Terminally unsaturated polyesters with C-O-Si bonds

Abstract

A composition contains an organosilyl-functional polyester, wherein the organosilyl-functional polyester is characterized by having a plurality of terminal carbon-carbon double bonds bonded to the polyester by carbon-oxygen-silicon bonds.

Description

Technical Field

[0001] The present invention relates to polyesters having terminal unsaturated groups and carbon-oxygen-silicon bonds, which can be used to prepare elastomer gels.

[0002] introduction

[0003] Compounds containing terminal unsaturated groups can be used to prepare polymers, such as elastomers. Elastomers are cross-linked polymers comprising a backbone polymer that is typically cross-linked to one another via a cross-linking polymer. Elastomers are typically prepared using a reaction mixture of the backbone polymer and a cross-linking agent in a solvent. Different applications benefit from using either an aqueous solvent or a reaction mixture using a non-aqueous solvent. Typically, reactants that are soluble in an aqueous solvent are insoluble in a non-aqueous solvent, and vice versa. In some applications, it is desirable to prepare elastomers in a non-aqueous solvent, and in some cases, solvent-swellable elastomers are prepared in a non-polar solvent.

[0004] One application where elastomers prepared in non-aqueous or even non-polar solvents are desirable is in the preparation of elastomer gels or pastes, which are sensory modifiers for personal care and cosmetic applications. The elastomers of such pastes typically comprise a polysiloxane backbone polymer that is cross-linked with a polysiloxane cross-linker to form a silicone elastomer. These are well-known sensory modifiers used to achieve a smooth, powdery, and dry sensory feel.

[0005] In the present invention, elastomer is prepared from the main chain polymer and has the terminal unsaturated reactive group that is connected to the main chain polymer by the key that is lower than the COC key of hydrolytic stability and cross-linking agent.It will advance the elastomer field, particularly can be used for preparing those elastomers of sensory organ regulation paste, and this elastomer comprises the key that hydrolytic stability is lower than the COC key.If elastomer contains the littler key of hydrolytic stability, then it is easier to decompose (degraded), makes it more environmentally friendly.Expectedly, the lower key of hydrolytic stability is between main chain and cross-linking agent, makes degraded destruction cross-linked.A kind of mode realizing this point is to prepare elastomer from main chain polymer, and this main chain polymer has the terminal unsaturated reactive group that is connected to main chain polymer by the key that hydrolytic stability is lower than the COC key.

[0006] Elastomer technology would benefit from the identification of backbone polymers that do not contain siloxane Si-O-Si linkages, contain terminal unsaturated groups attached to the backbone polymer via linkages that are less hydrolytically stable than C-O-C linkages, and are soluble in non-aqueous solvents to promote crosslinking in the presence of non-aqueous solvents to prepare solvent-swellable elastomers. Summary of the Invention

[0007] The present invention solves the problem of providing a backbone polymer free of siloxane Si-O-Si bonds, containing terminal unsaturated groups connected to the backbone polymer via bonds having lower hydrolytic stability than C-O-C bonds, and being soluble in non-aqueous solvents to promote crosslinking in the presence of non-aqueous solvents, thereby preparing solvent-swollen elastomers.

[0008] The present invention is the result of the discovery that polyester polyols can be functionalized with terminal unsaturated carbon-carbon bonds (C=C) through carbon-oxygen-silicon bonds (CO-Si) to provide organosilyl-functional polyester materials that are soluble in non-aqueous solvents, even non-polar solvents. CO-Si bonds are less hydrolytically stable than COC bonds.

[0009] In a first aspect, the present invention is a composition comprising an organosilyl-functional polyester, wherein the organosilyl-functional polyester is characterized by having a plurality of terminal carbon-carbon double bonds bonded to the polyester via carbon-oxygen-silicon bonds.

[0010] In a second aspect, the present invention is a method for preparing the composition of the first aspect, 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 a silylation catalyst, to silylate the polyester polyol to form the organosilyl-functional polyester.

[0011] The compositions of the invention are suitable for preparing elastomers by crosslinking with crosslinking agents which react with C=C bonds. DETAILED DESCRIPTION

[0012] When a test method number is not used to indicate a date, the test method refers to the most current test method as of the priority date of this document. Reference to a test method includes reference to both the testing association and the test method number. The following test method abbreviations and designations apply herein: ASTM refers to ASTM International methods; EN refers to European standards; DIN refers to the German Institute for Standardization; ISO refers to the International Organization for Standardization; and UL refers to Underwriters Laboratories.

[0013] Products identified by their trade names refer to compositions available under those trade names on the priority date of this document.

[0014] "A plurality of" means two or more. "And / or" means "and, or as an alternative." Unless otherwise indicated, all ranges are inclusive.

[0015] "Polyester" refers to a polymer containing multiple ester linkages.

[0016] "Organosilyl functional" refers to a group having at least one -SiR3 group, preferably a plurality of SiR3 groups, wherein each R is independently selected from a hydrocarbyl group, including an alkyl group, an alkenyl group, and an aryl group.

[0017] "Molecular weight," "MW," and "Mw" are interchangeable 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 refractometer. Two (300 mm x 7.5 mm) Polymer Laboratories PLgel 5 micron Mixed-C columns (molecular weight separation range of 200 to 2,000,000) were used, preceded by a PLgel 5 micron guard column (50 mm x 7.5 mm). Certified grade tetrahydrofuran (THF) flowing at 1.0 ml / min was used as the eluent while the column and detector were maintained at 35°C. Samples were prepared in THF at a concentration of approximately 0.15% by volume and allowed to solvate for two hours with occasional shaking, then filtered through a 0.45 micron polytetrafluoroethylene syringe filter prior to analysis. 100 microliters of sample were injected for analysis, and data were then collected for 30 minutes. Data were collected and analyzed using ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software.Molecular weight averages are relative to a calibration curve (third order) created using polystyrene standards covering the molecular weight range of 580 to 2,750,000.

[0018] The present invention includes a composition comprising an organosilyl-functional polyester. The composition may be solely an organosilyl-functional polyester or may comprise other components in addition to the organosilyl-functional polyester. The organosilyl-functional polyester is characterized in that it has multiple terminal carbon-carbon double bonds that are bound to the polyester via carbon-oxygen-silicon (CO-Si) bonds. The CO-Si bond may be directly attached to the ester group, and even include the carbon of the ester group, or may be indirectly attached to the ester group via another linking group such as a divalent hydrocarbon chain. The organosilyl-functional polyester may have a CO-Si bond with a terminal carbon-carbon 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 may be linear or branched. The organosilyl-functional polyester may be one organosilyl-functional polyester or a combination of more than one organosilyl-functional polyesters.

[0019] Examples of suitable organosilyl-functional polyesters include any one or any combination of more than one of the organosilyl-functional polyesters having the average chemical structure (I), (II), or (III):

[0020] CH2=CH-SiR2O-[(CH2) m OC(O)CH2(CH2) n CH2C(O)O-]o (CH2) m -OSiR2-CH=CH2 (I)

[0021] C(R)[CH2OX]3 (II)

[0022] CH3CH(OX)CH2CH2OX (III) wherein:

[0023] R is independently selected from the alkyl group with one to 8 carbon atom when occurring at every turn, and can be all identical or can be different from each other.The alkyl group can have one or more, two or more, three or more, four or more, 5 or more, 6 or more, even 7 or more carbon atoms, and contains 8 or still less and can contain 7 or still less, 6 or still less, 5 or still less, 4 or still less, 3 or still less, even 2 or still less carbon atoms usually simultaneously.Expectedly, the R group is selected from the group consisting of methyl, ethyl, propyl group and phenyl group.

[0024] X is independently selected at each occurrence from -H, -C(O)-(CH2)4C(O)OH, and -C(O)-(CH2)4C(O)OSiR2-CH=CH2, wherein R is as described above, provided that at least two X groups are -C(O)-(CH2)4C(O)OSiR2-CH=CH2 groups.

[0025] The subscript m independently at each occurrence has an average value ranging from 1 to 8, and preferably has a value of 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 is 2 at each occurrence.

[0026] The subscript n has an average value ranging from 2 to 5. The subscript n can have a value of 2 or greater, 3 or greater, 4 or greater, 5 or greater, 10 or greater, 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, or even 40 or greater, while typically having a value of 50 or less, 45 or less, 40 or less, 35 or less, 31 or less, 25 or less, 20 or less, 10 or less, or even 5 or less.

[0027] Subscript o has an average value ranging from 2 to 10. Subscript o can have a value of 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, 7 or greater, 8 or greater, or even 9 or greater, while typically having a value of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less.

[0028] The organosilyl-functional polyester desirably has an Mw in the range of 1000 to 5000 grams per mole (g / mol), preferably 1200 to 2500, and can be in the range of 1400 to 2300.

[0029] In addition to the organosilyl-functional polyester, the composition of the present invention may be free of or may include any one or any combination of one or more components. For example, the composition may be free of or include any one or any combination of more than one of the following components: a solvent, a hydrosilyl-functional polysiloxane, and a hydrosilylation catalyst.

[0030] The compositions of the present invention may include a solvent. Typically, the solvent is a non-aqueous solvent. The non-aqueous solvent contains less than one weight percent water based on the weight of the solvent and may be free of water. Desirably, the solvent is non-polar.

[0031] The solvent may be, for example, any one or any combination of fluids selected from the group consisting of hydrocarbons, ethers, esters, alcohols, and silicone fluids. Examples of suitable hydrocarbon fluids include farnesane, squalane, hemi-squalane, isohexadecane, undecane, tridecane, and isododecane. Examples of suitable ether fluids include those sold under the name CETIOL TM OE (CETIOL is a trademark of Cognis IP Management GMBH) is available from BASF, including materials sold by BASF, ethyl 3-(2,4-dimethyl-1,3-dioxolan-2-yl) propionate, ethyl glyceryl acetal levulinate, ethylphenethyl acetal, and isopropylglyceryl 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 trioctanoate, trimethylolpropane tricaprate, dipentaerythritol hexa-C5-9 ester, C12-15 alkyl benzoate, triisooctano ... Examples of suitable silicone fluids include 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 dicaprate, coco-caprylate, coco-caprate, ethylhexyl cocoate, oleyl erucate, propylheptyl caprylate, decyl oleate, hexyldecyl stearate, and propylene glycol laurate. Examples of suitable silicone fluids include cyclic siloxanes such as cyclotetrasiloxane, such as DOWSIL TM244 fluid (DOWSIL is a trademark of The Dow Chemical Company); cyclopentasiloxane, such as DOWSIL TM 245 fluid available; or cyclohexasiloxane, such as DOWSIL TM 246 fluid available; linear and branched alkyl and aryl siloxanes, such as caprylyl methicone, such as DOWSIL TM FZ-3196 available; and linear dimethyl siloxanes, such as DOWSIL TM 200 fluid available; and phenyl trimethicone, such as DOWSIL TM 556 fluids available.

[0032] The solvent may be a "high volatility" solvent selected from the group consisting of 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 having a higher washing durability than pastes made from conventional pure silicone elastomers.

[0033] In addition to the organosilyl-functional polyester, the composition of the present invention may include a SiH-functional polysiloxane. The SiH-functional polysiloxane contains two or more hydrosilyl (SiH) functional groups. The SiH functional groups can undergo hydrosilylation to add 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 one or more terminal SiH groups without pendent SiH groups, one or more pendent SiH groups without terminal SiH groups, or a combination of one or more terminal SiH groups and one or more pendent SiH groups.

[0034] Desirably, the SiH functional polysiloxane is linear and is one compound or any combination of more than one compounds selected from those having the following average chemical formula:

[0035] (R'3SiO 1 / 2 )2(R'2SiO 2 / 2 ) b

[0036] in:

[0037] R' is independently selected at each occurrence from the group consisting of hydrogen and R groups, wherein R is as described above, with the proviso that at least two R' groups are hydrogen;

[0038] Subscript b is the number of (R'2SiO 2 / 2 ) groups 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 at the same time typically is 120 or less, or even 100 or less and can be 70 or less, 50 or less, 30 or less, 20 or less, 15 or less, or even 10 or less.

[0039] Examples of suitable hydrosilyl-functional polysiloxanes include those having the following average molecular formula:

[0040] (H(CH3)2SiO 1 / 2 )2((CH3)SiO 2 / 2 ) 20 ,

[0041] ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 25 (H(CH3)SiO 2 / 2 )6,

[0042] ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 92 (H(CH3)SiO 2 / 2 )6, and

[0043] ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 3.3 (H(CH3)SiO 2 / 2 )6.

[0044] When present, the hydrosilyl-functional polysiloxane is desirably present in a concentration sufficient to provide a molar ratio of SiH groups from the hydrosilyl-functional polysiloxane to C=C 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.

[0045] The composition may comprise a hydrosilylation catalyst. Typically, the hydrosilylation catalyst is any one or any combination of more than one 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), H2PtCl6, di-μ.-carbonyldi-.π.-cyclopentadienyldinickerel, 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, bis(ethyl acetoacetate) platinum, bis(acetylacetonate) platinum, 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 comprising a platinum complex with a low molecular weight organopolysiloxane, including a platinum complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. These complexes can be microencapsulated in a resin matrix. The catalyst can be a platinum complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0046] The concentration of the platinum-based hydrosilylation catalyst is typically 5 million parts by weight (ppm) 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. It is typically 500 ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, and 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.

[0047] The present invention includes a method for preparing the organosilyl-functional polyester of the present invention. The method 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 a silylation catalyst, to silylate the polyester polyol, thereby forming the organosilyl-functional polyester.

[0048] Typically, it is desirable to react the vinyl functional silylating agent and the polyester polyol together (i.e., perform a silylation reaction) at 25 degrees Celsius (° C.) or higher, preferably 50° C. or higher, 75° C. or higher, 100° C. or higher, even 120° C. or higher, or 130° C. or higher, while typically mixing at a temperature of 200° C. or lower, preferably 175° C. or lower, 150° C. or lower, even 140° C. or lower, or 130° C. or lower. The reaction is carried out until silylation of the OH groups no longer occurs or a point is reached at which the reaction is desired to be stopped. Desirably, the silylation reaction continues until 80 to 100 mole percent of the OH groups on the polyester polyol are silylated, provided that there are multiple silylated OH groups per molecule. Nuclear magnetic resonance spectroscopy or Fourier transform infrared spectroscopy can be used to monitor the reaction mixture to determine the extent of OH silylation. When the reaction is complete, it is desirable to cool the reaction mixture to 23° C.

[0049] The vinyl functional silylating agent is desirably any one or more components selected from the group consisting of divinyldisilazane (e.g., 1,1,3,3,-tetraalkyl-1,3-divinyldisilazane), vinylchlorosilane, vinylalkoxysilane, divinylsilylamide, vinylsilylcarbamate, and vinylsilyl acetate. Typically, the concentration of the vinyl functional silylating agent is 1.5 to 4 moles per mole of polyester polyol.

[0050] The reaction of polyester polyol and vinyl functional silylating agent can be carried out under the presence or absence of silylation catalyst.Desirably, the reaction of polyester polyol and vinyl functional silylating agent is carried out under the presence of silylation catalyst.Suitable silylation catalyst comprises acid such as Lewis acid or alkali such as Lewis base.The example of suitable silylation catalyst comprises saccharin, imidazole, ammonium chloride, trifluoroacetic acid and ammonium sulfate.Usually, relative to the mole number of polyester polyol, silylation catalyst exists with following concentration: zero mole percent (mol%) or higher, preferably 0.001mol% or higher, and can be 0.005mol% or higher, and at the same time is usually 0.100mol% or lower, or even 0.050mol% or lower, 0.010mol% or lower, or even 0.005mol% or lower.

[0051] Polyester polyols are not limited to the broadest scope of the present invention. Desirably, examples of polyester polyols include any one or any combination of more than one polyester polyols having an average chemical structure selected from (IV), (V), and (VI):

[0052] HO-[(CH2) m OC(O)CH2(CH2)n CH2C(O)O-] o (CH2) m -OH (IV)

[0053] C(R)[CH2OH]3 (V)

[0054] CH3CH(OH)CH2CH2OH (VI) wherein:

[0055] R is independently selected from the alkyl group with one to 8 carbon atom when occurring at every turn, and can be all identical or can be different from each other.The alkyl group can have one or more, two or more, three or more, four or more, 5 or more, 6 or more, even 7 or more carbon atoms, and contains 8 or still less and can contain 7 or still less, 6 or still less, 5 or still less, 4 or still less, 3 or still less, even 2 or still less carbon atoms usually simultaneously.Expectedly, the R group is selected from the group consisting of methyl, ethyl, propyl group and phenyl group.

[0056] The subscript m independently at each occurrence has an average value ranging from 1 to 8, and preferably has a value of 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 is 2 at each occurrence.

[0057] The subscript n has an average value ranging from 2 to 5. The subscript n can have a value of 2 or greater, 3 or greater, 4 or greater, 5 or greater, 10 or greater, 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, or even 40 or greater, while typically having a value of 50 or less, 45 or less, 40 or less, 35 or less, 31 or less, 25 or less, 20 or less, 10 or less, or even 5 or less.

[0058] Subscript o has an average value ranging from 2 to 10. Subscript o can have a value of 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, 7 or greater, 8 or greater, or even 9 or greater, while typically having a value of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less.

[0059] Example

[0060] Table 1 lists the components used to prepare the following examples.

[0061] Table 1

[0062]

[0063] PRIPLAST is a trademark of Croda International PLC. DESMOPHEN is a trademark of Covestro Intellectual Property GMBH.

[0064] Preparation of Organosilyl Functional Polyesters

[0065] Table 2 provides the concentrations (in grams) of the polyester polyol, catalyst, and vinyl-functional silylating agent used to prepare each organosilyl-functional polyester, as well as the reaction time (in hours) and reaction temperature (° C.) for each of Examples 1 to 3. Additionally, Table 2 lists the average mole percent OH substitution (silylation) relative to the moles of OH in the polyester polyol, the weight percent of vinyl groups per molecule based on the weight of the organosilyl-functional polyester, and the average number of vinyl groups per organosilyl-functional polyester molecule.

[0066] Table 2

[0067]

[0068] Polyester polyol, vinyl functional silylating agent and catalyst are added to a 500 milliliter (mL) round-bottom flask. Add a polytetrafluoroethylene stirring rod, and purge the flask and contents with nitrogen, seal with a septum. Use a hot plate to heat the contents to the reaction temperature while stirring the reaction time. Make the mixture cool to 23 ℃, and remove residual vinyl functional silylating agent under vacuum (1.3 kPa) and 130 ℃ for 2 hours, to obtain the gained organosilyl functional polyester.

[0069] Through protons ( 1 H) Characterization of the obtained organosilyl-functional polyester by nuclear magnetic resonance (NMR) spectroscopy. A 10 mg sample of the organosilyl-functional polyester was dissolved in 0.6 mL of deuterated benzene (d6-benzene) and the NMR spectrum was obtained using a 400 MHz Varian 1HNMR spectrometer analysis. A 5 second acquisition time and a 15 second relaxation delay time were used. 16 scans were collected and averaged to obtain the resulting spectrum. The resulting spectrum was referenced to benzene at δ7.16 ppm. The regions of interest in the spectrum are: the vinyl region ("V") integrated from δ5.6-6.5 ppm; the methylene region adjacent to the hydroxyl group ("O") integrated at δ4.2-4.3 ppm to determine hydroxyl substitution. δ2.1-2.3 ppm describes the methylene region adjacent to the ester region ("E") and the methyl region at δ0.15-0.3 ppm describes silanization ("S"). The integrals were set based on the number of repeat units along the polyester polymer backbone: for polyester 1, region "E" was normalized to 16; for polyester 2, region "E" was normalized to 30; and for polyester 3, region "E" was normalized to 24. The mol% OH substitution was calculated as the integral of the region corresponding to "V" divided by the theoretical vinyl integral based on OH for each polyester polyol. The theoretical vinyl integral for polyester 1 and polyester 2 is 6, and for polyester 3 is 16.5. The following calculation is used:

[0070] Mol% OH substitution = [(V) / (OH per polyester polymer)*3]*100%

[0071] Wt% Vinyl = [Molecular weight of vinyl groups] * [mol% OH substitution] / [MW / OH of polyester], where MW / OH is 1000 for polyester 1 and polyester 2, and 260 for polyester 3.

[0072] Vinyl groups per polyester = [Mol % OH substitution] * [OH per polyester], where for polyester 1 and polyester 2 the OH per polyester is 2, and for polyester 3 the OH per polyester is 5.5.

[0073] Example 1 has an average chemical structure:

[0074] CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 31 CH2C(O)O-] 3.9 (CH2)2OSi(CH3)2-

[0075] CH=CH2

[0076] Example 2 has an average chemical structure:

[0077] CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 13 CH2C(O)O-] 7.5 (CH2)2OSi(CH3)2-

[0078] CH=CH2

[0079] Example 3 may have a combination of structures, but is intended to include materials having the following average chemical structure:

[0080]

[0081] Compositions having organosilyl-functional polyesters and other components

[0082] The organosilyl-functional polyester can be combined with a solvent, a SiH-functional polysiloxane having an average of at least two SiH functional groups per molecule, and a hydrosilylation catalyst to prepare a reaction mixture for preparing the elastomer. The organosilyl-functional polyester and SiH-functional polysiloxane can be soluble in the solvent.

Claims

1. A composition comprising an organosilyl-functional polyester, wherein the organosilyl-functional polyester is characterized by having a plurality of terminal carbon-carbon double bonds bonded to the polyester via carbon-oxygen-silicon bonds.

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, wherein the organosilyl-functional polyester has an average chemical structure of (I), (II) or (II): 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) wherein: R at each occurrence is independently selected from a hydrocarbyl group having from one to 8 carbon atoms; X is independently selected at each occurrence from -H, -C(O)-(CH2)4C(O)OH, and -C(O)-(CH2)4C(O)OSiR2-CH=CH2, wherein R is as described above, provided that at least two X groups are -C(O)-(CH2)4C(O)OSiR2-CH=CH2 groups; The subscript m, at each occurrence, independently has a mean value ranging from 1 to 8, The subscript n has an average value in the range of 2 to 50; and The subscript o has an average value ranging from 2 to 10.

4. A composition according to any preceding claim, wherein the organosilyl functional polyester has an average weight average molecular weight in the range of 1000 g / mol to 5000 g / mol.

5. A composition according to any preceding claim comprising the organosilyl-functional polyester in combination with a SiH-functional polysiloxane comprising at least two SiH functional groups.

6. The composition of claim 5, 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 method for preparing a composition according to claim 1, comprising the step of preparing an organosilyl-functional polyester by providing a polyester polyol, a vinyl-functional silylating agent and an optional 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 to form the organosilyl-functional polyester.

8. The method of claim 7, wherein the vinyl functional silylating agent is 1,1,3,3,-tetraalkyl-1,3-divinyldisilazane and saccharin is present as a catalyst.

9. The method according to claim 7 or claim 8, wherein the polyester polyol is selected from polyester polyols having an average chemical structure (IV), (V) or (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)where: R at each occurrence is independently selected from a hydrocarbyl group having from one to 8 carbon atoms; The subscript m, independently at each occurrence, has a mean value ranging from one to eight; The subscript n has an average value ranging from 2 to 5; and The subscript o has an average value ranging from 2 to 10.

10. The method of claim 7, 8 or 9, wherein there is sufficient vinyl functional silylating agent to silylate 80 to 100 mole percent of the hydroxyl groups on the polyester polyol, and 80 to 100 mole percent of the polyester polyol hydroxyl groups are silylated.

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