Elastomer with CO-Si bond between polyester main chain and crosslinking agent

Abstract

A composition containing an elastomer, wherein the elastomer has a polyester backbone crosslinked with a crosslinking agent and has a carbon-oxygen-silicon bond between the ester group and the crosslinking agent.

Description

[Technical Field]

[0001] The present invention relates to elastomers and gels and pastes comprising elastomers.

[0002] (Introduction) Polysiloxane elastomer materials are desirable in the cosmetics industry for thickening carrier fluids while imparting desirable sensory properties to cosmetics. Polysiloxane elastomers are crosslinked gel materials that thicken carrier fluids while imparting the smooth, dry, and fine feel desired in many cosmetic products. Polysiloxane elastomers comprise a polysiloxane backbone crosslinked by a polysiloxane crosslinker.

[0003] There is interest in identifying elastomeric materials that can provide similar sensory and thickening properties to polysiloxane elastomers, but that also have a higher organic content. Increasing the organic content can increase compatibility with non-aqueous solvents, which can be desirable to increase the versatility of formulations in which the elastomer is useful. In this regard, it is desirable to identify elastomers that have the thickening and sensory properties of polysiloxane elastomeric materials, but that include a siloxane-free backbone.

[0004] It is also desirable to increase the environmentally friendly properties of elastomers, for example, by reducing their hydrolytic stability so that they degrade more easily over time. Degradability, particularly between the backbone polymer and the crosslinker, can accelerate the degradation of the polymer over time.

[0005] Cosmetics rely on polysiloxane elastomers for their thickening and sensory properties and can further benefit from wash resistance so that they remain in place for a longer period of time when applied to the skin. One way to help increase the durability of cosmetics is to identify elastomeric gels that can be processed into pastes with desirable sensory properties and are wash-resistant (durable).

[0006] It is desirable to identify elastomers that provide similar thickening and sensory properties to polysiloxane elastomers, but have non-siloxane backbone polymers attached to a crosslinker through bonds that are less hydrolytically stable than carbon-oxygen-carbon (C-O-C) bonds, and that have durability to washing that is at least as good as or better than polysiloxane elastomers. Summary of the Invention

[0007] The present invention provides a solution to the problem of identifying elastomers that provide similar thickening and sensory properties to polysiloxane elastomers, but have a non-siloxane backbone polymer attached to a crosslinker through bonds that are less hydrolytically stable than carbon-oxygen-carbon (C-O-C) bonds, and that have durability to washing that is at least as good as, or better than, polysiloxane elastomers.

[0008] The present invention is the result of the discovery of a method for preparing elastomers having polyester backbones that are crosslinked through carbon-oxygen-silicon bonds (CO-Si), which are free of siloxane bonds and are less hydrolytically stable than C-O-C bonds, and which can result in elastomers with the desired properties described above.

[0009] In a first aspect, the invention is a composition comprising an elastomer, the elastomer having a polyester backbone crosslinked with a crosslinking agent, the elastomer being characterized by having a carbon-oxygen-silicon bond between the ester group and the crosslinking agent.

[0010] In a second aspect, the invention is a process for preparing the composition of any one of the preceding claims, the method comprising: (a) providing a backbone polymer having at least two terminal unsaturated carbon-carbon bonds separated from any polyester groups by a carbon-oxygen-silicon bond, and a crosslinker material containing a plurality of silyl hydride groups, wherein at least one of the backbone polymer or crosslinker material has an average unsaturated carbon-carbon bond functionality of 3 or greater and / or the crosslinker material has an average silyl hydride functionality of 3 or greater; and (b) crosslinking the backbone polymer with the crosslinker material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the backbone polymer and the silyl hydride groups of the crosslinker material to form an elastomer.

[0011] The elastomers of the present invention are useful as additives for cosmetics to achieve desired sensory properties for the cosmetic product, particularly to achieve a smooth, dry, fine feel while achieving durability with respect to wash resistance. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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, END refers to European Norm, DIN refers to Deutsches Institut fur Normung, ISO refers to International Organization for Standards, and UL refers to Underwriters Laboratory.

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

[0014] "Plurality" means two or more. "And / or" means "and, or alternatively." All ranges are inclusive of the endpoints unless otherwise indicated.

[0015] An "unsaturated carbon-carbon bond" can be a carbon-carbon triple bond, or preferably a carbon-carbon double bond (C=C).

[0016] In one aspect, the present invention is a composition comprising an elastomer. The composition can be an elastomer or a combination of components comprising an elastomer. Desirably, the composition is a solvent-swollen gel comprising an elastomer swollen with a solvent, typically a non-aqueous solvent (i.e., a solvent-swollen elastomer). The solvent-swollen elastomer can be in particulate form in a solvent, particularly a non-aqueous solvent, to form a paste. The paste can be formed by subjecting the solvent-swollen elastomer gel to shearing, typically in excess solvent, to break the elastomer gel into fine particles. The degree of shearing can determine the particle size of the elastomer gel in the paste. Typically, the finer the particle size, the smoother the resulting paste will feel, and therefore, a finer particle size is desirable for applications such as cosmetics that involve application to the skin.

[0017] The solvent is preferably a non-aqueous solvent and can be a non-polar solvent. The solvent can be, for example, 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, isohexadecane, undecane, tridecane, and isododecane. Examples of suitable ether fluids include materials 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.When the solvent contains siloxane fluid, it can also contain additional solvent.The solvent cannot also contain siloxane.

[0018] 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.

[0019] The concentration of solvent in the solvent-swollen elastomeric composition is desirably 25 weight percent (wt-%) or more, preferably 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, 75 wt% or more, or even 80 wt% or more, based on the combined weight of solvent and elastomer, while typically 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, 65 wt% or less, 60 wt% or less, 55 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, or 35 wt% or less.

[0020] Elastomers are crosslinked polymers that include backbone polymers ("backbones") interconnected to other backbone polymers through crosslinker polymers ("crosslinkers"). Desirably, each backbone polymer has at least three bonds with the crosslinker and / or each crosslinker has at least three bonds with the backbone polymer.

[0021] The backbone is a polyester, a molecule containing multiple polyester groups. The backbone polyester cannot contain siloxane (Si-O-Si) bonds between the ester groups. The elastomer may or may not contain a polysaccharide component.

[0022] The crosslinker is attached to the backbone via a linking group that contains or can be a carbon-oxygen-silicon (CO-Si) bond. The linking group is located between the ester group in the backbone and the crosslinker. The crosslinker is typically a polysiloxane, a molecule that contains multiple Si-O-Si bonds.

[0023] Desirably, the elastomer comprises a backbone free of Si-O-Si bonds and containing ester linkages, and a crosslinker containing Si-O-Si bonds. In such elastomers, the backbone is manifested as a moiety between ester groups free of Si-O-Si bonds, while the crosslinker is manifested as a moiety between C-O-Si bonds containing Si-O-Si bonds. Desirably, at least one C-O-Si bond exists between any polyester and any Si-O-Si bond in the elastomer.

[0024] The backbone component of the elastomer may comprise or consist of segments having any one or any combination of two or more of chemical structures (I), (II), and (III), where the dangling bonds indicated by "--" are attached to a crosslinker; -CH(CH3)-SiR2O-[(CH2) m OC(O)CH2(CH2) n CH2C(O)O-] o (CH2) m -OSiR2-CH(CH3)-- (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—CH2CH2—, where R is as defined above, except that at least two X groups are —C(O)—(CH2)4C(O)OSiR2—CH2CH2— 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.

[0025] The crosslinker segment of the elastomer may comprise or consist of any one or any combination of two or more of the following segments (IV) and (V), where "--" corresponds to the bond connecting the carbon atoms of the backbone and may correspond to the same bond shown as "--" in structures (I), (II) and (III): (--(CH3)2SiO 1 / 2 )2((CH3)SiO 2 / 2 ) b (IV) ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) c (--(CH3)SiO 2 / 2) d (V) During the ceremony, The subscript b represents the number of ((CH)SiO per crosslinker segment having structure (IV). 2 / 2 ) groups, typically having a value of 5 or more, and can have a value of 10 or more, 15 or more, or even 16 or more, while typically having a value of 30 or less, and can have a value of 25 or less, 20 or less, or even 17 or less, Subscript c represents the number of ((CH)SiO per crosslinker segment having structure (V). 2 / 2 ), which typically has a value of 2 or more, and can be 3 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, or even 90 or more, and at the same time is typically less than 100, and can be less than 95, less than 92, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 25, less than 20, less than 10, or even less than 5; The subscript d represents the number of (--(CH)SiO per crosslinker segment having structure (V). 2 / 2 ), typically has a value of 2 or more, and can be 3 or more, 4 or more, 5 or more, or even 6 or more, while typically has a value of 10 or less, and can be 9 or less, 8 or less, 7 or less, or even 6 or less.

[0026] In a second aspect, the present invention is a method for preparing the composition of the first aspect of the present invention. The method includes preparing the elastomer of the first aspect by (a) providing a backbone polymer having at least two terminal unsaturated carbon-carbon bonds separated from any polyester groups by a carbon-oxygen-silicon bond, and a crosslinker material containing a plurality of silyl hydride groups, wherein at least one of the backbone polymer or crosslinker material has an average unsaturated carbon-carbon bond functionality of 3 or greater, and / or the crosslinker material has an average silyl hydride functionality of 3 or greater; and (b) crosslinking the backbone polymer with the crosslinker material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the backbone polymer and the silyl hydride groups of the crosslinker material to form the elastomer. "Functional group" refers to the terminal unsaturated carbon-carbon bonds in the backbone polymer and the silyl hydride groups in the crosslinker material.

[0027] The backbone polymer is desirably an organosilyl-functional polyester containing at least two organosilyl-functional groups, each having at least one terminal unsaturated carbon-carbon bond. "Organosilyl-functional" refers to having at least one -SiR group, and preferably multiple -SiR groups, where each R is independently selected from hydrocarbyl groups, including alkyl, alkenyl, and aryl groups.

[0028] Examples of suitable organosilyl-functional polyesters include any one or any combination of two or more organosilyl-functional polyesters having average chemical structures (VI), (VII), or (VIII): CH2=CH-SiR2O-[(CH2) m OC(O)CH2(CH2) n CH2C(O)O-] o (CH2) m -OSiR2-CH=CH2(VI) C(R)[CH2OX]3(VII) CH3CH(OX)CH2CH2OX (VIII) 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.

[0029] The organosilyl-functional polyesters desirably have a Mw in the range of 1000 to 5000 grams per mole (g / mol), preferably in the range of 1200 to 2500, and can range from 1400 to 2300. Molecular weights for the organosilyl-functional polyesters are determined using gel permeation chromatography using a Waters 2695 Separation Module equipped 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 to 2,000,000) preceded by a PLgel 5 micrometer guard column (50 mm x 7.5 mm) are used. The eluents used were special-grade tetrahydrofuran (THF) for the polyester samples and toluene for the crosslinker samples, flowing at 1.0 mL / min, with the columns and detectors maintained at 35°C. Polyester samples were prepared in THF and crosslinker samples in toluene at approximately 0.15 volume percent, solvated for 2 hours with occasional shaking, and filtered through a 0.45 micrometer polytetrafluoroethylene syringe filter before analysis. A 100 microliter sample was injected for analysis, and data was collected for 30 minutes. ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software were used to collect data and perform the analysis. Average molecular weights were measured against a calibration curve (third order) generated using polystyrene standards spanning the molecular weight range of 580 to 2,750,000.

[0030] The crosslinker material is a silylhydride-functional (SiH-functional) compound, preferably a SiH-functional polysiloxane. The crosslinker material contains at least two SiH functional groups. 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.

[0031] 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.

[0032] 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)SiO2 / 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.

[0033] When present, the silylhydride functional polysiloxane is desirably present in a concentration sufficient to provide a molar ratio of SiH functional groups from the crosslinker material to unsaturated carbon-carbon bonds from the backbone polymer of 0.7 or greater, preferably 0.90 or greater, while typically 1.5 or less, preferably 1.0 or less, and even more preferably 0.95 or less.

[0034] The elastomer of the first aspect of the present invention is formed by crosslinking the backbone polymer with a crosslinker material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the backbone polymer and the silyl hydride groups of the crosslinker material.

[0035] It is typically desirable to carry out the hydrosilylation reaction in the presence of a hydrosilylation catalyst, which is typically 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.

[0036] The concentration of the platinum-based hydrosilylation catalyst is typically 5 weight-parts per million (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 combined weight of the crosslinker material and backbone polymer, 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.

[0037] It is desirable to carry out the hydrosilylation reaction in a non-aqueous solvent to produce a solvent-swollen elastomer. Examples of suitable solvents include those described herein above, including non-polar solvents. Desirably, when the solvent is a polysiloxane and the organosilyl-functional polyester contains more than two terminal carbon-carbon double bonds, the molecular weight of the crosslinker is less than 7500, and can have a molecular weight of 7400 or less, preferably 2400 or less, or even 2390 or less, more preferably 1400 or less, or even 1390 or less. The molecular weight of the crosslinker material is determined using the method described herein above for the organosilyl-functional polyester.

[0038] The method can include forming a solvent-swollen elastomer as described and then subjecting the solvent-swollen elastomer to shearing to break down the solvent-swollen elastomer into a particulate form and produce a paste. Optionally, a non-aqueous solvent can be added to the solvent-swollen elastomer before, during, and / or after subjecting the solvent-swollen elastomer to shearing. In the broadest sense, there is no limit to the manner in which the solvent-swollen elastomer is subjected to shearing. For example, shear can be applied to break down the solvent-swollen elastomer into a particulate form by mixing the solvent-swollen elastomer with a mixing blade. The degree of shearing can determine the particle size of the elastomer gel in the paste. Typically, the finer the particle size, the smoother (less gritty) the resulting paste will feel, and therefore, a finer particle size is desirable for applications such as cosmetics that involve application to the skin. [Example]

[0039] The main chain polymer is prepared according to the following method, and then the samples of the inventive examples (Ex) and comparative examples (CEx) are prepared according to the following subsequent procedures.

[0040] Preparation of organosilyl-functional polyester main chain polymers Table 1 lists the components for preparing the following examples.

[0041] [Table 1] PRIPLAST is a trademark of Croda International PLC. DESMOPHEN is a trademark of Covestro Intellectual Property GMBH.

[0042] Table 2 provides the concentrations of polyester polyol, catalyst, and divinyldisilazane in grams, as well as the reaction time (hours) and reaction temperature (° C.), used to prepare each organosilyl-functional polyester for each of Organosilyl-functional Polyesters 1-3. In addition, Table 2 lists the average OH substitution mole percent (mol%) (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.

[0043] [Table 2]

[0044] The polyester polyol, divinyldisilazane, 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 divinyldisilazane is removed under vacuum (1.3 kilopascals) at 130°C for 2 hours to yield the resulting organosilyl-functional polyester.

[0045] The resulting organosilyl functional polyester is reacted with protons ( 1H) 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. 1 Analysis 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. 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 from δ 4.2-4.3 ppm to determine hydroxyl substitution, the methylene region adjacent to the ester region ("E") from δ 2.1-2.3 ppm to account for methylene exclusion, and the methyl region at δ 0.15-0.3 ppm to account 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.

[0046] Organosilyl-functional polyester 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

[0047] Organosilyl-functional polyester 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

[0048] The organosilyl functional polyesters 3 can have a combination of structures, but are expected to include materials having the following average chemical structures:

[0049] [ka]

[0050] Preparation of Ex and CEx Table 3 lists the components for making the following Examples (Ex) and Comparative Examples (CEx).

[0051] [Table 3] CETIOL is a trademark of Cognis IP Management GMBH. CRODAMOL is a trademark of Croda, Inc. CERAPHYL is a trademark of ISP Investments, Inc. DOWSIL is a trademark of The Dow Chemical Company. SYL-OFF is a trademark of Dow Corning Corporation.

[0052] The following hydrosilylation procedure is used to prepare elastomer samples. The identity of each component and its concentration in grams per gram ("[g]") are shown in Table 4. The organosilyl-functional polyester ("OFP"), crosslinker, and solvent are combined in a 20-milliliter glass scintillation vial equipped with a magnetic stir bar, and the components are stirred at 250 revolutions per minute to form a mixture. The mixture is heated to the reaction temperature shown in Table 4, and then the hydrosilylation catalyst is added at the concentration shown in Table 4, by weight in parts per million of the mixture weight. The mixture is maintained at the reaction temperature for 3 hours and then allowed to cool to 25°C.

[0053] Successful formation of the solvent swollen elastomer (Rxn success = Y) is evident when the reaction product flows no more than 1 centimeter in a scintillation vial when inverted for 1 minute.

[0054] Table 4 reports the identity of each component, the amount of each component, the molar ratio of silyl hydride to carbon-carbon double bond (SiH:C=C), the reaction temperature (Temp), and whether the solvent-swollen elastomer was successfully formed.

[0055] CEx A reveals that if the backbone polymer has an average of two unsaturated carbon-carbon bonds and the crosslinker material has an average of two SiH groups, the reaction fails to cure to an elastomer. However, other examples reveal that as long as either the backbone polymer or the crosslinker material has an average of three or more functional groups, the other can have two, and the reaction will form an elastomer.

[0056] Exs 26-39 and CEx B and CEx C show that when using organosiloxane solvents with organosilyl-functional polyesters having more than two terminal C-C double bonds, it is desirable to use a crosslinker with a molecular weight less than 7400.

[0057] [Table 4]

[0058] Paste sample Pastes are prepared from the example materials above by subjecting them to shear using a Waring Model 7012 blender. For Paste 1 and Paste 2, the solvent is added gradually while shear is applied. Table 5 identifies exemplary compositions for making the pastes, including which example materials are used, how much (in grams), which solvent is added and how much (in grams), the resulting solids concentration as a weight percent of the paste weight, and millipascals x seconds (mPascals x seconds, mPa * Determine the final paste viscosity at 2.5 revolutions per minute at 25° C. using a Brookfield DV-II Plus Pro Programmable Viscometer equipped with a Helipath spindle (S94).

[0059] [Table 5]

[0060] Sensory Feeling The sensory feel of the paste sample and two commercially available dimethicone materials available from The Dow Chemical Company under the trade names DOWSIL™ 9041 (Ref 1) and DOWSIL™ 3901 (Ref 2) are characterized. Ref 1 serves as a siloxane material with a desirable sensory feel profile. Ref 2 is a siloxane material with an undesirable sensory feel profile.

[0061] A panel of 10 trained sensory evaluators conducts sensory feel evaluations. Prior to evaluation, panelists wash their forearms, hands, and fingers with 4.3% active sodium lauryl ether sulfate in water, then rinse with distilled water and dry with a paper towel. For evaluation, each panelist applies 50 milligrams of sample material to the inside of their forearm in a circular motion at a rate of 2 rubs per second for up to 120 rubs. Panelists characterize skin sensory parameters on a scale of 1 to 5, with 5 being most similar to the parameter descriptor and 1 being least similar to the parameter descriptor. Each sample is assigned a final value that is the average of the 10 trained sensory evaluators' values ​​for each parameter. The parameters and descriptors are as follows:

[0062] [Table 6]

[0063] For a "smooth, dry, fine feel," it is desirable for the sample to have a smoothness value greater than 3, a fineness value greater than 2, and a wetness value less than 3. Table 6 provides the sensory evaluation results for Pastes 1-4, Ref 1, and Ref 2. The results show that the pastes of the present invention, similar to the standard siloxane material of Ref 1, and in contrast to Ref 2, are successful in achieving the desired "smooth, dry, fine feel."

[0064] [Table 7]

[0065] durability The durability of the paste was evaluated according to the following procedure. Samples were prepared by adding 8 g of sample paste and 2 g of Skolar Glare™ Violet SG-7661E dye (manufactured by CQV Co. Ltd.; Skolar Glare is a trademark of CQV Co. Ltd.) to a dental cup. Mixing was performed at 2000 revolutions per minute for 20 seconds using a FlackTek DAC 150 speed mixer. 0.3 g of the resulting mixture was coated onto a 4.75 cm x 5 cm collagen-coated microscope slide. The coated sample was allowed to dry at 25°C for 24 hours. The coated slide was then cleaned by applying a solution of 0.07 g of DIAL™ dish soap (Henkel Corporation) in 0.07 g of water to the coated slide with a damp fingertip for 20 seconds. After cleaning, a digital image of the slide was taken and analyzed using Image J software to determine the area of ​​the slide on which the coating remained. The area of ​​coating remaining as a percentage of the originally coated area is reported, which is the durability percentage of the sample. Higher values ​​are more desirable for durability. Table 7 reports the durability percentages for the samples.

[0066] [Table 8]

[0067] The data in Table 7 demonstrate that the pastes of the present invention have greater durability than either of the siloxane reference materials. It is desirable that the pastes have a greater likelihood of remaining on the skin and providing the desired sensory feel even after washing.

[0068] Solvent Compatibility The solvent compatibility of samples is evaluated by combining 7.5 g of sample with 2.5 g of a particular solvent (see Table 8) in a dental cup and then mixing for 30 seconds using a FlackTek DAC 150 Speed ​​Mixer at 2300 revolutions per minute. The material is transferred to a 20 milliliter clear, glass vial and centrifuged for 20 minutes at 3000 revolutions per minute using an IEC Model K centrifuge. The samples are allowed to stand at 25°C for 24 hours, after which the samples are observed and characterized using the following scale, with lower values ​​being better: 1: Transparent. The sample is clear and can be easily read through when placing the lettering behind the vial containing the sample. 2: Slight haze. The sample is nearly clear with very slight haze detectable and when placed behind the vial containing the sample, the letter can still be easily read through the sample. 3: Cloudy. The sample is not transparent and the lettering placed on the back of the vial containing the sample can be detected but not read. 4: Opaque. White solid. Light cannot pass through and it is not possible to detect what is placed behind the vial. 5: Not compatible. Sample phases separated.

[0069] The results for the samples are shown in Table 8. The data reveal that the pastes of the present invention generally have broader solvent compatibility than either Ref 1 or Ref 2.

[0070] [Table 9]

[0071] Hydrolytic stability The relative hydrolytic stability of the CO-Si bond versus the CO-C bond in organosilyl-functional polyester 1 was evaluated. Fifteen milligrams of organosilyl-functional polyester 1 was placed in a glass nuclear magnetic resonance (NMR) tube and 0.75 milliliters of deuterated chloroform (CDCl) was added. Five microliters of a 10:1 mixture of deionized water / trifluoroacetic acid was then added. Proton NMR spectra were collected immediately after the addition of the water / acid mixture and at 5 and 25 hours later. A 400 MHz Varian 1 NMR spectra were collected 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 final spectrum for analysis. The reference peak was at δ 7.26 ppm relative to CDCl3. At each time point, the CO-Si hydrolysis mol% and CO-C hydrolysis mol% were determined. The CO-Si hydrolysis mol% was determined by integrating the dimethylvinylsilyl polyester peak (CO-Si(Me)2Vi) at δ 0.16-0.18 ppm and the hydrolyzed dimethylvinylsilyl group (HO-Si(Me)2Vi) at δ 0.21-0.22 ppm. The CO-Si hydrolysis mol% was determined by evaluating the growth of the resonance of the hydrolyzed dimethylvinylsilyl group (HO-Si(Me)2Vi) present at δ 0.21-0.22 in CDCl3 relative to the resonance of the unhydrolyzed dimethylvinylsilyl polyester peak at δ 0.16-0.18 ppm. The mole % COC hydrolysis is determined by integrating the proton resonances of the unhydrolyzed polyester (-CH2-OC(O)-C-) present at δ 4.21-4.26 ppm in CDCl3 relative to those resonances present at 9-11 ppm in the hydrolyzed composition (HO-C(O)-C) in CDCl3.

[0072] The results in Table 9 reveal that the CO-C bond remains hydrolytically stable, while the CO-Si bond is almost completely hydrolyzed in 25 hours, supporting the idea that the CO-Si bond is less hydrolytically stable than the CO-C bond.

[0073] [Table 10]

Claims

1. A composition comprising an elastomer, the elastomer having a polyester backbone crosslinked with a crosslinking agent, the composition having a carbon-oxygen-silicon bond between the ester group and the crosslinking agent.

2. The composition of claim 1, wherein the polyester backbone does not contain silicon-oxygen-silicon bonds.

3. 3. The composition of claim 1, wherein the crosslinker is a polysiloxane.

4. The composition of any one of claims 1 to 3, wherein there is at least one carbon-oxygen-silicon bond between any polyester and any siloxane bond in the elastomer.

5. 5. The composition of any one of claims 1 to 4, wherein each polyester backbone has at least three bonds with the crosslinker and / or each crosslinker has at least three bonds with the backbone polymer.

6. The composition of any one of claims 1 to 5, wherein the elastomer is solvent swollen with a non-aqueous solvent.

7. The composition of claim 5 , wherein the elastomer is present in particulate form and the composition is in the form of a paste.

8. A method for preparing a composition according to any one of claims 1 to 7, said method comprising: a. providing a backbone polymer having at least two terminal unsaturated carbon-carbon bonds separated from any polyester group by a carbon-oxygen-silicon bond, and a crosslinker material containing a plurality of silyl hydride groups, wherein at least one of the backbone polymer or crosslinker has an average unsaturated carbon-carbon bond functionality of 3 or greater, and / or the crosslinker has an average silyl hydride functionality of 3 or greater; b) crosslinking the backbone polymer with the crosslinker material to form the elastomer by hydrosilylation addition between unsaturated carbon-carbon bonds of the backbone polymer and silyl hydride groups of the crosslinker material.

9. 9. The method of claim 8, wherein the hydrosilylation reaction is carried out in a non-aqueous solvent to produce a solvent-swollen elastomer, and wherein the non-aqueous solvent is a polysiloxane and the organosilyl-functional polyester contains three or more terminal carbon-carbon bonds, and the crosslinker has a weight average molecular weight less than [the molecular weight for crosslinker 3].

10. a. optionally adding additional non-aqueous solvent to the solvent-swollen elastomer; 10. The process of claim 9, further comprising: subjecting the solvent-swollen elastomer to shear to break down the solvent-swollen elastomer into particulate form to produce a paste.

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