Terminally unsaturated polyesters with CO-Si bonds

Abstract

The composition contains an organosilyl-functional polyester characterized in that the organosilyl-functional polyester has a plurality of terminal carbon-carbon double bonds attached to the polyester through carbon-oxygen-silicon bonds.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to polyesters having terminal unsaturated groups and carbon-oxygen-silicon bonds, which are useful for making elastomeric gels.

[0002] (Introduction) Compounds containing terminal unsaturated groups are useful for preparing polymers such as elastomers. Elastomers are crosslinked polymers, often containing backbone polymers crosslinked to one another via crosslinking polymers. It is common to prepare elastomers using a reaction mixture containing the backbone polymer and a crosslinker in a solvent. Different applications benefit from reaction mixtures that utilize either aqueous or non-aqueous solvents. Generally, reactants that are soluble in aqueous solvents are not soluble in non-aqueous solvents, and vice versa. There are applications where it is desirable to prepare elastomers in non-aqueous solvents, and in some cases, it is desirable to prepare elastomers in non-polar solvents to prepare solvent-swollen elastomers.

[0003] One application where it is desirable to prepare elastomers in non-aqueous, or even non-polar, solvents is in preparing elastomer gels or pastes that are sensory modifiers for personal care and cosmetic applications. The elastomers in such pastes typically comprise polysiloxane backbone polymers crosslinked with polysiloxane crosslinkers to form siloxane elastomers. These are well-known sensory modifiers for achieving a smooth, powdery, and dry sensory feel.

[0004] The present invention advances elastomers containing linkages less hydrolytically stable than COC linkages, particularly those useful for preparing sensory-modifying pastes. When an elastomer contains less hydrolytically stable linkages, it breaks (degrades) more easily, making it more environmentally friendly. Desirably, the less hydrolytically stable linkages are between the backbone and the crosslinking agent, so that degradation disrupts the crosslinks. One way to achieve this is to prepare an elastomer from a backbone polymer with terminal unsaturated reactive groups attached to the backbone polymer through linkages less hydrolytically stable than COC linkages.

[0005] The elastomer technology would benefit from identifying backbone polymers that are free of siloxane Si-O-Si bonds, contain terminal unsaturated groups attached to the backbone polymer through bonds that are less hydrolytically stable than C-O-C bonds, and are soluble in non-aqueous solvents to promote crosslinking in the presence of non-aqueous solvents to create solvent-swollen elastomers. Summary of the Invention

[0006] The present invention solves the problem of providing a backbone polymer that is free of siloxane Si-O-Si bonds, contains terminal unsaturated groups attached to the backbone polymer through bonds that are less hydrolytically stable than C-O-C bonds, and is soluble in non-aqueous solvents to promote crosslinking in the presence of the non-aqueous solvent to produce a solvent-swollen elastomer.

[0007] The present invention is a result of the discovery that polyester polyols can be functionalized with terminally unsaturated carbon-carbon bonds (C=C) via carbon-oxygen-silicon linkages (CO-Si) to provide organosilyl-functional polyester materials that are soluble in non-aqueous, even non-polar, solvents. The CO-Si bond is less hydrolytically stable than the CO-C bond.

[0008] In a first aspect, the invention is a composition comprising an organosilyl-functional polyester, the organosilyl-functional polyester characterized in that it has a plurality of terminal carbon-carbon double bonds attached to the polyester through carbon-oxygen-silicon bonds.

[0009] In a second aspect, the invention is a process for preparing the composition of the first aspect, the process comprising the steps of preparing an organosilyl-functional polyester by providing a polyester polyol, a vinyl-functional silylating agent, and optionally a silylation catalyst, and then reacting the vinyl-functional silylating agent and the polyester polyol together, optionally in the presence of the silylation catalyst, to silylate the polyester polyol and form the organosilyl-functional polyester.

[0010] The compositions of the present invention are suitable for use in making elastomers by crosslinking with crosslinking agents that react with C=C bonds. DETAILED DESCRIPTION OF THE INVENTION

[0011] Test methods, unless a date is given with the test method number, refer to the test method most recent as of the priority date of this document. Reference to a test method includes both a reference to the testing society and the test method number. The following test method abbreviations and identifiers apply herein: ASTM refers to American Society for Testing and Materials test methods, EN refers to European Norm, DIN refers to Deutsches Institut fur Normung, ISO refers to International Organization for Standards, and UL refers to Underwriters Laboratory.

[0012] Products identified by trade names refer to compositions available under those trade names as of the priority date of this document.

[0013] "Plurality" means two or more. "And / or" means "and, or alternatively." All ranges are inclusive of the endpoints unless otherwise indicated.

[0014] "Polyester" refers to a polymer containing multiple ester linkages.

[0015] "Organosilyl-functional" refers to having at least one -SiR group, preferably multiple -SiR groups, where each R is independently selected from hydrocarbyl groups, including alkyl groups, alkenyl groups, and aryl groups.

[0016] "Molecular weight," "MW," and "Mw" are used interchangeably and refer to the weight-average molecular weight of a polymer. Molecular weights were determined using gel permeation chromatography using a Waters 2695 Separation Module with a vacuum degasser and a Waters 2410 differential refractive index detector. Two (300 mm x 7.5 mm) Polymer Laboratories PLgel 5-micrometer Mixed-C columns (molecular weight separation range 200-2,000,000) were used, preceded by PLgel 5-micrometer guard columns (50 mm x 7.5 mm). The eluent was tetrahydrofuran (THF) flowing at 1.0 ml / min, with the columns and detector maintained at 35°C. Samples were prepared in THF at approximately 0.15 volume percent, solvated for 2 hours with occasional shaking, and filtered through 0.45-micrometer polytetrafluoroethylene syringe filters before analysis. A 100 microliter sample is injected for analysis, and data is collected for 30 minutes. ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software are used to collect data and perform the analysis. Molecular weight averages are measured against a calibration curve (third order) generated using polystyrene standards spanning the molecular weight range of 580 to 2,750,000.

[0017] The present invention includes compositions containing organosilyl-functional polyesters. The compositions can be solely organosilyl-functional polyesters, or can include other components in addition to the organosilyl-functional polyesters. Organosilyl-functional polyesters are characterized by having multiple terminal carbon-carbon double bonds attached to the polyester via carbon-oxygen-silicon (CO-Si) bonds. The CO-Si bonds can be directly attached to the ester groups, can even include carbons in the ester groups, or can be indirectly attached to the ester groups via another linking group, such as a divalent hydrocarbyl chain. The organosilyl-functional polyesters can have CO-Si bonds with a terminal double bond (C=C group) attached to each ester group. The C=C group is desirably part of a vinyl or allyl group. The organosilyl-functional polyester can be linear or branched. The organosilyl-functional polyester can be one or a combination of two or more organosilyl-functional polyesters.

[0018] Examples of suitable organosilyl-functional polyesters include any one or any combination of two or more organosilyl-functional polyesters having average chemical structures (I), (II), or (III): CH2=CH-SiR2O-[(CH2) m OC(O)CH2(CH2) n CH2C(O)O-] o (CH2) m -OSiR2-CH=CH2(I) C(R)[CH2OX]3(II) CH3CH(OX)CH2CH2OX (III) During the ceremony, R, in each occurrence, is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms, and can all be the same or different from one another. The hydrocarbyl can have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or even 7 or more carbon atoms, while typically containing 8 or fewer carbon atoms, and can contain 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, or even 2 or fewer carbon atoms. Desirably, the R group is selected from the group consisting of methyl, ethyl, propyl, and phenyl groups. X is independently, at each occurrence, selected from -H, -C(O)-(CH2)4C(O)OH, and -C(O)-(CH2)4C(O)OSiR2-CH=CH2, and R is as defined above, except that at least two X groups are -C(O)-(CH2)4C(O)OSiR2-CH=CH2 groups. The subscript m independently in each occurrence has an average value in the range of 1 to 8, preferably 2 or greater, and can have a value of 3 or greater, 4 or greater, 5 or greater, 6 or greater, or even 7 or greater, while typically having a value of 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or even 2 or less. Desirably, the subscript m in each occurrence is 2. The subscript n has an average value in the range of 2 to 5. The subscript n can have a value of 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, or even 40 or more, but at the same time typically has a value of less than 50, less than 45, less than 40, less than 35, less than 31, less than 25, less than 20, less than 10, or even less than 5. The subscript o has an average value in the range of 2 to 10. The subscript o can have a value of 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or even 9 or more, but at the same time typically has a value of less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, or even less than 3.

[0019] The organosilyl functional polyesters desirably have a Mw in the range of 1000 to 5000 grams per mole (g / mol), preferably 1200 to 2500, and can range from 1400 to 2300.

[0020] The compositions of the present invention may include no, or any one or any combination of, one or more components in addition to the organosilyl-functional polyester. For example, the compositions may include no, or any one or any combination of two or more of the following components: a solvent, a silylhydride-functional polysiloxane, and a hydrosilylation catalyst.

[0021] The composition of the present invention can contain a solvent. Typically, the solvent is a non-aqueous solvent. A non-aqueous solvent contains less than 1 weight percent water based on the weight of the solvent, and can be free of water. The solvent is preferably non-polar.

[0022] The solvent can be any one or any combination of fluids selected from the group consisting of hydrocarbons, ethers, esters, alcohols, and siloxane fluids. Examples of suitable hydrocarbon fluids include farnesane, squalane, hemisqualane, isohexadecane, undecane, tridecane, and isododecane. Examples of suitable ether fluids include the material sold by BASF under the name CETIOL™ OE (CETIOL is a trademark of Cognis IP Management GMBH), ethyl 3-(2,4-dimethyl-1,3-dioxolan-2-yl)propanoate, ethyl glycerin acetal levulinate, ethyl phenethyl acetal, and isopropylidene glyceryl cocoate. Examples of suitable ester fluids include isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, ethyl acetate, capric triglyceride, caprylic triglyceride, triheptanoin, triisostearin, diisopropyl acetate, diisopropyl adipate, diisobutyl adipate, diethylhexyl adipate, n-propyl acetate, isobutyl acetate, n-butyl acetate, trimethylolpropane tricaprylate, trimethylolpropane tricaprate, dipentaerythrityl hexa C5-9 acid ester, C12-15 alkyl benzoate, triethylhexanoin, neopentyl glycol diheptanoate, diheptyl succinate, heptyl undecylenate, propylene glycol dibenzoate, dipropylene glycol dibenzoate, ethylhexyl palmitate, ethylhexyl stearate, isopropyl laurate, hexyl laurate, isopropyl myristate, isopropyl palmitate, n-butyl stearate, propylene glycol dicaprylate, propylene glycol dicarbonate, cococaprylate, cococaprate, ethylhexyl cocoate, oleyl erucate, propyl butyl caprylate, decyl oleate, hexyldecyl stearate, and propylene glycol laurate.Examples of suitable siloxane fluids include cyclic siloxanes, such as cyclotetrasiloxane available as DOWSIL™ 244 Fluid (DOWSIL is a registered trademark of The Dow Chemical Company), cyclopentasiloxane available as DOWSIL™ 245 Fluid, or cyclohexasiloxane available as DOWSIL™ 246 Fluid, linear and branched alkyl and aryl siloxanes, such as caprylmethicone available as DOWSIL™ FZ-3196, and linear dimethyl siloxanes, such as linear dimethyl siloxane available as DOWSIL™ 200 Fluids, and phenyl trimethicone available as DOWSIL™ 556 Fluid.

[0023] The solvent can be a "highly volatile" solvent selected from isododecane (boiling point 210°C at 101 MPa), farnesane (boiling point 252°C at 101 MPa), undecane (boiling point 195°C at 101 MPa), n-dodecane (boiling point 216°C at 101 MPa), and tridecane (boiling point 234°C at 101 MPa). These solvents form gels that can be converted into pastes with higher wash durability than pastes made from typical pure silicone elastomers.

[0024] The compositions of the present invention can include an SiH-functional polysiloxane in addition to the organosilyl-functional polyester. The SiH-functional polysiloxane contains two or more silylhydride (SiH) functional groups. The SiH-functional groups can undergo hydrosilylation addition to the terminal C=C bonds of the organosilyl-functional polyester to form a crosslinked polymer, preferably a crosslinked elastomeric material. The SiH-functional polysiloxane can be branched or linear, but is preferably linear. The SiH-functional polysiloxane can have zero pendant SiH groups and one or more terminal SiH groups, zero terminal SiH groups and one or more pendant SiH groups, or a combination of one or more terminal SiH groups and one or more pendant SiH groups.

[0025] Desirably, the SiH-functional polysiloxane is linear and is one or any combination of two or more compounds selected from those having the following average chemical formula: (R'3SiO 1 / 2 )2(R'2SiO 2 / 2 ) b During the ceremony, R' is independently, at each occurrence, selected from the group consisting of hydrogen and R groups, where R is as defined above, with the proviso that at least two R' groups are hydrogen; The subscript b represents the (R'SiO 2 / 2 ) and typically has a value of 5 or more, and can be 10 or more, 15 or more, 20 or more, 30 or more, 50 or more, 70 or more, or even 90 or more, while typically being less than 120, or even less than 100, and can be less than 70, less than 50, less than 30, less than 20, less than 15, or even less than 10.

[0026] Examples of suitable silylhydride-functional polysiloxanes include those having the following average molecular formula: (H(CH3)2SiO 1 / 2 )2((CH3)SiO 2 / 2 ) 20, ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 25 (H(CH3)SiO 2 / 2 )6, ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 92 (H(CH3)SiO 2 / 2 )6, and ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 3.3 (H(CH3)SiO 2 / 2 )6.

[0027] The silylhydride-functional polysiloxane, when present, is desirably present in a concentration sufficient to provide a molar ratio of SiH groups from the silylhydride-functional polysiloxane to C=C groups from the organosilyl-functional polyester (SiH:C=C molar ratio) of 0.70 or greater, preferably 0.90 or greater, while typically 1.5 or less, preferably 1.0 or less, and more preferably 0.95 or less.

[0028] The composition can include a hydrosilylation catalyst. Typically, the hydrosilylation catalyst is any one or any combination of two or more platinum-based hydrosilylation catalysts. Platinum-based hydrosilylation catalysts include compounds and complexes such as platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst), HPtCl, di-μ-carbonyldi-π-cyclopentadienyldinickel, platinum-carbonyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum cyclovinylmethylsiloxane complexes, platinum acetylacetonate (acac), platinum black, platinum compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum dichloride, and complexes of platinum compounds with olefins or low molecular weight organopolysiloxanes, or platinum compounds microencapsulated in a matrix or core-shell structure. The hydrosilylation catalyst can be part of a solution containing a complex of platinum with a low molecular weight organopolysiloxane, including a platinum complex with 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. These complexes can be microencapsulated in a resin matrix. The catalyst can be a platinum complex with 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.

[0029] The concentration of the platinum-based hydrosilylation catalyst is typically 5 parts per million (ppm) by weight or more, preferably 10 ppm or more, and can be 25 ppm or more, 50 ppm or more, or even 75 ppm or more, based on the weight of the composition, while typically 500 ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, preferably 100 ppm or less, and can be 90 ppm or less, 80 ppm or less, 70 ppm or less, 60 ppm or less, or even 50 ppm or less.

[0030] The present invention includes a process for preparing the organosilyl-functional polyester of the present invention, which process includes the steps of preparing the organosilyl-functional polyester by providing a polyester polyol, a vinyl-functional silylating agent, and optionally a silylation catalyst, and then reacting the vinyl-functional silylating agent and the polyester polyol together, optionally in the presence of the silylation catalyst, to silylate the polyester polyol and form the organosilyl-functional polyester.

[0031] Generally, it is desirable to react (i.e., carry out the silylation reaction) the vinyl-functional silylating agent and the polyester polyol together at a temperature of 25 degrees Celsius (°C) or higher, preferably 50°C or higher, 75°C or higher, 100°C or higher, or even 120°C or higher, or 130°C or higher, while simultaneously mixing at a temperature typically below 200°C, preferably below 175°C, 150°C or lower, or even below 140°C, or below 130°C. The reaction proceeds until silylation of OH groups is no longer occurring or a desired point for stopping the reaction has been reached. Desirably, the silylation reaction continues until 80-100 mole percent of the OH groups on the polyester polyol are silylated, provided there are multiple silylated OH groups per molecule. Nuclear magnetic resonance spectroscopy or Fourier transform infrared spectroscopy is useful for monitoring the reaction mixture to determine the degree of OH silylation. When the reaction is complete, it is desirable to cool the reaction mixture to 23°C.

[0032] The vinyl-functional silylating agent is preferably any one or any combination of two or more components selected from divinyldisilazanes (such as 1,1,3,3-tetraalkyl-1,3-divinyldisilazanes), vinylchlorosilanes, vinylalkyoxysilanes, divinylsilylamides, vinylsilylcarbamates, and vinylsilyl acetates. Typically, the concentration of the vinyl-functional silylating agent is in the range of 1.5 to 4 moles per mole of polyester polyol.

[0033] The reaction between the polyester polyol and the vinyl-functional silylating agent can occur in the presence or absence of a silylation catalyst. Desirably, the reaction between the polyester polyol and the vinyl-functional silylating agent is carried out in the presence of a silylation catalyst. Suitable silylation catalysts include acids such as Lewis acids or bases such as Lewis bases. Examples of suitable catalysts include saccharin, imidazole, ammonium chloride, trifluoroacetic acid, and ammonium sulfate. Generally, the silylation catalyst is present in a concentration of zero mole percent (mol%) or more, preferably 0.001 mol% or more, relative to the moles of polyester polyol, and can be 0.005 mol% or more, but is typically 0.100 mol% or less, or even 0.050 mol% or less, 0.010 mol% or less, or even 0.005 mol% or less.

[0034] The polyester polyol is not limited in the broadest scope of the present invention. Examples of desirable polyester polyols include any one or any combination of two or more polyester polyols having an average chemical structure selected from (IV), (V), and (VI): HO-[(CH2) m OC(O)CH2(CH2) n CH2C(O)O-] o (CH2) m -OH (IV) C(R)[CH2OH]3(V) CH3CH(OH)CH2CH2OH (VI) During the ceremony, R, in each occurrence, is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms, and can all be the same or different from one another. The hydrocarbyl can have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or even 7 or more carbon atoms, while typically containing 8 or fewer carbon atoms, and can contain 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, or even 2 or fewer carbon atoms. Desirably, the R group is selected from the group consisting of methyl, ethyl, propyl, and phenyl groups. The subscript m independently in each occurrence has an average value in the range of 1 to 8, preferably 2 or greater, and can have a value of 3 or greater, 4 or greater, 5 or greater, 6 or greater, or even 7 or greater, while typically having a value of 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or even 2 or less. Desirably, the subscript m in each occurrence is 2. The subscript n has an average value in the range of 2 to 5. The subscript n can have a value of 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, or even 40 or more, but at the same time typically has a value of less than 50, less than 45, less than 40, less than 35, less than 31, less than 25, less than 20, less than 10, or even less than 5. The subscript o has an average value in the range of 2 to 10. The subscript o can have a value of 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or even 9 or more, but at the same time typically has a value of less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, or even less than 3. [Example]

[0035] Table 1 lists the components for preparing the following examples.

[0036] [Table 1] PRIPLAST is a trademark of Croda International PLC. DESMOPHEN is a trademark of Covestro Intellectual Property GMBH.

[0037] Preparation of organosilyl-functional polyesters Table 2 provides the concentrations in grams of polyester polyol, catalyst, and vinyl-functional silylating agent used to prepare each organosilyl-functional polyester, as well as the reaction time (hours) and reaction temperature (° C.) for each of Examples 1-3. In addition, Table 2 lists the average OH substitution mole percent (silylation) relative to the OH moles in the polyester polyol, the weight percent vinyl groups per molecule based on the organosilyl-functional polyester weight, and the average number of vinyl groups per organosilyl-functional polyester molecule.

[0038] [Table 2]

[0039] The polyester polyol, vinyl-functional silylating agent, and catalyst are added to a 500 milliliter (mL) round-bottom flask. A polytetrafluoroethylene stir bar is added, and the flask and contents are purged with nitrogen and sealed with a septum. The contents are heated to the reaction temperature using a heating plate while stirring for the reaction time. The mixture is cooled to 23°C, and residual vinyl-functional silylating agent is removed under vacuum (1.3 kilopascals) at 130°C for 2 hours to yield the resulting organosilyl-functional polyester.

[0040] The resulting organosilyl functional polyester is reacted with protons ( 1 H) Characterization by nuclear magnetic resonance (NMR) spectroscopy. A 10 milligram sample of organosilyl-functional polyester was dissolved in 0.6 milliliters of deuterated benzene (d6-benzene) and analyzed using a 400 megahertz Varian microscope. 1Analysis was performed using a H NMR spectrometer. A 5-second acquisition time and a 15-second relaxation delay were used. Sixteen scans were collected and averaged to obtain the resulting spectrum. The resulting spectrum was referenced to benzene at δ 7.16 ppm. The regions of interest in the spectrum were the vinyl region ("V"), integrated from δ 5.6-6.5 ppm; the methylene region adjacent to the hydroxyl ("O"), integrated over δ 4.2-4.3 ppm to determine hydroxyl substitution; the methylene region adjacent to the ester region ("E"), δ 2.1-2.3 ppm; and the methyl region at δ 0.15-0.3 ppm, which accounts for silylation ("S"). Integration was set based on the number of repeat units along the polyester polymer backbone; for polyester 1, the region "E" was normalized to 16; for polyester 2, the region "E" was normalized to 30; and for polyester 3, the region "E" was normalized to 24. Calculate the mole % OH substitution as the integral from the area corresponding to "V" divided by the theoretical vinyl integral based on OH per polyester polyol. The theoretical vinyl integral for polyesters 1 and 2 is 6, and for polyester 3 it is 16.5. Use the following calculation: OH substitution mole %=[(V) / (OH per polyester) × 3] × 100% Wt% vinyl = [molecular weight of vinyl group] x [mol% OH substitution] / [MW / OH of polyester], where MW / OH of polyesters 1 and 2 is 1000, and that of polyester 3 is 260. Vinyl groups per polyester = [mol % OH substitution] x [OH per polyester], where OH per polyester is 2 for polyesters 1 and 2 and 5.5 for polyester 3.

[0041] Example 1 has the following average chemical structure: CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 31 CH2C(O)O-] 3.9 (CH2)2OSi(CH3)2-CH=CH2 Example 2 has the following average chemical structure: CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 13 CH2C(O)O-] 7.5 (CH2)2OSi(CH3)2-CH=CH2

[0042] Example 3 is expected to include materials having the following average chemical structure, although it may have a combination of structures.

[0043] [ka]

[0044] Compositions having organosilyl-functionalized polyesters and other components The organosilyl-functionalized polyester can be prepared by combining a solvent, a SiH-functional polysiloxane containing an average of at least two SiH functional groups per molecule, and a hydrosilylation catalyst to form a reaction mixture for preparing the elastomer. The organosilyl-functionalized polyester and the SiH-functional polysiloxane can be soluble in the solvent. The present invention can provide the following aspects. [1] 1. A composition comprising an organosilyl-functional polyester, wherein the organosilyl-functional polyester has a plurality of terminal carbon-carbon double bonds attached to the polyester through carbon-oxygen-silicon bonds. [2] The composition according to [1] above, wherein the terminal carbon-carbon double bond is part of a vinyl group. [3] The organosilyl-functional polyester has an average chemical structure (I), (II), or (II): CH 2 =CH-SiR 2 O-[(CH 2 ) m OC(O)CH 2 (CH 2 ) n CH 2 C(O)O-] o (CH 2 ) m -OSiR 2 -CH=CH 2 (I) C(R)[CH 2 OX] 3 (II) CH 3 CH(OX)CH 2 CH 2 OX (III) wherein R is independently, in each occurrence, selected from hydrocarbyl groups having 1 to 8 carbon atoms; X is independently, at each occurrence, -H, -C(O)-(CH 2 ) 4 C(O)OH, and -C(O)-(CH 2 ) 4 C(O)OSiR 2 -CH=CH 2 and R is as defined above, with the proviso that at least two X groups are selected from -C(O)-(CH 2 ) 4 C(O)OSiR 2 -CH=CH 2 It is the basis, the subscript m, independently at each occurrence, has a mean value ranging from 1 to 8; the subscript n has an average value in the range of 2 to 50; The composition according to [1] above, wherein the subscript o has an average value in the range of 2 to 10. [4] The composition according to any one of the above [1] to [3], wherein the organosilyl-functional polyester has an average weight-average molecular weight in the range of 1000 to 5000 g / mol. [5] The composition according to any one of the above [1] to [4], wherein the composition comprises the organosilyl-functional polyester in combination with a SiH-functional polysiloxane containing at least two SiH functional groups. [6] The composition according to [5] above, further comprising a hydrosilylation catalyst and a solvent, wherein the organosilyl-functional polyester and SiH-functional polysiloxane are dissolved in the solvent to form a solution. [7] A process for preparing the composition described in [1] above, the process comprising the steps of: providing a polyester polyol, a vinyl-functional silylating agent, and optionally a silylation catalyst; and then reacting the vinyl-functional silylating agent and polyester polyol together, optionally in the presence of the silylation catalyst, to silylate the polyester polyol and form the organosilyl-functional polyester. [8] The process according to [7] above, wherein the vinyl-functional silylating agent is a 1,1,3,3-tetraalkyl-1,3-divinyldisilazane and saccharin is present as a catalyst. [9] The polyester polyol has an average chemical structure (IV), (V), or (VI): HO-[(CH 2 ) m OC(O)CH 2 (CH 2 ) n CH 2 C(O)O-] o (CH 2 ) m -OH (IV) C(R)[CH 2 OH] 3 (V) CH 3 CH(OH)CH 2 CH 2 OH (VI) and selected from polyester polyols having the formula: R is independently, in each occurrence, selected from hydrocarbyl groups having 1 to 8 carbon atoms; the subscript m has an average value in the range of 1 to 8; the subscript n has an average value in the range of 2 to 5; The process according to [7] or [8] above, wherein the subscript o has an average value in the range of 2 to 10.

[10]

[0023] The process of any one of [7] to [9] above, wherein sufficient vinyl-functional silylating agent is present to silylate 80 to 100 mole percent of the hydroxyl groups in the polyester polyol, resulting in 80 to 100 mole percent silylation of the polyester polyol hydroxyl groups.

Claims

1. 1. A composition comprising an organosilyl-functional polyester, the organosilyl-functional polyester being characterized in that the organosilyl-functional polyester has a plurality of terminal carbon-carbon double bonds attached to the polyester through carbon-oxygen-silicon bonds, the organosilyl-functional polyester having an average chemical structure (I), (II), or (III): CH ２ =CH-SiR ２ O-[(CH ２ ) ｍ OC(O)CH ２ (CH ２ ) ｎ CH ２ C(O)O-] ｏ (CH ２ ) ｍ -OSiR ２ -CH=CH ２ (I) ((2) [|) ２ ﯁] ３ (=) CH ３ CH(OX)CH ２ CH ２ OX (III) wherein R is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms; X is independently —H, —C(O)—(CH ２ ) ４ C(O)OH, and —C(O)—(CH ２ ) ４ C(O)OSiR ２ -CH=CH ２ and R is as defined above, with the proviso that at least two X groups are selected from -C(O)-(CH ２ ) ４ C(O)OSiR ２ -CH=CH ２ It is the basis, the subscript m independently has an average value ranging from 1 to 8; the subscript n has an average value in the range of 2 to 50; A composition wherein the subscript o has an average value in the range of 2 to 10.

2. The composition of claim 1, wherein the terminal carbon-carbon double bond is part of a vinyl group.

3. The composition of claim 1 or 2, wherein the organosilyl-functional polyester has a weight average molecular weight in the range of 1000 to 5000 g / mol.

4. 3. The composition of claim 1 or 2, wherein the composition comprises the organosilyl-functional polyester in combination with a SiH-functional polysiloxane containing at least two SiH functional groups.

5. 5. The composition of claim 4, further comprising a hydrosilylation catalyst and a solvent, wherein the organosilyl-functional polyester and SiH-functional polysiloxane are dissolved in the solvent to form a solution.

6. 10. A process for preparing the composition of claim 1, comprising the steps of preparing the organosilyl-functional polyester by providing a polyester polyol and a vinyl-functional silylating agent, and then reacting the vinyl-functional silylating agent and polyester polyol to silylate the polyester polyol to form the organosilyl-functional polyester, wherein the vinyl-functional silylating agent is 1,1,3,3-tetraalkyl-1,3-divinyldisilazane.

7. The polyester polyol has an average chemical structure (IV), (V), or (VI): HO-[CH] ２ ) ｍ OC(O)CH ２ (CH) ２ ) ｎ CH ２ C(O)(O-) ｏ (CH) ２ ) ｍ -OH (IV) C(R)[CH ２ OH] ３ (V) CH ３ CH(OH)CH ２ CH ２ OH (VI) and selected from polyester polyols having the formula: R is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms; the subscript m has an average value in the range of 1 to 8; the subscript n has an average value in the range of 2 to 5; 7. The process of claim 6, wherein the subscript o has an average value in the range of 2 to 10.

8. 8. The process of claim 6 or 7, wherein sufficient vinyl-functional silylating agent is present to silylate from 80 to 100 mole percent of the hydroxyl groups in the polyester polyol, resulting in 80 to 100 mole percent of the polyester polyol hydroxyl groups becoming silylated.

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