room temperature.

[0157] Comparative Example A Into a resin kettle, 250 grams of the alkoxysilyl-containing polyurethane polymer composition of Example 1 and 2.50 grams of vinyltrimethoxysilane (Silquest * available as A-171 silane from Momentive Performance Materials Inc.) were placed. The mixture was blended twice at room temperature for 2 minutes in a speed mixer. The mixture was stored at room temperature.

[0158] Examples 3 and 4, Comparative Example B Preparation and Testing of Sealants A masterbatch of the basic sealant formulation was prepared. In a loss-in-weight mixer, 199.5 grams of diisodecyl phthalate, a plasticizer (available from Exxon-Mobil as Jaflex DIDP), a mixture of 1.14 grams of alpha-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-omega-hydroxypoly(oxy-1,2-ethanediyl); alpha-[3-[3-(2H-benzotriazol-2-yl)-5-(1, dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-omega-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl); polyethylene glycol with a molecular weight of 300, a UV absorber (available as Eversorb 80), and 1.14 grams of a mixture of bis-(N-methyl,2,2,6,6-tetramethyl-4-piperidinyl) sebacate and methyl-(N-methyl,2,2,6,6-tetramethyl-4-piperidinyl) sebacate, a hindered amine light stabilizer (available as Eversorb 765) were added. The mixture was mixed for 10 minutes, and then 294.5 grams of dry precipitated calcium carbonate (available from Cary Company as Ultra-Pflex) and 294.5 grams of dry ground limestone, a filler (available from Cary Company as Hi-Pflex) were added and mixed. Titanium dioxide pigment (28.5 grams, available from Chemours Company as TiPure 960) and 10.45 grams of a thermoplastic silicone polycarbonate urethane, a thermoplastic urethane copolymer containing silicone as a soft segment stabilizer (available from Cabot Corporation as Carbo-SilTS 720) were added and mixed until homogeneous. To the mixture, 5.415 grams of 2-aminoether-3-aminopropyltrimethoxysilane (from Momentive Performance Materials, Inc. as Silquest *(available as A-1120J silane) and 4.37 grams of vinyltrimethoxysilane (available as Silquest A-171 silane from Momentive Performance Materials, Inc.) were added and mixed for 15 minutes. The masterbatch was packed into cartridges. *

[0159] Into a speed mixer were placed 11.5 grams of the moisture-stabilized alkoxysilyl-containing polyurethane polymer composition prepared in Example 2 and 38.46 grams of the masterbatch, and they were mixed in the speed mixer at 2700 rpm for 2 minutes. The walls were scraped down with a wooden stirrer and mixed for an additional 2 minutes. Finally, 0.08 weight percent of dibutyltin dilaurate (available as Fomrez SUL-4 from Galata Chemicals) was added to the sealant mixture and mixed at 2700 rpm for 1 minute. Using the compositions of Example 3 and Comparative Example A, similar sealant formulations were prepared. The formulations are shown in Table 1.

[0160]

Table 1

[0161] Test for moisture sensitivity

[0162] The stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition was placed in an aluminum open pan to a thickness of 3 to 4 millimeters. The sample in the aluminum pan was placed in a humidity chamber at 23 °C and 50% relative humidity. The initial viscosity was measured, and then measured every other day for a total of 12 days. The data are shown in Table 2. Unless otherwise specified, the viscosities reported in this specification were measured at 25 °C using a Brookfield DV3T viscometer equipped with a CPA-52Z cone at 50% torque.

[0163]

Table 2

[0164] ​The change in viscosity of the moisture-curable alkoxysilyl-containing polyurethane polymer composition is an indicator of the effectiveness of the mercapto-containing compound in stabilizing the composition. Examples 2 and 3 showed only a slight increase in viscosity, and particularly in Example 3, the viscosity increased by only 18 percent. In contrast, the composition stabilized with vinyltrimethoxysilane showed a 240 percent increase in viscosity.

[0165] Mechanical properties of sealants prepared from moisture-curable alkoxysilyl-containing polyurethane polymer compositions

[0166] The sealant prepared above was cast into an HDPE mold to form a film with a thickness of about 2.5 mm. The film was cured in a humidity chamber at 23 °C and 50% relative humidity. The skin time was determined by touching the sample and measuring the tack. Next, the film was cured for 7 days and removed from the mold.

[0167] Tensile physical properties were determined according to the procedures of ASTM D412, Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers, and ASTM C661-06, Standard Test Method for Indentation Hardness of Elastomeric-Type Sealants by Durometer. The data are shown in Table 3.

[0168]

Table 3

[0169] As shown in Table 4, the tensile strength, elongation, elastic modulus, and Shore A hardness of Sealant Examples 3 and 4 were equivalent to those of the sealant of Comparative Example B. However, the skin time was significantly shortened. The skin time of Comparative Example B was twice as long as that of Example 3. Therefore, a small amount of mercapto-containing compound can stabilize the stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition. Thus, when a small amount of mercapto-containing compound is activated by adding a hydrolysis and condensation catalyst, it can cure quickly as measured by the skin time without affecting the mechanical properties.

[0170] Although the present invention has been described with reference to specific embodiments, it is understood that those skilled in the art can make various changes and replace elements with equivalents without departing from the scope of the present invention. Furthermore, modifications can be made to adapt a particular situation or material to the teachings of the present invention without departing from its essential scope. Therefore, the present invention is not limited to the specific embodiments disclosed herein, and the present invention is intended to include all embodiments included in the appended claims.

Claims

1. (a) at least one alkoxysilyl-containing polyurethane polymer; (b) at least one urethane-forming organometallic catalyst; and (c) at least one mercapto-containing compound; 1. A stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition comprising:

2. The alkoxysilyl-containing polyurethane polymer has the general formula (I): 【Chemistry 1】 where Each R １ are independently monovalent alkyl groups of 1 to 6 carbon atoms: Each R ２ are independently monovalent alkyl or phenyl groups of 1 to 4 carbon atoms; Each R ３ are independently a divalent alkyl group of 1 to 12 carbon atoms; Each R ４ are independently a monovalent alkyl group of 1 to 6 carbon atoms, a phenyl group, hydrogen, or -R ３ SiR ２ ３－ａ (OR １ ) ａ is a group; Each R ５ are independently a divalent alkyl group having 1 to 16 carbon atoms, a divalent cycloalkyl group having 5 to 16 carbon atoms, and a group X having the general formula (II): １ is a divalent organic group selected from the group consisting of 【Chemistry 2】 Here, each R ６ is independently an alkylene group of 1 to 12 carbon atoms or a cycloalkylene group of 5 to 16 carbon atoms, and each R ７ is independently a divalent organic radical selected from the group consisting of divalent alkyl radicals having 1 to 16 carbon atoms and divalent cycloalkyl radicals having 5 to 16 carbon atoms; Each G is a polyvalent organic group derived from a polyol or a monovalent organic group derived from a monool; and The subscripts a, b, and c are integers, where a is 1, 2, or 3, b is 0 or 1, and c is 0 to 5, except that when b is 0, R ４ The composition of claim 1 , with the proviso that:

3. 3. The composition of claim 2, wherein G is a polyvalent organic group derived from a polyol or monol and formed by removing the hydroxyl groups of the polyol, wherein the polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, polybutylene polyols, polyols derived from polystyrene / butadiene copolymers, polyisoprene polyols, poly(meth)acrylate polyols, polyisocyanate-extended polyester polyols, polyisocyanate-extended polyether polyols, polyisocyanate-extended polycarbonate polyols, polyisocyanate-extended polyols derived from polystyrene / butadiene copolymers, polyisocyanate-extended polyisoprene polyols, polyisocyanate-extended poly(meth)acrylate polyols, polyisocyanate-extended polybutadiene polyols, polyisocyanate-extended polybutylene polyols, and mixtures thereof.

4. The composition of claim 1 , wherein the urethane-forming organometallic catalyst is selected from the group consisting of organometallic salts and organometallic complexes.

5. The urethane-forming organometallic catalysts include acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, salicylaldehyde imine chelates, and metal complexes obtained from metals selected from the group consisting of Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn; Zr(OR ７ ) ２ , Sn(OR ７ ) ４ , Sn(OR ７ ) ２ , Bi(OR ７ ) ３ , Zr(O(C=O)R ７ ) ２ , Sn(O(C=O)R ７ ) ４ , Sn(O(C=O)R ７ ) ２ , Bi(O(C=O)R ７ ) ３ , R ８ ２ Sn(O(C=O)R ７ ) ２ where R is an organometallic salt selected from the group consisting of ７ is a monovalent alkyl or aryl of 1 to 18 carbon atoms, and R ８ The composition of claim 4, wherein is a monovalent alkyl or aryl of 1 to 18 carbon atoms and combinations thereof.

6. 6. The composition of claim 5, wherein the organometallic salt is selected from the group consisting of dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin bis(4-methylaminobenzoate), dibutyltin bis(6-methylaminocaproate), and combinations thereof.

7. 6. The composition of claim 5, wherein the organometallic salt is selected from the group consisting of trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride, and combinations thereof.

8. 8. The composition of claim 7, wherein the organometallic salt is selected from the group consisting of trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and combinations thereof.

9. 10. The composition of claim 1, wherein the urethane-forming catalyst is used in an amount of from 1 to 100 ppm based on the weight of metal added to the polyol.

10. 10. The composition of claim 9, wherein the urethane-forming catalyst is used in an amount of from 5 to 50 ppm based on the weight of metal added to the polyol.

11. The mercapto-containing compound has the general formula (IX): (HS) ｏ R １１ X ２ ｐ (IX) where Each R １１ is independently a divalent or polyvalent hydrocarbon containing from 1 to 20 carbon atoms or a divalent or polyvalent hydrocarbon containing from 1 to 20 carbon atoms and at least one oxygen atom; Each X ２ are independently hydroxyl (-OH), carboxyl (-C(=O)OH), ester (-C(=O)OR １７ , where R １７ is a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group), a carboxylate (-C(=O)O － HN ＋ (R １２ ) (R １３ ) ２ , where R １２ is R １１ , hydrogen, or a monovalent hydrocarbon radical of 1 to 12 carbon atoms, and each R １３ are independently hydrogen or a monovalent hydrocarbon radical of 1 to 12 carbon atoms), amino-NR １３ ２ , where each R １３ are independently hydrogen, a hydrocarbon group of 1 to 12 carbon atoms, and an alkoxysilyl group (-Si(OR １４ ) ｅ (R １５ ) ３－ｅ , where each R １４ are independently a monovalent alkyl group of 1 to 10 carbon atoms, a monovalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, a monovalent alkyl group containing 3 to 30 carbon atoms and at least one oxygen atom, or -R １６ O[Si(R １１ (S.H.) ｏ ) (OR １７ ) ｆ (R １５ ) １－ｆ ] ｑ OR １８ group, where each R １５ is independently methyl or phenyl; １６ are independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group; each R １７ are independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group; １８ are independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, and the subscripts f and q are integers, where f is 0 or 1 and q is 1 to about 5, with the proviso that (i) R １３ When R is a monovalent hydrocarbon radical of 1 to 12 carbon atoms, two R １３ A divalent group -R １３ -R １３ - may form; (ii) When f is 1, R １７ and R １８ is a divalent group -R covalently bonded to form a ring containing a silicon atom and two oxygen atoms １７ -R １８ - may form; (iii) R １４ is an alkyl group of 1 to 10 carbon atoms and e is 2 or 3, two R １４ The group is a divalent -R covalently linked ring that contains a silicon atom and two oxygen atoms. １４ -R １４ -capable of forming a -group; and the subscripts o and p are integers, where o is 1, 2, or 3 and p is 0, 1, or 2; The composition of claim 1.

12. R １１ is a divalent alkyl group of 1 to 20 carbons; X ２ is -OH, -C(=O)OR １７ , where R １７ is independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, or C(=O)OH, o is 1, and p is 1.

13. R １１ is a divalent alkyl group of 1 to 20 carbon atoms; X ２ is Si(OR １４ ) ｅ (R １５ ) ３－ｅ where each R １４ are independently a monovalent alkyl group of 1 to 6 carbon atoms, a monovalent alkyl group of 1 to 6 carbon atoms substituted with one hydroxyl group, or a monovalent alkyl group containing from 3 to 30 carbon atoms and from 1 to 13 oxygen atoms, with the proviso that the oxygen atoms are separated from one another by at least two carbon atoms; R １５ The composition of claim 11 , wherein is methyl, e is 2 or 3, o is 1, and p is 1.

14. R １１ is a divalent alkyl group of 1 to 20 carbon atoms; X ２ is Si(OR １４ ) ｅ (R １５ ) ３－ｅ where each R １４ is a monovalent alkyl group of 1 to 10 carbon atoms substituted with one hydroxyl group, or where one R １４ , each R １４ is a monovalent alkyl group of 1 to 10 carbon atoms substituted with one hydroxyl group, and the other two R １４ The group is a divalent group -R １４ -R １４ -, e is 3, o is 1, and p is 1.

15. R １１ is a divalent alkyl group of 1 to 20 carbon atoms; X ２ is Si(OR １４ ) ｅ (R １５ ) ３－ｅ where each R １４ is a monovalent alkyl group of 1 to 10 carbon atoms substituted with one hydroxyl group, or -R １６ O[Si(R １１ (S.H.) ｏ ) (OR １７ ) ｆ (R １５ ) １－ｆ ] ｑ OR １８ group, where each R １５ is methyl, and each R １６ are independently a divalent alkyl group of 1 to 10 carbon atoms; each R １７ are independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group; １８ are independently a divalent alkyl group of 1 to 10 carbon atoms or a divalent alkyl group of 1 to 10 carbon atoms substituted with at least one hydroxyl group, and the subscripts e, f, and q are integers, where e is 2 or 3, f is 0 or 1, and q is 1 to about 5, with the proviso that when f is 1, R １７ and R １８ is a divalent group -R covalently bonded to form a ring containing a silicon atom and two oxygen atoms １７ -R １８ The composition of claim 11, wherein the compound is a carboxyl group.

16. The mercapto-containing compounds include 1-mercaptododecane, 1-mercapto-2-hydroxyethane, 1-mercapto-3-hydroxypropane, 2-mercaptoacetic acid, methyl 3-mercaptopropanoate, cysteine, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltrisec-butoxysilane, 3-mercaptopropyltri-t-butoxysilane, and the like. silane, 3-mercaptopropyl triisopropoxy silane, 2-mercaptoethyl dimethoxy ethoxy silane, 3-mercaptopropyl methoxy ethoxy propoxy silane, 3-mercaptopropyl dimethoxy methyl silane, 3-mercaptopropyl methoxy dimethyl silane, 3-mercaptopropyl ethoxy dimethyl silane, 3-mercaptopropyl diethoxy methyl silane, 3-mercaptopropyl cyclohexoxy dimethyl silane, 4-mercaptobutyl trimethoxy silane, 3-mercapto-3-methylpropyl trimethoxy silane silane, 3-mercapto-3-methylpropyl-tripropoxysilane, 3-mercapto-3-ethylpropyl-dimethoxymethylsilane, 3-mercapto-2-methylpropyltrimethoxysilane, 3-mercapto-2-methylpropyldimethoxyphenylsilane, 3-mercaptocyclohexyl-trimethoxysilane, 12-mercaptododecyltrimethoxysilane, 12-mercaptododecyltriethoxysilane, 2-mercapto-2-methylethyl-tripropoxysilane, 2-mercaptophenyltrimethoxysilane, 2-mercapto Phenyltriethoxysilane, 2-mercaptotolyltrimethoxysilane, 2-mercaptotolyltriethoxysilane, 1-mercaptomethyltolyltrimethoxysilane, 1-mercaptomethyltolyltriethoxysilane, 2-mercaptoethylphenyltrimethoxysilane, 2-mercaptoethylphenyltriethoxysilane, 2-mercaptoethyltolyltrimethoxysilane, 2-mercaptoethyltolyltriethoxysilane, 3-mercaptopropylphenyltrimethoxysilane, 3-mercaptopropylphenyltriethoxysilane;3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; 3-(2-{3-[2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-thiol; 3-(2-{3-[2-(3-mercapto -propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; 3-({3-[2-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanyl)-propane-1-thiol; 3-[{3-[{3-bis-(3-hydroxy-2-methyl-propyl)-(3- mercapto-propyl)-silanyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propan-1-ol; 3-[[3-((3-hydroxy-3-methyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-2-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)- 3-mercapto-propyl)-silanyl]-2-methylpropan-1-ol; 3-(2-{3-[2-(3-mercapto-butyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-[1,3,2]dioxasilinan-2-yl)-butane-1-thiol; 3-(2-{3-[2-(3-mercapto-phenyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-3-benzene-thiol;3-(2-{3-[2-(3-mercapto-cyclohexyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-cyclohexane-1-thiol; 3-({3-[2-mercapto-methyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-cyclohexane-1-thiol 3-[{3-[{3-bis-(3-hydroxy-2,2-dimethyl-propyl)-(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propane 12. The composition of claim 11, wherein the aryl group is selected from the group consisting of 3-[[3-((3-hydroxy-3-phenyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-phenyl-[1,3,2]dioxasilinan-2-yloxy]-2-phenyl-1-propoxy}-silanyloxy)-2-phenyl-propoxy-(3-hydroxy-2-phenyl-propoxy)-3-mercapto-propyl)-silanyl]-2-phenylpropan-1-ol; 3-[{3-[(methyl)-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-methyl)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propan-1-ol and combinations thereof.

17. The composition of claim 1, wherein the mercapto-containing compound is in an amount of from about 4 to about 100 equivalents of mercapto (--SH) per equivalent of metal in the urethane-forming organometallic catalyst.

18. The composition of claim 1, wherein the mercapto-containing compound is in an amount of from about 12 to about 25 equivalents of mercapto (--SH) per equivalent of metal in the urethane-forming organometallic catalyst.

19. 10. The composition of claim 1, wherein the mercapto-containing compound is in an amount of from about 100 to about 5,000 parts per million (pmp) based on the weight of the alkoxysilyl-containing polyurethane polymer.

20. The composition of claim 1 further comprising a hydrolysis and condensation catalyst.

21. 21. The composition of claim 20, wherein the hydrolysis and condensation catalyst is an organometallic salt or an organometallic complex.

22. Hydrolysis and condensation catalysts include complexes derived from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, and salicylaldehydeimine complexed with Ti, Al, Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn; ８ ) ４ , Al(OR ８ ) ３ , Zr(OR ８ ) ２ , Sn(OR ８ ) ４ , Sn(OR ８ ) ２ , Bi(OR ８ ) ３ , Zr(O(C=O)R ８ ) ２ , Sn(O(C=O)R ８ ) ４ , Sn(O(C=O)R ８ ) ２ , Bi(O(C=O)R ８ ) ３ , R ９ ２ Sn(O(C=O)R ８ ) ２ , where R ８ is a monovalent alkyl or aryl of 1 to 18 carbon atoms, and R ９ is a monovalent alkyl or aryl of 1 to 18 carbon atoms; selected from the group consisting of dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin bis(4-methylaminobenzoate), dibutyltin bis(6-methylaminocaproate), trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin bis(isopropoxide), dibutyltin bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and combinations thereof.

23. 21. The composition of claim 20, wherein the hydrolysis and condensation catalyst is in an amount of from about 0.02 to about 1.0 weight percent metal, based on the weight of the alkoxysilyl-containing polyurethane polymer.

24. 24. The composition of claim 23, wherein the hydrolysis and condensation catalyst is preferably in an amount of from about 0.05 to about 0.3 weight percent metal, based on the weight of the alkoxysilyl-containing polyurethane polymer.

25. The composition of claim 1 further comprising at least one additional additive.

26. 26. The composition of claim 25, wherein the composition is a moisture curable composition selected from the group consisting of a coating, an adhesive, a sealant, a consumer product, or an industrial product.

27. 2. The composition of claim 1, wherein the mercapto-containing compound is present in an amount effective to enhance stability when exposed to up to about 50% relative humidity for 12 days compared to a composition not comprising an effective amount of the mercapto-containing compound.

28. (i) reacting a polyol with an isocyanato-containing alkoxysilane in the presence of a urethane-forming catalyst to form an alkoxysilyl-containing polyurethane polymer composition; and (ii) adding a mercapto-containing compound to the product of step (i) to form a stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition; 2. A method for preparing the composition of claim 1 comprising:

29. (i) reacting a polyol with an excess of a polyisocyanate in the presence of a urethane-forming catalyst to form an isocyanato-containing polyurethane prepolymer composition; (ii) reacting the isocyanato-containing polyurethane prepolymer of step (i) with an amino-containing alkoxysilane to form an alkoxysilyl-containing polyurethane polymer composition; (iii) adding a mercapto-containing compound to the product of step (i) or step (ii) to form a stabilized moisture-curable alkoxysilyl-containing polyurethane polymer composition; 2. A method for preparing the composition of claim 1 comprising:

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