WO2013003051A2 - Silane terminated polycarbonate-polyester copolymers for coating, adhesives, sealant and elastomer applications - Google Patents

Abstract

Crosslinkable silyl group-containing polymers that may be made using polycarbonate-polyester copolymer polyols and methods for making the same are provided. The crosslinkable silane-terminated polymer is the reaction product of a polycarbonate-polyester copolymer polyol and an isocyanate capped hydrosilylated polymer. The isocyanate capped hydrosilylated polymer is the reaction product of at least one isocyanate and a hydrosilylated polymer. The hydrosilylated polymer is the reaction product of a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule and a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule. The crosslinkable silane-terminated polymer exhibits improved viscosity properties, UV stability and weatherability.

Description

SILANE TERMINATED POLYCARBONATE-POLYESTER COPOLYMERS FOR COATING, ADHESIVES, SEALANT AND ELASTOMER APPLICATIONS

BACKGROUND OF THE INVENTION

Field of the Invention

[0001] Embodiments of the invention relate to silane-terminated polymers and methods for producing the same.

Description of the Related Art

[0002] Crosslinkable silane-terminated polymers (STPs) are widely used as raw material polymers in coating materials, adhesives, sealing materials, elastomers and the like (CASE applications) for architectural or industrial use. Currently, the majority of silane-terminated polymers in the marketplace are derived from polyethers making the silane-terminated polymers susceptible to UV degradation and weather elements. To prolong the useful life of materials containing silane- terminated polymers, additives, such as UV absorber and thermal stabilizer may be added to the silane-terminated polymers. However, these additives increase the complexity of processing, increased product cost and may also alter the properties of the final product. Silane-terminated polymers can be made from polycarbonates, however, such polymers suffer from increased viscosity, which leads to processing challenges.

[0003] Therefore there is a need for crosslinkable silane-terminated polymers and methods for making such silane-terminated polymers with improved viscosity properties, UV stability and weatherability.

SUMMARY OF THE INVENTION

[0004] Embodiments of the invention provide for crosslinkable silyl group- containing polymers that may be made using polycarbonate-polyester copolymer polyols. In one embodiment, a crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule is provided. The crosslinkable silane-terminated polymer is the reaction product of a polycarbonate-polyester copolymer polyol and an isocyanate capped hydrosilylated polymer. The isocyanate capped hydrosilylated polymer is the reaction product of at least one isocyanate and a hydrosilylated polymer. The hydrosilylated polymer is the reaction product of a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule and a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule.

[0005] In another embodiment, a method of producing a crosslinkable silane- terminated polymer having at least one crosslinkable silyl group in each molecule is provided. The method comprises providing a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule and having a number average molecular weight of between about 100 and about 5,000, adding to the polymer a compound having a hydrogen-silicon bond and a crosslinkable. silyl group in each molecule and a hydrosilylation catalyst to thereby carry out a hydrosilylation reaction to form a composition comprising hydrosilylated polymer, capping the hydrosilylated polymer by exposing the hydrosilylated polymer to at least one isocyanate at an isocyanate index of between about 100 and about 250 to form a composition comprising isocyanate capped hydrosilylated polymers, and reacting the isocyanate capped hydrosilylated polymer with a polycarbonate- polyester copolymer polyol having a nominal functionality of at least 2 to form the composition comprising a crosslinkable silane-terminated polymer.

DETAILED DESCRIPTION

[0006] Embodiments of the invention provide for silane-terminated polymers (STP) made using polycarbonate-polyester copolymer polyols and methods for making the same. The resulting silane-terminated polymer, referred to as silane terminated polycarbonate-polyester copolymer polyol, is useful in CASE applications and also offers an environmentally friendly curing mechanism. In addition, the silane terminated polycarbonate-polyester copolymer polyol exhibits performance advantages over conventional silane terminated polymers derived from polyethers, such as UV stability, chemical resistance, and improved weatherability. [0007] In certain embodiments, the silane terminated polycarbonate-polyester copolymer polyol is represented by the general formula (I), shown below:

(R2)(r-3:,(RiO)nS - 3- -R.i O-ⁱⁱ- «-¹¹-0-R, JU— R-ss X-Ra-S OR^Rz:

m

(I) wherein R-_\ and F½ independently represent hydrogen, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyi group containing 7 to 20 carbon atoms, and when there are a plurality of Ri or F¾ groups, each R or F½ may be the same or different, wherein R₃ through R₁₀ independently represent a divalent hydrocarbon containing 1 to 20 carbon atoms, and wherein x is a divalent chemical linkage that may contain a non-carbon bond (e.g., urethane, urea, and thiol). In certain embodiments, where a polycarbonate-polyester is present, p represents an integer from 1 to 100, m represents an integer from 1 to 100, and w represents an integer from 0 to 100. In certain embodiments, where lactone is present, w represents an integer from 1 to 100. In certain embodiments, where a polycarbonate-lactone is present, p represents an integer from 0 to 100, m represents an integer from 1 to 100, and w represents an integer from 1 to 100.

[0008] In certain embodiments, the silane terminated polycarbonate-polyester copolymer polyol is represented by the general formula (II), shown below:

(ll)

[0009] . wherein Ri and R2 independently represent hydrogen, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyi group containing 7 to 20 carbon atoms, and when there are a plurality of or R₂ groups, each Ri or R₂ may be the same or different, wherein R3 through R?, and R10 independently represent a divalent hydrocarbon containing 1 to 20 carbon atoms, and wherein x is a divalent chemical linkage that may contain a non-carbon bond (e.g., urethane, urea, and thiol). In certain embodiments, where a polycarbonate-polyester is present, p represents an integer from 1 to 100 and m represents an integer from 1 to 100. [0010] As used herein, the term "hydrosilylation efficiency" = [100 x ((number of unsaturation groups on the polyol hydrosilylated)/(total number of unsaturation groups on the polyol that were initially available for hydrosilylation))], and may be measured using ¹ H-NMR or IR spectroscopy.

[0011] Hydrosilylation :

[0012] In certain embodiments described herein, the silane terminated polycarbonate-polyester copolymer polyol may be obtained by the hydrosilylation of a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule. The hydrosilylated polymers may then be capped by exposing the hydrosilylated polymer to at least one isocyanate to form a composition including isocyanate capped hydrosilylated polymers. The isocyanate capped hydrosilylated polymers may then be reacted with a polycarbonate-polyester copolymer to form the STP.

[0013] The polymer having at least one unsaturated group and at least one alcohol hydroxyl group is not particularly restricted, and may include any polymer as long as they include at least one unsaturated group (such as a carbon-carbon double bond or carbon-carbon triple bond) and at least one alcohol hydroxyl group.

[0014] The polymer having at least one unsaturated group and at least one alcohol hydroxyl group may have a molecular weight of 44 gram/mol or greater, preferably greater than 58 gram/mol, and more preferably greater than 100 gram/mol.

[0015] The polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule may have a number average molecular weight of between about 100 and about 5,000. All individual values and sub-ranges from 100 to 5,000 are included herein and disclosed herein; for example, the number average molecular weight can be from a lower limit of 100, 200, 300, 400, 500, 600, 700, 800, 900, 1 ,000, 1 ,250, 1 ,500, or 1 ,750 to, independently, an upper limit of 1 ,000, 1 ,250, 1 ,500, 1 ,750, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, or 5,000. [0016] In one embodiment, the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule may be a polyoxyalkylene polymer as described in co-pending PCT Patent Application No. PCT/US1 1/038065, entitled "Methods for Producing Crosslinkable Silyl Group-Containing Polyoxyalkylene Polymers," which is hereby incorporated by reference in its entirety.

[0017] In one embodiment, the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule may be made by subjecting an epoxy compound to ring opening polymerization using an unsaturated group- and active hydrogen-containing compound as a polymerization initiator in presence of a catalyst. Catalysis for this polymerization can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound. The active hydrogen-containing compound that may be used as a polymerization initiator is not restricted but may be any of those compounds which are applicable in association with double metal cyanide complexes, such as, for example, compounds including an alcohol hydroxyl, phenolic hydroxyl or carboxyl group.

[0018] The polymer having at least one unsaturated group and at least one alcohol hydroxyl group may include allyl alcohol, methallyl alcohol, •trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerol monoallyl ether, glycerol diallyl ether, ethylene oxide adducts or propylene oxide adducts thereof and like compounds containing at least one unsaturated group and at least one alcohol hydroxyl group in each molecule, hydroxyl-terminated hydrocarbon compounds such as hydroxyl-terminated polybutadiene, and the like. Such active hydrogen-containing compounds serving as polymerization initiators may be used singly or a plurality thereof may be used in combination.

[0019] The monoepoxide which may be used in the ring opening polymerization may include, among others, monoepoxides having no unsaturated group such as ethylene oxide, propylene oxide, butene oxide, isobutene oxide, epichlorohydrin and styrene oxide; and unsaturated group-containing monoepoxides such as allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide and cyclopentadiene monoxide. These may be used singly or a plurality thereof may be used in combination.

[0020] In one embodiment, the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule may be a propylene glycol monoallyl ether having a number average molecular weight between about 600 and about 1 ,000, and an OH number of between about 50 and about 90.

[0021] The polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule may be hydrosilylated by reacting the polymer with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in the presence of a hydrosilylation catalyst.

[0022] The compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule, may be represented by the general formula (III) shown below:

H-(Si(R¹ ₂._b)(X_b)0)_mSi(R²3-a)Xa (HI)

[0023] where R¹ and R² are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group represented by R³ ₃SiO- and, when there are a plurality of R or R² groups, they may be the same or different; R³ is a univalent hydrocarbon group containing 1 to 20 carbon atoms and the three R³ groups may be the same or different with one another; X represents a hydroxyl group or a hydrolyzable group and, when there are two or more X groups, they may be the same or different with each other or one another; a represents 0, 1 , 2 or 3 and b represents 0, 1 or 2; b's in the m of -Si R¹2- b)(Xb)0-groups may be the same or different with each other or one another; and m represents an integer from 0 to 19 provided that the relation a+∑b≥1 should be satisfied.

[0024] The hydrolyzable group represented by X may be any of those hydrolyzable groups known in the art, for example halogen atoms and alkoxy, acyloxy, ketoximato, amino, amido, acid amide, aminoxy, mercapto and alkenyloxy groups. Among them, alkoxy groups such as methoxy, ethoxy, propoxy and isopropoxy are preferred in view of their mild hydrolability and the ease of handling. One to three such hydrolyzable groups may be bonded to one silicon atom and the sum (a+∑b) is preferably 1 to 5. When there are two or more hydrolyzable groups, they may be the same or different with each other or one another. The number of silicon atoms in the crosslinkable silyl group may be about 1 to 30.

[0025] In some embodiments, the compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule represented by the above general formula (II) may include the compounds represented by the general formula (IV):

wherein R⁴represents an alkyl containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group represented by R³ ₃SiO- and, when there are a plurality of R⁴ groups, they may be the same or different; R³ is a univalent hydrocarbon group containing 1 to 20 carbon atoms and the three R³ groups may be the same or different with one another; X represents a hydroxyl group or a hydrolyzable group and, when there are two or more X groups, they may be the same or different with each other or one another; and c represents 1 , 2 or 3.

[0026] As specific examples of the compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule, there may be mentioned halosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane and 1 ,1 ,3,3-tetramethyl-1 - bromodisiloxane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane and trimethylsiloxydiethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane and trimethylsiloxydiacetoxysilane; ketoximatosilanes such as bis(dimethyl ketoximato)methylsilane, bis(cyclohexyl ketoximato)methylsjlane, bis(diethyl ketoximato)trimethylsiloxysilane, bis(methyl ethyl ketoximato)methylsilane and tris(acetoximato)silane; alkenyloxysilanes such as methylisopropenyloxysilane; and the like. Preferred among them from the mild reactivity and ease of handling viewpoint are alkoxysilanes such as methyldimethoxysilane, trimethoxysilane, methyldiethoxysilane and triethoxysilane; and halosilanes such as trichlorosilane and methyldichlorosilane.

[0027] After the reaction with an unsaturated group in the manner of hydrosilylation, the halogen atom(s) in the halosilanes may be converted to some other hydrolyzable group(s) by reacting with an active hydrogen-containing compound such as a carboxylic acid, oxime, amide or hydroxylamine or a ketone- derived alkali metal enolate by an appropriate method known in the art.

[0028] The hydrosilylation catalyst may be any of those metal complexes the metal of which is selected from among the group VIII transition metals such as platinum, rhodium, cobalt, palladium and nickel. From the hydrosilylation reactivity viewpoint, H₂PtCl6.6H₂0, platinum-divinylsiloxane complexes, platinum-olefin complexes, Pt metal, RhCI(PPh₃)₃, RhCI₃, Rh/Al₂0₃, RuCI₃, lrCI₃, FeCI₃, AICI₃, PdCI₂.2H₂ O, NiCI₂, TiCU and the like are preferred, H₂PtCI₆.6H₂0, platinum- vinylsiloxane complexes and platinum-olefin complexes are more preferred and platinum-vinylsiloxane complexes and platinum-olefin complexes are particularly preferred. The platinum-vinylsiloxane complexes collectively refer to compounds resulting from coordination of an intramolecular vinyl-containing siloxane, polysiloxane or cyclic siloxane, as a ligand, to a platinum atom. As typical examples of the ligand, there may be mentioned 1 ,1 ,3,3-tetramethyl-1 ,3-divinylsiloxane and the like. As specific examples of the olefin ligand in the platinum-olefin complex, there may be mentioned 1 ,5-hexadiene, 1 ,7-octadiene, 1 ,9-decadiene, 1 ,1 1 - dodecadiene and 1 ,5-cyclooctadiene. Among the ligands specifically mentioned above, 1 ,1 ,3,3-tetramethyl-1 ,3-divinylsiloxane and 1 ,9-decadiene are preferred from the hydrosilylation reactivity viewpoint. The hydrosilylation catalyst to be used in the practice of the invention may be used singly or a combination of a plurality of species may be used.

[0029] The amount of the hydrosilylation catalyst to be used is not particularly restricted but generally is 0.00001 to 1 part by weight, preferably 0.00005 to 0.05 part by weight, more preferably 0.0001 to 0.01 part by weight, based on the weight of the metal in the catalyst, per 100 parts by weight of the polyoxyalkylene polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule. When the amount is less than 0.00001 parts by weight, any sufficient reaction activity may not be obtained in some instances and an amount exceeding 1 part by weight may be economically disadvantageous or cause discoloration of the polymer in certain instances.

[0030] In the above reaction, the use of a solvent is essentially unnecessary. For uniformly dissolving the catalyst and/or substrate, for controlling the reaction system temperature and/or for facilitating the addition of the substrate and/or catalyst components, however, a solvent can be used. Solvents suited for these purposes include, but are not limited to, hydrocarbon compounds such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, dodecane, benzene, toluene, xylene and dodecylbenzene; haogenated hydrocarbon compounds such as chloroform, methylene chloride, chlorobenzene and o-dichlorobenzene; and ethers such as ethyl ether, tetrahydrofuran and ethylene glycoldimethyl ether, among others. Those plasticizers which can be used as plasticizers for the polyoxyalkylene polymer, such as phthalate esters and polyethers, can also be used as the reaction solvents. These may be used singly or a plurality of them may be used in combination.

[0031] The hydrosilylation reaction temperature is not particularly restricted but may for example be within the range of 0°C to 150°C., or between the range of 20 °C to 100°C. At below 0°C, the rate of reaction may be low in some instances and, at above Ι δΟ'Ό., side reactions involving the hydroxyl group, hydrogen-silicon bond and/or crosslinkable silyl group may proceed in certain instances. In one embodiment, the hydrosilylation reaction temperature is about 60°C.

[0032] In embodiments of the invention the polymers having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule are hydrosilylated with a hydrosilylation efficiency of at least about 70%, such as between about 70 % and about 100%. All individual values and subranges from about 70 to about 100 are included herein and disclosed herein; for example, the hydrosilylation efficiency can be from a lower limit of about 70, 75, 80, 90, or 92 %, to, independently, an upper limit of about 80, 85, 90, 92, 94, 95, 96, 98, 99, or 100

%. This includes polymers hydrosilylated with a hydrosilylation efficiency of 80 to 95% and further includes hydrosilylated polymers capped with a hydrosilylation efficiency of 85 to 95%. As used herein, the "hydrosilylation efficiency" = [100 x ((number of unsaturation groups on the polyol hydrosilylated)/(total number of unsaturation groups on the polyol that were initially available for hydrosilylation))], and may be measured using ¹H-NMR.

[0033] The hydrosilylated polymers having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule (hereinafter referred to as "hydrosilylated polymer") as produced by the above described process can react with water or atmospheric moisture to give crosslinked cured products and therefore is useful as a raw material or raw material intermediate for sealing, adhesive, coating and like materials or compositions for architectural or industrial use. However, the high remaining hydroxyl group percentage of this polymer having at least one crosslinkable silyl group and at least one hydroxyl may be capped with a polyisocyanate compound.

[0034] Capping:

[0035] Among the capping agents usable in the practice of the embodiments of the invention, the polyisocyanate compounds, namely compounds having two or more isocyanate groups in each molecule, include, but are not limited to, aliphatic, cycloaliphatic, arylaliphatic and aromatic isocyanates.

[0036] Examples of suitable aromatic isocyanates include the 4,4'-, 2,4' and 2,2'- isomers of diphenylmethane diisocyante (MDI), blends thereof and polymeric and monomeric MDI blends, toluene-2,4- and 2,6-diisocyanates (TDI), m- and p- phenylenediisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4'- diisocyanate, 4,4'-diisocyanate-3,3'-dimehtyldiphenyl, 3-methyldiphenyl-methane- 4,4'-diisocyanate and diphenyletherdiisocyanate and 2,4,6-triisocyanatotoluene and 2,4,4'-triisocyanatodiphenylether.

[0037] Mixtures of isocyanates may be used, such as the commercially available mixtures of 2,4- and 2,6-isomers of toluene diisocyantes. A crude polyisocyanate may also be used in the practice of the embodiments of the invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. TDI/MDI blends may also be used.

[0038] Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1 ,6- hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1 ,4- diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1 ,3- bis(isocyanatomethyl)cyclohexane, 1 ,4- bis(isocyanatomethyl)cyclohexane, saturated analogues of the above mentioned aromatic isocyanates, and mixtures thereof.

[0039] Suitable TDI products are available from the Dow Chemical Company under the trade name VORANATE®. Suitable commercially available products of that type include VORANATE® T-80 which is also available from The Dow Chemical Company. Suitable MDI products are available from The Dow Chemical Company under the trade names PAPI®, VORANATE® and ISONATE®.

[0040] The isocyanate may have a functionality of at least greater than one, preferably greater than 1 .2, and more preferably greater than 1 .8.

[0041] The capping reaction may be performed at an isocyanate index of between about 100 and about 250. All individual values and sub-ranges from 100 to 250 are included herein and disclosed herein; for example, the isocyanate index can be from a lower limit of 100, 105, 1 10, 125, 140, 150, 160, 170, 175, 180, 190, 200, 225, to, independently, an upper limit of 150, 175, 200, 225, or 250. In some embodiments the index may be between about 160 and about 200, between about 140 and about 170, or between about 150 and about 180.

[0042] When, in the practice of the embodiments of the invention, the hydrosilylated polymer is reacted with a coupling agent such as a compound having two or more isocyanate groups in each molecule, it is not always necessary to use a catalyst. In certain embodiments, it may be preferable to perform the capping reaction without a catalyst. It has been found that performing the capping reaction without a catalyst leads to a reduction of by-products {e.g., aliophanates and isocyanurates) in the capped material. For increasing the rate of reaction or improving the degree of conversion, however, a catalyst may be used. The catalyst to be used in carrying out the coupling reaction using a polyisocyanate compound includes, but is not limited to, those catalysts mentioned in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, for instance.

[0043] Preferred as the urethane formation reaction catalysts usable in effecting the coupling reaction using a polyisocyanate compound because of their high activity are tin catalysts such as stannous octylate, stannous stearate, dibutyltin dioctoate, dimethyl tin dineodecanoate (Metatin catalyst), dibutyltin dioleylmaleate, dibutyltin dibutylmaleate, dibutyltin dilaurate, 1 ,1 ,3,3-tetrabutyl-1 ,3- dilauryloxycarbonyldistannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin oxide, dibutyltin bis(triethoxysilicate), dibutyltin distearate, dibutyltin bis(isononyl 3-mercaptopropionate), dibutyltinbis(isooctyl thioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate and dioctyltin diversatate. Further, it is preferable to use catalysts low in activity against crosslinkable silyl groups and, thus, for example, sulfur atom- containing tin catalysts such as dibutyltin bis(isononyl 3-mercaptopropionate) and dibutyltin bis(isooctyl thioglycolate) are particularly preferred.

[0044] Coupling

[0045] The isocyanate capped polymers may be coupled with a polycarbonate- polyester copolymer polyol to form the final silane-terminated polymers.

[0046] Polycarbonate-Polyester Copolymer Polyol

[0047] The polycarbonate-polyester copolymer polyol may be the reaction product of. (a) a polyester polyol and (b) one or more polycarbonate polyols.

[0048] The polycarbonate-polyester polyol may have at least a functionality of one, more preferably greater than one, and most preferably greater than two. The polycarbonate repeating units may account for 0 to 100% of the total polycarbonate- polyester copolymer polyol, more preferably the polycarbonate repeating units may account for 0 to 75% of the total polycarbonate-polyester copolymer polyol. [0049] In certain embodiments, the polyester polyol may be the reaction product of (i) one or more organic acids and (ii) one or more alcohols having an OH functionality of two or more.

[0050] The one of more organic acids (i) may be a multifunctional organic acid. The one or more organic acids (i) may include at least one of aliphatic acids and aromatic acids. The one or more organic acids (i) may be selected from the group comprising for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, malic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 3,3- dimethylglutaric acid, 2,2-dimethylglutaric acid, maleic acid, fumaric acid, itaconic acid, fatty acids (linolic, oleic and the like) and combinations thereof. Anhydrides of the above acids, where they exist, can also be employed. In addition, certain materials which react in a manner similar to acids to form polyester polyol oligomers are also useful. Such materials include lactones such as caprolactone, and methcaprolactone, and hydroxy acids such as tartaric acid and dimethylolpropionic acid. If a triol or higher hydric alcohol is used, a monocarboxylic acid, such as acetic acid, may be used in the preparation of the polyester polyol oligomer, and for some purposes, such as polyester polyol oligomer may be desirable. Preferably, the one or more organic acids is adipic acid.

[0051] The at least one of one or organic acids (i) may comprise at least 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or 55 wt.% of the hydrophobic polyester polyol (a). The at least one of one or more organic acids may comprise up to 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, or 60 wt.% of the hydrophobic polyester polyol.

[0052] The one or more alcohols (ii) having an OH functionality of 2 or more (ii) may be selected from the group comprising, for example, ethylene glycol, propylene glycol, 1 ,2-butylene glycol, 2,3-butylene glycol, 1 ,3-propanediol, 1 ,3-butanediol, 1 ,4- butanediol, 1 ,6-hexanediol, neopentylglycol, 1 ,2-ethylhexyldiol, 1 ,5-pentanediol,

1 ,10-decanediol, 1 ,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol (CHDM), glycerine, trimethylolpropane, hexanetriol-(1 ,2,6) butane triol-(1 ,2,4), trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methylglycoside, also diethylene glycol, ethylene glycol, tetrathylene glycol, polyethylene glycols, dibutylene glycol, polybutylene glycols, and combinations thereof. .

[0053] The one or more alcohols (ii) may comprise at least 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt. %, or 55 wt. % of the hydrophobic polyester polyol (a). The one or more alcohols (iii) may comprise up to 10 wt.%; 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt. %, or 60 wt. % of the hydrophobic polyester polyol.

[0054] Preferably, the polyester polyol is made by reacting adipic acid, hexanediol, and a titanium acetylacetonate catalyst.

[0055] In certain embodiments where the polyester polyol (a) is hydrophobic, the polyester polyol (a) may further comprise the reaction product of (iii) at least one hydrophobic monomer.

[0056] The at least one hydrophobic monomer (iii) may include at least one of one or more dimer acids, dimer diols, hydroxy stearic acid, one or more hydroxymethylated fatty acids or esters thereof, or combinations thereof.

[0057] The one or more dimer acids may include dimer acids containing from about 18 to about 44 carbon atoms. Dimer acids (and esters thereof) are a well known commercially available class of dicarboxylic acids (or esters). They are normally prepared by dimerizing unsaturated long chain aliphatic monocarboxylic acids, usually of 13 to 22 carbon atoms, or their esters (alkyl esters). Not to be bound by theory but it is believed that the dimerization is thought to proceed by possible mechanisms which include Diels Alder, free radical, and carbonium ion mechanisms. The dimer acid material will usually contain 26 to 44 carbon atoms. Particularly, examples include dimer acids (or esters) derived from Cie and C22 unsaturated monocarboxylic acids (or esters) which will yield, respectively, C36 and C₄₄ dimer acids (or esters). Dimer acids derived from Cie unsaturated acids, which include acids such as linoleic and linolenic are particularly well known (yielding C36 dimer acids). For example, DELTA 9, 1 1 and DELTA 9, 12 linoleic acids can dimerize to a cyclic unsaturated structure (although this is only one possible structure; other structures, including acyclic structures are also possible). The dimer acid products may also contain a proportion of trimer acids (Cs₄ acids when using Ci8 starting acids), possibly even higher oligomers and also small amounts of the monomer acids. Several different grades of dimer acids are available from commercial sources and these differ from each other primarily in the amount of monobasic and trimer acid fractions and the degree of unsaturation. The various dimers may be selected from crude grade dimer acids, hydrogenated dimer acids, purified/hydrogenated dimer acids, and combinations thereof.

[0058] Exemplary dimer acids are available from Croda under the tradename PRIPOL™ acids and from Cognis under the tradename EMPOL® acids. Suitable commercially available products of that type include PRIPOL™ 1017 (C36 dimer fatty acid), PRIPOL™ 1013 (C36 distilled dimer fatty acid), and PRIPOL™ 1006 (hydrogenated C36 dimer fatty acid).

[0059] The dimer diols may include dimer acids which have been reduced to the corresponding dimer diols. Exemplary dimer diols are available from Croda under the tradename PRIPOL™ diols. Suitable commercially available products of that type include PRIPOL™ 2030 and PRIPOL™ 2033.

[0060] The hydroxyl stearic acid may include 12 hydroxy stearic acid (12-HSA). Saturated monobasic secondary hydroxy fatty acids, especially 12-HSA, are commercially available.

[0061] The one or more hydroxymethylated fatty acids or esters thereof may be based on or derived from renewable feedstock resources such as natural and/or genetically modified plant vegetable seed oils and/or animal source fats. Suitable hydroxymethylated fatty acids or esters thereof may be obtained through hydroformylation and hydrogenation methods such as described in United States Patent Nos. 4,731 ,486 and 4,633,021 , for example, and in U.S. Published Patent Application No. 2006/0193802.

[0062] In one embodiment the one or more hydroxymethylated fatty acids or esters thereof is a monol-rich monomer. "Monol-rich monomer" and like terms means a composition comprising at least 50, typically at least 75 and more typically at least 85, weight percent (wt.%) mono-hydroxy functional fatty acid alkyl ester such as, but not limited to, that of formula I:

(I)

The length of the carbon backbone of formula I can vary, e.g., C12-C20, but it is typically C18, as can the placement of the hydroxymethyl group along its length. The monol-rich monomer used in the practice of this invention can comprise a mixture of mono-hydroxy functional fatty acid alkyl esters varying in both carbon backbone length and hydroxy group placement along the length of the various carbon backbones. The monomer can also be an alkyl ester other than methyl, e.g., a C2- Ce alkyl ester. Other components of the composition include, but are not limited to, poly (e.g., di-, tri-, tetra-, etc.) hydroxy functional fatty acid alkyl esters.

[0063] The source of the monol-rich monomer can vary widely and includes, but is not limited to, high oleic feedstock or distillation of a low oleic feedstock, e.g., a natural seed oil such as soy as, for example, disclosed in co-pending application "PURIFICATION OF HYDROFORMYLATED AND HYDROGENATED FATTY ALKYL ESTER COMPOSITIONS" by George Frycek, Shawn Feist, Zenon Lysenko, Bruce Pynnonen and Tim Frank, filed June 20, 2008, application number PCT/US08/67585, published as WO 2009/009271 .

[0064] The monol-rich monomer may be derived by first hydroformylating and hydrogenating the fatty alkyl esters or acids, followed by purification to obtain monol rich monomer. Alternatively, the fatty alkyl esters or acids may first be purified to obtain mono-unsaturated rich monomer and then hydroformylated and hydrogenated.

[0065] The at least one hydrophobic monomer (i) may comprise at least 5 wt.%. 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, or 75 wt.% of the polyester polyol (a). The at least one hydrophobic monomer (i) may comprise up to 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, or 80 wt.% of the polyester polyol.

[0066] The polyester polyol may be formed by a polymerization reaction. With respect to the method for performing the polymerization reaction, there is no particular limitation, and the polymerization reaction can be performed by using conventional methods known in the art. The polymerization reaction may be aided by a catalyst. Examples of the catalyst may include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, cobalt, zinc, aluminum, germanium, tin, lead, antimony, arsenic, and cerium and compounds thereof. As the metallic compounds, oxides, hydroxides, salts, alkoxides, organic compounds, and the like may be mentioned. Of these catalysts, it is preferred to use titanium compounds such as titanium tetrabutoxide, titanium tetra-n-propoxide, titanium tetra-isopropoxide, titanium 2-ethyl hexanoate, and titanium acetylacetonate tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide, and dibutyitin diacetate, lead compounds such as. lead acetate and lead stearate. Exemplary titanium catalysts are available from DUPONT™ under the tradename TYZOR® titanium acetylacetonates. Suitable commercially available products of that type include TYZOR® AA-105.

[0067] The polyester polyol (a) may comprise at least 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or 90 wt.% of the polycarbonate- polyester polyol. The polyester polyol (a) may comprise up to 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, or 95 wt.% of the polycarbonate-polyester polyol.

[0068] Component (b) may comprise one or more polycarbonate polyols. The one or more polycarbonate polyols may comprise repeating units from one or more alkane diols having 2 to 50 carbon atoms. The one or more polycarbonate polyols may comprise repeating units from one or more alkane diols having 2 to 20 carbon atoms. The one or more polycarbonate polyols may be difunctional polycarbonate polyols. [0069] The one or more polycarbonate polyols may have a number average molecular weight from about 500 to about 5,000, preferably, from about 500 to about 3,000, more preferably, from about 1 ,800 to about 2,200.

[0070] The one or more polycarbonate polyols may have a hydroxyl number average from about 22 to about 220 mg KOH/g, for example, from about 51 to 61 mg KOH/g.

[0071] The. one or more polycarbonate polyols may have a viscosity from about 4,000 to about 15,000 centipose (cp) measured at 60 degrees Celsius by parallel plate rheometry.

[0072] The one or more polycarbonate polyols (b) may be prepared by reacting at least one polyol mixture comprising (i) one or more alkane diols (ii) with at least one organic carbonate. The one or more polycarbonate polyols may be obtained by subjecting the at least one polyol mixture and the at least one carbonate compound to a polymerization reaction. With respect to the method for performing the polymerization reaction, there is no particular limitation, and the polymerization reaction can be performed by using conventional methods known in the art.

[0073] The one or more alkane diols (i) may be selected from the group comprising: aliphatic diols having 2 to 50 carbon atoms in the chain (branched or unbranched) which may also be interrupted by additional heteroatoms such as oxygen (O), sulphur (S) or nitrogen (N). Examples of suitable diols are 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexandiol, 1 ,7-heptanediol, 1 ,2- dodecanediol, cyclohexanedimethanol, 3-methyl-1 ,5-pentanediol, 2, 4-diethyl-1 ,5- pentanediol, bis(2-hydroxyethyl)ether, bis(6-hydroxyhexyl)ether or short-chain C₂, C₃ or C₄ polyether diols having a number average molecular weight of less than 700 g/mol, combinations thereof, and isomers thereof.

[0074] The at least one carbonate compound (ii) may be selected from alkylene carbonates, diaryl carbonates, dialkyl carbonates, dioxolanones, hexanediol bis- chlorocarbonates, phosgene and urea. Examples of suitable alkylene carbonates may include ethylene carbonate, trimethylene carbonate, 1 ,2-propylene carbonate, 5-methyl-1 ,3-dioxane-2-one, 1 ,2-butylene carbonate, 1 ,3-butylene carbonate, 1 ,2- pentylene carbonate, and the like. Examples of suitable dialkyl carbonates may include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, and the like and the diaryl carbonates may include diphenyl carbonate.

[0075] The polymerization reaction for the polycarbonate polyol may be aided by a catalyst. With respect to the method for performing the polymerization reaction, there is no particular limitation, and the polymerization reaction can be performed by using conventional methods known in the art. The polymerization reaction may be a transesterification reaction. In a transesterification reaction, one preferably contacts reactants in the presence of a transesterification catalyst and under reaction conditions. In principle, all soluble catalysts which are known for transesterification reactions may be used as catalysts (homogeneous catalysis), and heterogeneous transesterification catalysts can also be used. The process according to the invention is preferably conducted in the presence of a catalyst.

[0076] Hydroxides, oxides, metal alcoholates, carbonates and organometallic compounds of metals of main groups I, II, III and IV of the periodic table of the elements, of subgroups III and IV, and elements from the rare earth group, particularly compounds of Ti, Zr, Pb, Sn and Sb, are particularly suitable for the processes described herein.

[0077] Suitable examples include: LiOH, Li₂C0₃, K₂C0_3> KOH, NaOH, KOMe, NaOMe, MeOMgOAc, CaO, BaO, KOt-Bu, TiCI₄, titanium tetraalcoholates or terephthalates, zirconium tetraalcoholates, tin octoate, dibutyltin dilaurate, dibutyltin, bistributyltin oxide, tin oxalate, lead stearate, antimony trioxide, and zirconium tetraisopropylate.

[0078] Aromatic nitrogen heterocycles can also be used in the process described herein, as can tertiary amines corresponding to R1 R2R3N, where R _-3 independently represents a C C₃o hydroxyalkyl, a C₄-C₃₀ aryl or a Ci-C₃₀ alkyl, particularly trimethylamine, triethylamine, tributylamine, Ν,Ν-dimethylcyclohexylamine, N,N- dimethyl-ethanolamine, 1 ,8-diaza-bicyclo-(5.4.0)undec-7-ene, 1 ,4-diazabicyclo- (2.2.2)octane, 1 ,2-bis(N,N-dimethyl-amino)-ethane, 1 ,3-bis(N-dimethyl- amino)propane and pyridine. [0079] Alcoholates and hydroxides of sodium and potassium (NaOH, KOH, KOMe, NaOMe), alcoholates of titanium, tin or zirconium (e.g. Ti(OPr)₄), as well as organotin compounds may also be used, wherein titanium, tin and zirconium tetraalcoholates may be used with diols which contain ester functions or with mixtures of diols with lactones.

[0080] The amount of catalyst present depends on the type of catalyst. In certain embodiments described herein, the homogeneous catalyst is used in concentrations (expressed as percent by weight of metal with respect to the aliphatic diol used) of up to 1 ,000 ppm (0.1 %), preferably between 1 ppm and 500 ppm (0.05%), most preferably between 5 ppm and 100 ppm (0.01 %). After the reaction is complete, the catalyst may be left in the product, or can be separated, neutralized or masked. The catalyst may be left in the product.

[0081] Temperatures for the transesterification reaction may be between 120 degrees Celsius and 240 degrees Celsius. The transesterification reaction is typically performed at atmospheric pressure but lower or higher pressures may be used. Vacuum may be applied at the end of the activation cycle to remove any volatiles. Reaction time depends on variables such as temperature, pressure, type of catalyst and catalyst concentration.

[0082] Exemplary polycarbonate polyols comprising repeating units from one or more alkane diol components are available from Arch Chemicals, Inc., under the trade name Poly-CD™220 carbonate diol and from Bayer MaterialScience, LLC, under the tradename DESMOPHEN® polyols.

[0083] The one or more polycarbonate polyols (b) may comprise at least 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or 90 wt.% of the polycarbonate-polyester polyol. The one or more polycarbonate polyols (b) may comprise up to 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, or 95 wt.% of the polycarbonate-polyester polyol. [0084] The polycarbonate-polyester polyol may be prepared by subjecting the one or more polyols (a) and the one or more polycarbonate polyols (b) to a polymerization reaction. The polymerization reaction may be a transesterification reaction. In principle, all soluble catalysts which are known for transesterification reactions may be used as catalysts (homogeneous catalysis), and heterogeneous transesterification catalysts can also be used. The exemplary catalysts described above for formation of the polycarbonate polyol may also be used for formation of the polycarbonate-polyester polyol.

[0085] As described above, temperatures for the transesterification reaction may be between 120 degrees Celsius and 240 degrees Celsius. The transesterification reaction is typically performed at atmospheric pressure but lower or higher pressures may also be useful. Vacuum may be applied at the end of the activation cycle to remove any volatiles. Reaction time depends on variables such as temperature, pressure, type of catalyst and catalyst concentration. In certain embodiments, where titanium catalysts are used in the production of the polycarbonate polyol, any residual titanium catalyst in the polycarbonate may assist with the transesterification reaction for formation of the polycarbonate-polyester polyol.

[0086] The silane-terminated polycarbonate-polyester copolymer may be prepared by subjecting the polycarbonate-polyester polyol and the isocyanate capped polymer to a reaction at 70 °C for 2 hours in the presence of dibutyl tin dilaurate catalyst. After the reaction is complete as checked by the disappearance of the isocyanate peak (1740 cm-1 ) in IR spectrum, the polymer is isolated.

[0087] According to the embodiments of the invention, the resulting silane- terminated polymers may be useful, among other things, to be reacted with one another to further lengthen the molecular chains for uses such as sealants, adhesives, and coatings, and combinations thereof. When silyl polymers are exposed to moisture, for example, the moisture from the atmosphere, the hydrolyzable groups which are bonded to the silicon atoms are hydrolyzed, being replaced by silicon bonded hydroxyl groups. The hydroxyl groups in turn react with each other or with other hydrolyzable groups to form siloxane (Si-O-Si) linkages. By this process the polymer molecules of the composition of the embodiments of the invention are bonded to form an infusible elastomeric material. To avoid premature curing, the compositions of the embodiments of the invention may be stored and maintained in the absence of moisture until cure is desired. Then, when cure is desired, the polymer may be exposed to atmospheric or other moisture.

[0088] Furthermore, the reaction of curing of the silyl polymer may be facilitated by use of a silanol condensation catalyst or curing accelerator. Silanol condensation catalysts or accelerators are well known in the art such as those disclosed in US6,355,127 and include the following: titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, and the like; organotin compounds, such as dibutyltin ^'dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, dimethyl tin dineodecanoate (Metatin catalyst), reaction products of dibutyltin oxide and phthalic acid esters, dialkyltin diacetyl acetonates, such as dibutyltin bis(acetylacetonate); dialkyltinoxides, such as dibutyltinoxide; organoaluminum compounds, such as aluminum trisacetylacetonate, aluminum trisethylacetonate, and the like; reaction products, such as bismuth salts and organic carboxylic acids, such as bismuth tris(2-ethylhexoate), bismuth tri(neodeconate), and the like; chelate compounds, such as zirconium tetracetylacetonoate, titanium tetracetylacetonate, and the like; amine compounds, such as butylamine, octylamine, dibutylamine, monethanolamine, diethanolamine, triethanolamine, diethylenetriamine, cyclohexylamine, benzylamine, and the like, or their salts with carboxylic acids, ^"and the like. These compounds are not limited; one can use any silanol condensation catalyst which is in general use. These silanol condensation catalysts may be used individually or in combinations. Such catalysts and accelerators include tetrabutyltitanate, dibutyltin dilaurate, dibutyltin bis(acetylacetonate), and the like. The catalyst may be present in an amount of about at least about 0.1 percent by weight of the polymer, at least about 0.5 percent by weight of the polymer, at least about 1 percent by weight of the polymer, at least about 1 .5 percent by weight of the polymer, or at least about 2 percent by weight of the polymer and at most about 8 percent by weight of the polymer, at most about 6 percent by weight of the polymer, at most about 5 percent by weight of the polymer, at most about 4 percent by weight of the polymer, or at most about 3.5 percent based on weight of the polymer. Such catalysts may be combined with the polymer by means within the skill in the art during the formulation of the sealant, coating, or adhesive. [0089] The resulting cured silyl polymers are also embodiments of the invention. Similarly, the embodiments of the invention include the sealants, adhesives, and coatings and other end uses comprising these polymers or prepolymers. Preferred properties for the silyl polymers may differ somewhat for each end use as do other components that are optionally present in compositions suitable for each.

[0090] In certain embodiments, the process comprises (1 ) a hydrosilylation reaction of a vinyl-terminated monol with an alkoxysilane in the presence of a catalyst to produce an alkoxysilyl terminated monol, (2) a capping reaction of the alkoxysilyl terminated monol with an isocyanate, such as TDI (toluene diisocyanate), in a sequence of adding the alkoxysilyl monol to the isocyanate at a first temperature (e.g., 60 °C) and a certain rate without the addition of catalysts. The reaction reaches completion at 85 °C producing an isocyanate capped prepolymer of 2.69 to 3.18 %NCO and (3) a coupling reaction obtained by reacting the isocyanate capped prepolymer with the polycarbonate-polyester polyol to produce the STP. In certain embodiments, the vinyl-terminated monol has a basicity from 0 to 4.7 x 10^~3 mgKOH/g, preferably from 0 to 1.9 x 10^"3 mgKOH/g, more preferably from 0 to 1 .4 x 10^"3 mgKOH/g, and most preferably from 0 to 1.0 x 10^"3 mgKOH/g.

[0091] EXAMPLES

[0092] Objects and advantages of the embodiments described herein are further illustrated by the following examples. The particular materials and amounts thereof, as well as other conditions and details, recited in these examples should not be used to limit the embodiments described herein. Examples of the invention are identified by the letter "E" followed by the sample number while comparative samples, which are not examples of the invention are designated by the letter "C" followed by the sample number.

[0093] A description of the raw materials used in the examples is as follows:

ACCLAIM Polyol 2200 A difunctional polyether polyol based on propylene oxide with a molecular weight of about 2000 and a hydroxyl number of 56 mg KOH/g, available from Bayer MaterialScience. Adipic acid Available from SIGMA-ALDRICH®. Allyl Monol A propylene glycol monoallyl ether having an allylic content of 3.5 wt% (0.998 mol of unsat/mol monol), a number average molecular weight of about 800, and an OH number of 70 or 2.1 wt% OH commercially available from the Dow Chemical Company under the tradename UCON™ Hydrolube APPG 800.

ASAHI 2000 A polycarbonate polyol which is a copolymer of 1 ,6- hexanediol and 1 ,5-pentane diol (50/50 mol%) commercially available from Asahi Glass Company.

DABCO T-12 A dibutyltin dilaurate catalyst available from Air Products. DBTA Dibutyltin bis(acetylacetonate), Available from SIGMA- ALDRICH®.

DDBSA Dodecyl benzene sulfonic acid. Available from SIGMA- ALDRICH®.

Dimethyl carbonate Available from SIGMA-ALDRICH®. Hexane^'diol Available from SIGMA-ALDRICH®. Karstedt's catalyst Platinum-divinyltetramethyldisiloxane and xylene as carrier solvent, the Pt loading in the catalyst is 2 wt%, available from Gelest, Inc.

Methyldimethoxysilane Available from Gelest, Inc. POLYCAT 41 A trimerization catalyst available from Air Products. SnAcAc Tin (II) Acetylacetonate, available from Sigma Aldrich.

TOYOCAT-DB30 Acid blocked tertiary amine (1 ,8- Diazabicyclo[5.4.0]undec-7-ene) catalyst available from Tosoh Corporation. TYZOR® TPT A tetra-isopropyl titanate catalyst which is a reactive organic alkoxy titanate with 100% active content commercially available from DuPont™.

TYZOR® OGT An octyleneglycol tinanate catalyst which is a reactive organic alkoxy titanate with 100% active content-, commercially available from DuPont™.

VORANATE™ T-80 A toluene diisocyanate (80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate by weight) composition, available from The Dow Chemical Company.

Zn Octoate Available from Shepherd Chemical Corporation.

[0094] Test Methods:

[0095] Tensile strength was measured according to ASTM standard test D1708. Elongation at break was measured according to ASTM standard test D1708. 100% According to ASTM standard test D1708 four dog bone samples were prepared, and analyzed for mechanical properties. The results are reported as the average of the four samples with a standard deviation. The number average molecular weight was determined by gel permeation chromatograpy using PEG standards, according to ASTM standard test D5296. Viscosity was measured using a rheometer AR2000 by TA Instruments. Approximately 1 ml_ of sample was dispensed into a 60mm diameter 60-degree cone and plate geometry. After removal of any excess material, the viscosity test was performed by heating the sample from 20^QC to 100 ^SC at 3 ^sC/min. Shear rate of the test was kept constant at 0.1 s^'1.

[0096] Synthesis of Polycarbonate-Polyester Copolymer Polypi:

[0097] Synthesis of Hexanediol based PC Polvol (HDPC):

[0098] A 1 ,000 mL four-neck round-bottom flask was equipped with a Dean-Stark trap, thermocouple, and mechanical stirrer. The fourth port was used to add dimethyl carbonate (DMC). The flask was heated with a heating mantle and monitored in the reaction via the thermocouple. 834 g of hexane diol (7.055 mol) was added to the flask and was heated to 150 degrees Celsius while sweeping with N₂ to inert the flask and remove water present in the butane diol. TYZOR® TPT catalyst (188 mg) was added via syringe to the reaction flask. DMC was added via peristaltic pump and within 45 minutes DMC and methanol began to distill over at 62 degrees Celsius. In total, 1 ,079 g of DMC (1 1 .994 mol, 1 .7 eq wrt HDO) was added at a rate sufficient to maintain the overhead temperature between 62 to 65 degrees Celsius. Upon completion of the DMC add, the temperature was increased, in 10 degrees Celsius increments, to 200 degrees Celsius. Upon reaching 200 degrees Celsius, the pot temp was immediately reduced to 170 degrees Celsius and a nitrogen sweep was begun (overnight). The molecular weight (Mn) was found to be 3,065 g/mol (pdi 2.28) by GPC analysis and 3,660 g/mol via 1 H NMR end-group analysis.

[0099] Next 27.3 g of Hexane diol (HDO) was added to the reaction mixture with stirring at 170 degrees Celsius. After two hours of reaction under these conditions, the Mn was found to be 1 ,590 g/mol by 1 H NMR end-group analysis with 9 mole% carbonate end-groups. The reaction pressure was reduced to 120 torr and the reaction was stirred at 180 degrees Celsius for two hours resulting in an increase in molecular weight to 2,159 g/mol (1 H NMR end-group analysis) with 3.9 mole% carbonate end-groups. HDO (3.9 g) was added and the reaction was stirred at 170 degrees Celsius for two hours before reducing the pressure to 80 torr and increasing the temperature to 200 degrees Celsius for an additional two hours. The molecular weight increased to 2,275 g/mol (1 H NMR end-group analysis) and the hydroxyl number was determined to be 49.36 mg KOH/g. A final HDO add of 5.2 g was made and the reaction was stirred for an additional two hours at 180 degrees Celsius. The molecular weight was reduced to 1 ,773 g/mol (1 H NMR end-group analysis) and the carbonate end-groups were non-detect by 1 H NMR. The hydroxyl number of the final polymer was 55 mg KOH/g.

[0100] Table I. Hexane Diol Polycarbonate (HDPC) Polyol Formulations:

Raw Materials Amount

Alkane Diol 120 g Titanium Catalyst 185 mg

Dimethyl Carbonate 141 .6 g

Table I: HDPC formulations.

[0101] A 500 mL 4-neck RBF was equipped with a Dean-Stark trap, thermocouple, and mechanical stirrer. The fourth port was used to add dimethyl carbonate. The flask was heated with a heating mantle monitored in the reaction via the thermocouple. To the flask was added 120 g hexane diol (1 .015 mol) and -185 mg of TYZOR® OGT catalyst. The mixture was heated to 150 °C and the addition of DMC via peristaltic pump was begun at a rate of 0.433 mL/min. In total 141.6 g of dimethyl carbonate (1 .577 mol, 1 .55 eq wrt HDO) was added over 295 min. After 36 min. overheads began to distill and the overhead temperature increased to -63 °C. The pot temperature was maintained at 150 °C over the course of the DMC addition. Upon completion of DMC addition, the temperature was increase to 200 °C at a rate sufficient to maintain the overhead temperature at about 65 C. Upon reaching 200 °C the pot temp was reduced to 170 °C and a nitrogen sweep was begun (overnight). The Mn was found to be 3270 (Xn =22.7) relative to PEG standards. Hexanediol (5 g) was added at 170 °C to reduce the Mn to 1800 g/mol. After 70 minutes of digestion at 170 °C, the Mn was found to be 1833 g/mol.

[0102] Synthesis of polyester (PE)

[0103] A designated amount of raw materials were added into a 4 neck-round bottom flask, and then the flask was placed on the heating mantle and the mechanical stirrer was set up on the center neck. A nitrogen gas needle was inserted through the rubber septum with the nitrogen flow rate at 0.1 L/min. In order to remove the by-product (H₂0) effectively as well as selectively (i.e. minimizing raw material losses), the specially designed separation column (vacuum jacketed column) was utilized. The water by-product was collected using a distilling head. The reaction temperature was controlled by the temperature controller which was connected with a thermocouple and a heating mantle. The reaction temperature was set at 210 degrees Celsius. The raw materials were melted before applying mechanical stirring condition, and then the reaction was started with a mild stirring condition (300 rpm) and lower nitrogen stripping rate (0.1 L/min) to minimize the loss of raw materials. When the reaction achieved 80 to 90 % conversion, both stirring and nitrogen gas stripping rate were increased up to 600 rpm and 0.7 L min, respectively, until the reaction was completed. The reaction was monitored by measuring acidity, and was regarded as complete when the acidity become less than 2 mgKOH/g.

[0104] Table II. Polyester Polyol Formulations:

Table II: PE polyol formulations.

[0105] Synthesis of polyester polycarbonate (PC ester) copolymer via transesterification route

[0106] Designated amount of HDPC and 1 , 6 Polyester Polyol was weighed in a 3L flask. The mixture was heated to 185 degrees Celsius for six hours under nitrogen. The mixture was cooled to 100 degrees Celsius and 0.26g of dibutyl phosphate was added to quench the residual Ti catalyst. The resulting copolymer was mixed for one hour. Vacuum 'was applied for 30 minutes to strip off any volatiles.

[0107] Table III. Polyester Polycarbonate (PC ester) Formulations:

Raw Materials 50/50 75/25

HDPC 600 g 600 g

PE Polyol 600 g 200 g

Dibutyl Phosphate 0.26 g 0.26 g Table III: PC ester formulations.

[0108] Hvdrosilylation:

[0109] A hydrosilylation reaction was performed by charging propylene glycol monoallyl ether (343.20 g; 800 MW) into a 4-necked 250mL pre-dried glass reactor equipped with a mechanical stirrer. Karstedt's catalyst (Approximately 0.03 g) was then added to the reactor and mixed for 2 minutes under a continuous nitrogen purge. Methyldimethoxysilane (50.02 g; 106 MW) was added last and mixed for 5 minutes before the entire reactor was heated to 60 °C for 2 hours. The hydrosilylation product (hereinafter referred to as Hydrosilylated Polyether) was analyzed using ¹H-showing a hydrosilylation efficiency of >95%.

[0110] Prepolymer Synthesis (NCO capping):

[0111] The Hydrosilylated Polyether (299.8 g) was then reacted with excess VORANATE T-80 (49.00 g) in at 85 °C and at 300 rpm mixing speed for minimum of 6 hours to produce NCO-capped prepolymers.

[0112] Coupling:

[0113] The NCO-capped prepolymers (348.81 g) obtained above were exposed to a coupling reaction, in which the NCO-capped prepolymers were reacted with the polycarbonate-polyester copolymer polyol (231 .63 g) in the presence of DABCO T- 12 catalyst (0.0695 g) at 70°C for 2 hours to produce the silane terminated polycarbonate-polyester copolymer polyol.

[0114] Curing:

[0115] The curing of the materials was achieved by addition of tin acetyl acetanoate (SnAcAc), dodecyl benzene sulfonic acid (DDBSA), or DB-30 acrylic acid blocked amine catalyst in the presence of moisture. Films of the silane terminated polymer materials were drawn down on polypropylene sheets to 25 Mil thickness and cured at 25^QC and 50% relative humidity for a minimum of one week.

[0116] Table IV depicts the components involved in the coupling and curing reactions for Examplel through Example 5 (E1 , E2, E3, E4, and E5). As shown in Table IV, Examples 1 -3 are based on the (75/25) Polycarbonate-Polyester Copolymer Polyol and Examples 4 and 5 are based on the (50/50) Polycarbonate- Polyester Copolymer Polyol.

Table IV. Example 1-5 - Coupling/Curing Formulations:

Table IV.

[0118] Table IV depicts the components involved in the coupling reaction for Examplel through Example 5 (E1 , E2, E3, E4, and E5). As shown in Table IV, Examples 1 -3 are based on the (75/25) Polycarbonate-Polyester Copolymer Polyol and Examples 4 and 5 are based on the (50/50) Polycarbonate-Polyester Copolymer Polyol.

Table V. Controls 1-6 - Coupling/Curing Formulations:

Table V.

[0120] Table V depicts the components involved in the coupling reaction for Control 1 through Control 6 (C1 , C2, C3, C4, C5, C6). As shown in Table V, Controls 1 -3 are based on a polycarbonate polyol and Controls 4-6 are based on a polyester polyol.

[0121] The silane-terminated Polycarbonate-Polyester Copolymers (E1 -E5) exhibited significantly reduced viscosity when compared with the silane-terminated polycarbonate based polymers (C1 -C3).

[0122] Certain film samples were also submerged in water at 100°C for 1 week, and the physical properties measured on surviving samples. The tensile data, elongation data, and modulus data for Examplel through Example 5 are depicted in Table VI and the tensile data, elongation data, and modulus data for Control 1 through Control 6 are depicted in Table VII.

[0123] Table VI. Examples 1-5 - Data:

E1 E2 E3 E4 E5

Tensile Data

Tensile Strength (psi) 97.2 36.7 47.9 47.4 48.3

Tensile Strength (psi) Water 18.9 21 .4

Treatment

Standard Deviation 35.4 6.7 7.2 29 5.1

Standard Deviation after Water 1 .2 4.7 Uptake

Elongation Data

% Elongation at Break 221 906.3 325.2 264.4 270.2

% Elongation at Break Water 343.8 478.8

Treatment

Standard Deviation 67.6 54.1 37.1 136.8 18

Standard Deviation after Water 13.7 53.2

Uptake

Modulus Data

Stress @ 100 psi 47.4 6.4 20.1 20.2 20.7

Stress @ 100 psi Water ' 7.72 2.5

Treatment

Standard Deviation 2.5 2.6 1.7 0.6 1 .6

Standard Deviation after Water 7.72 1 .6

Uptake

Table VI

[0124] Table VII. Controls 1-6 - Data:

Table VII.

[0125] As demonstrated in Table VI, E3 and E4 which were cured in the presence of an amine catalyst exhibited superior mechanical integrity relative to samples cured in the presence of SnAcAc (E1 ) and in the presence of DDBSA (E2) which both exhibited loss of mechanical integrity.

[0126] The samples were also exposed to ultraviolet light for a period of twenty- four hours at 50 degrees Celsius. The silane-terminated Polycarbonate-Polyester Copolymer (75/25) and the silane-terminated Polycarbonate-Polyester copolymer (50/50) exhibited no damage and slight yellowing. The silane-terminated polycarbonate based polymer also exhibited no damage and slight yellowing. However, the silane-terminated polyether based polymer became liquid. The silane- terminated Polycarbonate-Polyester Copolymers described herein exhibited superior UV stability relative to the silane-terminated polyether based polymer.

[0127] While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof.

Claims

What is claimed is:

1 . A crosslinkable silane-terminated polymer composition comprising at least one molecule having the structure:

(Rz>₍r-3i(RiO>„S— Rj-X-R_t

wherein and R2 independently represent hydrogen, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms;

wherein R3-R10 independently represent a divalent hydrocarbon containing 1 to 20 carbon atoms;

wherein p = 1 to 100, m = 1 to 100, and w = 0 to 100; and

wherein x is a divalent linkage that may contain a non-carbon bond.

2. The composition of claim 2, wherein X is selected from the group consisting of urethane, urea, and thiol.

3. A method of producing a composition comprising a crosslinkable silane- terminated polymer having at least one crosslinkable silyl group in each molecule, the method comprising:

providing a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule and having a number average molecular weight of between about 100 and about 5,000;

adding to the polymer a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule and a hydrosilylation catalyst to thereby carry out a hydrosilylation reaction to form a composition comprising hydrosilylated polymer;

capping the hydrosilylated polymer by exposing the hydrosilylated polymer to at least one isocyanate at an isocyanate index of between about 100 and about 250 to form a composition comprising isocyanate capped hydrosilylated polymers; and reacting the isocyanate capped hydrosilylated polymer with a polycarbonate- polyester copolymer polyol having a nominal functionality of at least 2 to form the composition comprising a crosslinkable silane-terminated polymer.

4. A composition comprising:

a crosslinkable silane-terminated polymer that is the reaction product of:

a polycarbonate-polyester copolymer polyol; and

an isocyanate capped hydrosilylated polymer comprising a reaction product of:

at least one isocyanate; and

a hydrosilylated polymer comprising a reaction product of:

a polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule; and

a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule.

5. The method of claim 3 or the composition of claim 4, wherein the crosslinkable silane-terminated polymer has the following formula:

(R₂>,'r-3:.(Ri°>nS

wherein Ri and R2 independently represent hydrogen, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms;

wherein R3-R10 independently represent a divalent hydrocarbon containing 1 to 20 carbon atoms;

wherein x is a divalent linkage that may contain non-carbon bonds.

6. The method or composition of any of claims 3-5, wherein X is selected from the group consisting of urethane, urea, and thiol.

7. The composition of any of claims 4 to 6, wherein the hydrosilylated polymer is reacted with the isocyanate at an isocyanate index of between about 100 and about 250.

8. The method or composition of any of claims 3 to 7, wherein the hydrosilylated polymer is a reaction product of a hydrosilylation reaction having a hydrosilylation efficiency of at least about 70% as determined by H-NMR.

9. The composition of claims 4 to 8, wherein the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule has having a number average molecular weight of between about 100 and about 5,000.

10. The method or composition of any one of claims 3 to 9, wherein the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule has a number average molecular weight of between about 200 and about 2,000.

1 1. The method or composition of any one of claims 3 to 10, wherein the polymer having at least one unsaturated group and at least one alcohol hydroxyl group in each molecule comprises a propylene glycol monoallyl ether having a number average molecular weight between about 600 and about 1 ,000, and an OH number of between about 50 and about 90.

12. The method or composition of any one of claims 3-1 1 , wherein the isocyanate index is between about 160 and about 200.

13. The method or composition of any one of claims 3-12, wherein the hydrosilylation efficiency is at least about 85%.

14. The method or composition of any one of claims 3-13, wherein the compound having a hydrogen-silicon bond and a crosslinkable silyl group comprises at least one of trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane and trimethylsiloxydiethoxysilane.

15. The method or composition of any. one of claims 3-14, wherein the isocyanate comprises at least one of 4,4'-, 2,4' and 2,2'-isomers of diphenylmethane diisocyanate, 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate, or blends thereof.

16. The method or composition of any one of claims 3-15, wherein the crosslinkable silane-terminated polymer is cured with an amine containing catalyst to form a cured polymer.

17. The method or composition of any one of claims 3-16, wherein the polyester- polycarbonate polyol is the reaction product of:

(a) a polyester polyol which is the reaction product of

(i) one or more organic acids;

(ii) one or more alcohols having an OH functionality of 2 or more; and

(b) one or more polycarbonate polyols.

18. The method or composition of claim 17, further comprising one or more hydrophobic monomers comprising at least one of dimer acids, dimer diols, hydroxy stearic acid, hydroxymethylated fatty acids, or esters thereof.

19. The method or composition of any one of claims 17 or 18, wherein the one or more organic acids comprises adipic acid and the one more alcohols comprises at least one of 1 ,4-butanediol and 1 ,6 hexanediol.

20. The method or composition of any one of claims 17-19, wherein the one or more polycarbonate polyols comprise the reaction product of at least:

(a) one or more alkane diols having 2 to 50 carbon atoms with a number average molecular weight between 500 and 3,000; and

(b) at least one carbonate compound.

21 . The method of any one of claims 17-20, wherein the one or more alkane diols is selected from 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexandiol, 1 ,7- heptanediol, 1 ,2-dodecanediol, cyclohexanedimethanol, 3-methyl-1 ,5-pentanediol,

2,4-diethyl-1 ,5-pentanediol, bis(2-hydroxyethyl)ether, bis(6-hydroxyhexyl)ether, dimer diols, short-chain C₂, C3 or C₄ polyether diols having a number average molecular weight of less than 700 g/mol, or combinations thereof.

22. The method of any one of claims 17-21 , wherein the at least one carbonate compound is selected from alkylene carbonates, diaryl carbonates, dialkyl carbonates, dioxolanones, hexanediol bis-chlorocarbonates, phosgene, urea, or combinations thereof.

23. An article comprising the crosslinkable silane-terminated polymer of any one of claims 3-22.

24. The article of claim 23 wherein the article is an elastomer, a sealant, an adhesive, a coating or a combination thereof.