Silicone-vinyl ester functional compounds and methods for their preparation and use in personal care compositions

Abstract

Provided is a silicone-vinyl ester copolymer, and a method for its preparation and use. The silicone-vinyl ester copolymer can be made using a vinyl ester functional siloxane macromonomer, which can be prepared by a process that includes hydroformylation of an alkenyl functional polyorganosiloxane to form an aldehyde functional polyorganosiloxane, oxidation of the aldehyde functional polyorganosiloxane to form a carboxy functional polyorganosiloxane, and transvinylation of the carboxy functional polyorganosiloxane to form a vinyl ester functional siloxane macromonomer. The silicone-vinyl ester copolymer is useful in personal care compositions.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 63 / 330511, filed April 13, 2022. U.S. Provisional Application No. 63 / 330511 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to vinyl ester-functional siloxane macromonomers (macromonomers) that can be copolymerized with vinyl esters of aliphatic fatty acids to form silicone-vinyl ester copolymers (copolymers), and methods for the preparation of the macromonomers and copolymers. The copolymers can be added to personal care compositions suitable for application to human skin. [Background technology]

[0003] Introduction Film formers are important cosmetic ingredients and are widely used in personal care compositions, such as leave-on products that are applied to human skin, such as skin care, sunscreens, and color cosmetic products. DOWSIL silicone acrylate FA series products, such as DOWSIL FA 4004 and DOWSIL FA 4012 provided by Dow Silicones Corporation (Midland, Michigan, USA), are used as film formers in personal care compositions. However, the cosmetic industry continues to need sustainable and / or naturally derived ingredients that have one or more of the following properties: potential biodegradability, water resistance, sebum resistance, rub-off resistance, and favorable sensory properties. Summary of the Invention

[0004] Vinyl ester functional siloxane macromonomers (macromonomers) and silicone-vinyl ester copolymers (copolymers) are disclosed. Methods for the preparation of the macromonomers and copolymers are provided. The copolymers are useful in personal care compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] The copolymer can be obtained by a process comprising copolymerizing a mixture of M1) a vinyl ester functional siloxane macromonomer (introduced above) and M2) a monomer comprising a vinyl ester of an aliphatic fatty acid. The copolymer can be used in personal care compositions.

[0006] Starting Material M1) Vinyl Ester Functional Siloxane Macromonomer The starting material M1) is the vinyl ester functional siloxane macromonomer (macromonomer) introduced above. The amount of M1) macromonomer in the monomer mixture depends on various factors, including the selection and amount of other monomers in the mixture, as well as the desired end use of the copolymer. However, the amount of M1) macromonomer can be 1% to 99%, alternatively 30% to 60%, based on the total weight of all monomers in the monomer mixture (e.g., based on the total weight of M1), M2), and M3) as described herein).

[0007] The macromonomer has the formula (M1-1):

[0008] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation, and each R 12 However, independently, -OSi(R 14 )3 and R 13 Each R 13 is a monovalent hydrocarbon group, where each R 14 But R 13 , -OSi(R 15)3, and -[OSiR 13 2] ii OSiR 13 3, wherein each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 3, wherein each R 16 But R 13 and -[OSiR 13 2] ii OSiR 13 3, where each subscript ii independently has a value such that 0≦ii≦100, with the proviso that R 12 At least two of -OSi(R 14 )3, provided that the macromonomer has 4 to 16 silicon atoms per molecule. Alternatively, each R 13 can be independently selected alkyl groups. Alternatively, each R 13 R can be methyl. 12 At least two of -OSi(R 14 ) 3. Alternatively, R 12 All three of the -OSi(R 14 )3.

[0009] Examples of divalent hydrocarbon groups for G include the empirical formula -C r H 2r -, where the subscript r is 2 to 8. The alkylene group can be a straight chain alkylene, for example, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkylene, for example,

[0010] [ka] Alternatively, the divalent hydrocarbon group for G can be an arylene group, such as phenylene, or

[0011] [ka] Alternatively, G can be an alkylene group such as ethylene.

[0012] Each R 13 R is an independently selected monovalent hydrocarbon group. 13 The monovalent hydrocarbon groups for R may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms. 13 Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and saturated branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 13 The alkyl groups for may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl and ethyl. Alternatively, R 13 The alkyl group for can be methyl.

[0013] R 13 Suitable aryl groups for may be monocyclic or polycyclic and may have pendant hydrocarbyl groups. For example, R 13 Aryl groups for R include phenyl, tolyl, xylyl, and naphthyl, as well as aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. 13 The aryl group for R may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively, R 13 The aryl group for can be phenyl.

[0014] Alternatively, in formula (M1-1), each R 12 -OSi(R 14 )3, and each R 14 -OSi(R 15 )3, the macromonomer has the structure (M1-2):

[0015] [ka] where G and R 15 Alternatively, in this structure, each R 15 As above, R 13 Each R 13 can be methyl.

[0016] Alternatively, in formula (M1-1), each R 12 -OSi(R 14 )3, then one R 14 is each R 12 -OSiR 13 (R 14 )2 for each -OSi(R 14 )3 in R 13 Alternatively, -OSiR 13 (R 14 )2 R's 14 Each of the macromonomers has the following structure (M1-3):

[0017] [ka] -OSi(R 15 ) three moieties, where G, R 13 , and R 15 Alternatively, in this structure, each R 15 As above, R 13 Each R 13 can be methyl.

[0018] Alternatively, in formula (M1-1), one R 12 is R 13 R 12 Two of them are -OSi(R 14 )3. R 12 Two of them are -OSi(R 14 )3, then one R 14 Each -OSi(R 14 )3 in R 13 Therefore, R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 has the following structure (M1-4):

[0019] [ka] -OSi(R 15 )3, wherein G, R 13 , and R 15 Alternatively, in this formula, each R 15 is R 13 Each R 13 can be methyl.

[0020] Examples of macromonomers include those of formula (M1-6):

[0021] [ka] (M1-5): vinyl 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanoate, Formula (M1-7):

[0022] [ka] vinyl 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propanoate having Formula (M1-8):

[0023] [ka] vinyl 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propanoate, formula

[0024] [ka] and vinyl 7-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane)-5-yl)heptanoate,

[0025] Alternatively, the macromonomer of the starting material M1) can be linear. Alternatively, the macromonomer (M1-9) can comprise a linear polydiorganosiloxane having at least one vinyl ester functional group, alternatively at least two vinyl ester functional groups, per molecule. For example, the polydiorganosiloxane can be represented by the unit formula (M1-10): (R 4 3SiO 1 / 2 ) a (R VE R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R VE R 4 SiO 2 / 2 ) d wherein R VE but,

[0026] [ka] wherein G is a divalent hydrocarbon group free of aliphatic unsaturation as described above for formula (M1-1), and each R 4 are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscripts a, b, c, and d represent the average number of each unit in the formula, with subscript a having a value such that subscript b is 0, 1, or 2, subscript c≧0, and subscript d≧0, provided that the quantity (b+d)≧1, the quantity (a+b)=2, and the quantity (a+b+c+d)≧2. The quantity (a+b+c+d) can be at least 3, alternatively at least 4, and alternatively >50. At the same time, in the unit formula (M1-1), the quantity (a+b+c+d) can be 10,000 or less, alternatively 4,000 or less, alternatively 2,000 or less, alternatively 1,000 or less, alternatively 500 or less, and alternatively 250 or less.

[0027] R 4 Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 4 The alkyl groups for may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl and ethyl. Alternatively, R 4 The alkyl group in may be methyl.

[0028] R4 Suitable aryl groups for may be monocyclic or polycyclic and may have pendant hydrocarbyl groups. For example, R 4 Aryl groups of R include phenyl, tolyl, xylyl, and naphthyl, as well as aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. 4 The aryl group of R may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively, R 4 The aryl group can be phenyl.

[0029] Alternatively, the linear vinyl ester functional polydiorganosiloxane of the unit formula (M1-10) may be represented by the unit formula (M1-11): (R 4 2R VE SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R VE SiO 2 / 2 ) n , Unit formula (M1-12): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R VE SiO 2 / 2 ) p In formulae (M1-11) and (M1-12), each R VE and each R 4is as described above for formula (M1-10), and the subscripts m, n, o, and p represent the average number of each unit in unit formulas (M1-11) and (M1-12). The subscripts m, n, o, and p have the following values, where subscript m can be 0 or a positive number. Alternatively, subscript m can be at least 2. Alternatively, subscript m can be 2 to 2,000. Subscript n can be 0 or a positive number. Alternatively, subscript n can be 0 to 2000. Subscript o can be 0 or a positive number. Alternatively, subscript o can be 0 to 2000. Subscript p is at least 2. Alternatively, subscript p can be 2 to 2000.

[0030] Alternatively, the polydiorganosiloxane of the unit formula (M1-10) may have the formula (M1-13):

[0031] [ka] In the formula, each R 2’’’ But independently, R 4 and R VE with the proviso that at least one R 2’’’ But R VE And each R 4 and each R VE is as above for formula (M1-10), provided that the subscript zz=the quantity (c+d). Alternatively, the subscript zz may have a value from 0 to 2,000, alternatively from 0 to 1,000, alternatively from 50 to 2,000, alternatively from 50 to 1,000, alternatively from 80 to 800.

[0032] Alternatively, the polydiorganosiloxane of formula (M1-10) may contain two different end groups, i.e., when subscript a = 1 and subscript b = 1. Alternatively, the polydiorganosiloxane may be monofunctional, having one vinyl ester functional group per molecule, for example, when subscript a = 1, b = 1, and d = 0 in unit formula (M1-10). The polydiorganosiloxane may be represented by formula (M1-14):

[0033] [ka] wherein each R 4 and each R VE and subscript c are as described above for formula (M1-1). Alternatively, in formula (M1-14), subscript c may have a value from 0 to 2,000, alternatively from 0 to 1,000, alternatively from 50 to 2,000, alternatively from 50 to 1,000, or alternatively from 80 to 800.

[0034] The starting material M1) macromonomers are i) bis-dimethyl(propanoate)siloxy terminated polydimethylsiloxane, ii) bis-dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / methyl(propanoate)siloxane), iii) bis-dimethyl(propanoate)siloxy terminated polymethyl(propanoate)siloxane, iv) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(propanoate)siloxane), v) bis-trimethylsiloxy terminated polymethyl(propanoate)siloxane, vi) bis -dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(propanoate)siloxane), vii) bis-dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, (propanoate)-siloxy terminated polydimethylsiloxane, x) bis-dimethyl(heptanoate)siloxy terminated polydimethylsiloxane xi) bis-dimethyl(heptanoate)siloxy terminated poly(dimethylsiloxane / methyl(heptanoate)siloxane), xii) bis-dimethyl(heptanoate)siloxy terminated polymethyl(heptanoate)siloxane), xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(heptanoate)siloxane), xiv) bis-trimethylsiloxy terminated polymethyl(heptanoate)siloxane, xv) bis-dimethyl(heptanoate)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(heptanoate)siloxane), xvi) bis-dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / methyl(heptanoate)siloxane), xvii) bis-dimethyl(heptanoate)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) bis-dimethyl(heptanoate)-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), xix) alpha-dimethyl(n-butyl)siloxy-omega-dimethyl(propanoate)siloxy terminated poly(dimethylsiloxane),and xx) a vinyl ester functional polydiorganosiloxane such as a combination of two or more of i) to xix).

[0035] Process for making vinyl ester functional siloxane macromonomers The above macromonomers are Optionally, 1) combining starting materials including: (A) a gas comprising hydrogen and carbon monoxide; (B) an alkenyl-functional polyorganosiloxane; (C) a rhodium / bisphosphite ligand complex catalyst; and (D) a solvent under conditions to catalyze a hydroformylation reaction, thereby forming (E) an aldehyde-functional polyorganosiloxane; Optionally, 2) recovering the aldehyde-functional polyorganosiloxane (E); and Optionally, 3) combining starting materials including (E) an aldehyde-functional polyorganosiloxane, (F) an oxygen source, optionally (G) an oxidation reaction catalyst, and optionally (H) a second solvent under conditions conducive to an oxidation reaction, thereby forming an oxidation reaction product including (I) a carboxy-functional polyorganosiloxane; optionally 4) (I) recovering the carboxy-functional polyorganosiloxane; 5) combining starting materials including (I) a carboxy-functional polyorganosiloxane, (J) an alkenyl acetate, (K) a transvinylation catalyst, optionally (L) a third solvent, and optionally (X) an inhibitor under conditions conducive to a transvinylation reaction, thereby producing a transvinylation reaction product including (M1) the macromonomer described above; and optionally 6) recovering the (M1) macromonomer.

[0036] Hydroformylation In the transvinylation reaction process for making the macromonomer described herein, a process can be carried out that includes hydroformylation of an alkenyl-functional polyorganosiloxane to form an aldehyde-functional polyorganosiloxane, followed by oxidation of the aldehyde-functional polyorganosiloxane to form a starting material (I) that is a carboxy-functional polyorganosiloxane. The hydroformylation reaction in step 1) can be carried out at a relatively low temperature. For example, the hydroformylation in step 1) can be carried out at a temperature of at least 30°C, alternatively at least 50°C, alternatively at least 70°C. At the same time, the temperature for the hydroformylation reaction can be up to 150°C, alternatively at most 100°C, alternatively at most 90°C, alternatively at most 80°C. Without wishing to be bound by theory, it is believed that lower temperatures, for example, 30°C to 90°C, alternatively 40°C to 90°C, alternatively 50°C to 90°C, alternatively 60°C to 90°C, alternatively 70°C to 90°C, alternatively 80°C to 90°C, alternatively 30°C to 60°C, alternatively 50°C to 60°C, may be desirable to obtain high selectivity and ligand stability.

[0037] In the process described herein, the hydroformylation reaction in step 1) can be carried out at a pressure of at least 101 kPa (ambient pressure), alternatively at least 206 kPa (30 psi), alternatively at least 344 kPa (50 psi). At the same time, the pressure in step 1) can be up to 6,895 kPa (1,000 psi), alternatively up to 1,379 kPa (200 psi), alternatively up to 1000 kPa (145 psi), alternatively up to 689 kPa (100 psi). Alternatively, step 1) can be carried out at 101 kPa to 6,895 kPa, alternatively 344 kPa to 1,379 kPa, alternatively 101 kPa to 1000 kPa, alternatively 344 kPa to 689 kPa. Without wishing to be bound by theory, it is believed that it may be beneficial to use relatively low pressures, e.g., <6,895 kPa, in the hydroformylation reaction step of the processes herein, and the ligands described herein enable low pressure hydroformylation reactions, which have the advantages of lower cost and better safety than high pressure hydroformylation reactions.

[0038] The hydroformylation reaction step of the process may be carried out in batch, semi-batch, or continuous mode using one or more suitable reactors, such as a fixed bed reactor, a fluidized bed reactor, a continuous stirred tank reactor (CSTR), or a slurry reactor. (B) The alkenyl-functional polyorganosiloxane, and (C) the choice of catalyst, and (D) whether a solvent is used, may affect the size and type of reactor used. One reactor, or two or more different reactors may be used. The hydroformylation process may be carried out in one or more steps, which may be influenced by balancing capital costs, achieving high catalyst selectivity, activity, life, and ease of operation, as well as the reactivity of the particular starting materials and the reaction conditions selected, and the desired products.

[0039] Alternatively, the hydroformylation reaction can be carried out in a continuous manner. For example, the hydroformylation reaction step of the process used can be as described in U.S. Patent No. 10,023,516, except that the olefin feed stream and catalyst described therein are replaced with (B) the alkenyl-functional polyorganosiloxane and (C) the rhodium / bisphosphite ligand complex catalyst described herein, respectively.

[0040] Step 1) of the process forms a hydroformylation reaction product comprising (E) an aldehyde-functional polyorganosiloxane. The hydroformylation reaction product may further include additional materials, such as those intentionally used during step 1) of the process or those formed in situ. Examples of such materials that may also be present include unreacted (B) alkenyl-functional polyorganosiloxane, unreacted (A) carbon monoxide and hydrogen gas, and / or by-products formed in situ, such as ligand decomposition products and their adducts, and high-boiling liquid aldehyde condensation by-products, and (D) solvent, if used. The term "ligand decomposition products" includes, but is not limited to, any and all compounds resulting from one or more chemical transformations of at least one of the ligand molecules used in the process.

[0041] This process may further include additional steps such as 2) recovering (E) aldehyde-functional polyorganosiloxane from the hydroformylation reaction product. This may be carried out by separating (C) the rhodium / bisphosphite ligand complex catalyst from the hydroformylation reaction product. Separating (C) the rhodium / bisphosphite ligand complex catalyst may be carried out by methods known in the art, including but not limited to adsorption and / or membrane separation (e.g., nanofiltration). Suitable recovery methods are described, for example, in U.S. Patent No. 5,681,473 to Miller et al., U.S. Patent No. 8,748,643 to Priske et al., and U.S. Patent No. 10,155,200 to Geilen et al.

[0042] However, one advantage of the process described herein is that it is not necessary to remove and reuse (C) hydroformylation catalyst.Due to the low level of Rh required, it may be more cost-effective not to recover and reuse (C) hydroformylation catalyst, and the aldehyde-functional polyorganosiloxane produced by this process may be stable even if the hydroformylation catalyst is not removed.Furthermore, without wishing to be bound by theory, it is believed that (C) hydroformylation catalyst may also catalyze the oxidation reaction of the aldehyde-functional polyorganosiloxane, as described herein below.Therefore, alternatively, the above hydroformylation process may be carried out without removing the hydroformylation catalyst in step 2).

[0043] Alternatively, the optional step 2) of this process may include purifying the hydroformylation reaction product. For example, the aldehyde-functional polyorganosiloxane may be isolated from the additional materials by any convenient means, such as stripping and / or distillation, optionally using reduced pressure. Alternatively, step 2) may be omitted, leaving the hydroformylation catalyst (C) in the hydroformylation reaction product, for example, containing the aldehyde-functional polyorganosiloxane.

[0044] (A) Synthetic gas The gas starting material (A) used in the hydroformylation process includes carbon monoxide (CO) and hydrogen gas (H2). For example, the gas can be synthesis gas. As used herein, "syngas" (from synthesis gas) refers to a gas mixture containing various amounts of CO and H2. Production methods are well known and include, for example, (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons, and (2) gasification of coal and / or biomass. CO and H2 are typically the major components of synthesis gas, but synthesis gas can contain carbon dioxide and inert gases such as CH4, N2, and Ar. The molar ratio of H2 to CO (H2:CO molar ratio) varies widely but can range from 1:100 to 100:1, alternatively 1:10 to 10:1. Synthesis gas is commercially available and is often used as a fuel source or as an intermediate for producing other chemicals. Alternatively, CO and H2 from other sources (i.e., other than syngas) may be used as starting material (A) herein. Alternatively, the H2:CO molar ratio in starting material (A) for use herein may be 3:1 to 1:3, alternatively 2:1 to 1:2, alternatively 1:1.

[0045] (B) Alkenyl-functional polyorganosiloxane The starting material (B) used in the process described herein is an alkenyl-functional polyorganosiloxane. The alkenyl-functional polyorganosiloxane may be branched. The branched alkenyl-functional polyorganosiloxane is represented by the general formula (B1-1): R A SiR 12 3, where R A is an alkenyl group, and each R 12 But, -OSi(R 14 )3 and R 13 Each R 13 is a monovalent hydrocarbon group, where each R 14 But R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 133, wherein each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 16 is R 13 and -[OSiR 13 2] ii OSiR 13 3, where the subscript ii has a value such that 0≦ii≦100. 12 At least two of -OSi(R 14 ) 3. Alternatively, R 12 All three of the -OSi(R 14 )3.

[0046] Each R A R is an independently selected alkenyl group. The alkenyl group can have 2 to 8 carbon atoms. A The alkenyl group of R may have a terminal alkenyl functionality, e.g., A is the formula

[0047] [ka] where subscript y is 0 to 6. Alternatively, each R A may be independently selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R A may be independently selected from the group consisting of vinyl and allyl. Alternatively, each R A Alternatively, each R A can be allyl.

[0048] Alternatively, in formula (B1-1), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure (B1-2):

[0049] [ka] -OSi(R 15 ) 3 moieties, where R A and R 15 Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0050] Alternatively, in formula (B1-1), each R 12 -OSi(R 14 )3, then one R 14 is each R 12 -OSiR 13 (R 14 )2 for each -OSi(R 14 )3 in R 13 Alternatively, -OSiR 13 (R 14 )2 R's 14 Each of the branched polyorganosiloxane oligomers has the following structure (B1-3):

[0051] [ka] -OSi(R 15 ) 3 moieties, where R A , R 13 , and R 15 Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0052] Alternatively, in formula (B1-1), one R 12 is R 13 R 12 Two of them are -OSi(R 14 )3. R 12 Two of them are -OSi(R 14 )3, then one R14 Each -OSi(R 14 )3 in R 13 Therefore, R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (B1-4):

[0053] [ka] -OSi(R 15 )3, wherein R A , R 13 , and R 15 Alternatively, each R 15 is R 13 Each R 13 can be methyl. Alternatively, the alkenyl-functional branched polyorganosiloxane can have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule, alternatively 7 to 16 silicon atoms per molecule, alternatively 7 to 10 silicon atoms per molecule, alternatively 10 to 16 silicon atoms per molecule. Examples of alkenyl-functional branched polyorganosiloxane oligomers include those having the formula (B1-5):

[0054] [ka] vinyl-tris(trimethylsiloxy)silane having the formula Formula (B1-6):

[0055] [ka] (1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane), Formula (B1-7):

[0056] [ka] (5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane) having (Si10Vi), and Formula (B1-8):

[0057] [ka] (Si10-hexenyl) and 5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-5-(hex-5-en-1-yl)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane.

[0058] The branched alkenyl-functional polyorganosiloxane oligomers described above can be prepared by known methods such as those disclosed in "Testing the Functional Tolerance of the Piers-Rubinsztajn Reaction: A new Strategy for Functional Silicones" by Grande et al., Supplementary Material (ESI) for Chemical Communications, © The Royal Society of Chemistry 2010.

[0059] Alternatively, the (B) alkenyl-functional polyorganosiloxane may comprise a linear polydiorganosiloxane having at least one alkenyl group, alternatively at least two alkenyl groups, per (B2) molecule. For example, the polydiorganosiloxane may have the unit formula (B2-1): (R 4 3SiO 1 / 2 ) a (R A R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R A R 4 SiO 2 / 2 ) d wherein R A and R 4 is as above, subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c≧0, and subscript d≧0, provided that the quantity (b+d)≧1, the quantity (a+b)=2, and the quantity (a+b+c+d)≧2. Alternatively, in unit formula (B2-1), the quantity (a+b+c+d) can be at least 3, alternatively at least 4, and alternatively >50. At the same time, in unit formula (B2-1), the quantity (a+b+c+d) can be 10,000 or less, alternatively 4,000 or less, alternatively 2,000 or less, alternatively 1,000 or less, alternatively 500 or less, and alternatively 250 or less. Alternatively, in unit formula (B2-1), each R 4 may be independently selected from the group consisting of alkyl and aryl, alternatively methyl and phenyl. Alternatively, each R in the unit formula (B2-1) 4 may be an alkyl group, alternatively each R 4 can be methyl.

[0060] Alternatively, the polydiorganosiloxane of the unit formula (B2-1) has the formula (B2-2):

[0061] [ka] wherein R4 is as above, and R 2 But the above R A and R 4 with the proviso that at least one R 2 But R A and provided that the subscript zz=the quantity (c+d). Alternatively, the subscript zz may have a value from 0 to 2,000, alternatively from 0 to 1,000, alternatively from 50 to 2,000, alternatively from 50 to 1,000, alternatively from 80 to 800.

[0062] Alternatively, the polydiorganosiloxane may contain two different end groups, i.e., when subscript a = 1 and subscript b = 1. Alternatively, the polydiorganosiloxane may be monofunctional, with one alkenyl group per molecule, for example, when subscript a = 1, b = 1, and d = 0 in the unit formula (B2-1). The polydiorganosiloxane may be represented by the formula (B2-3):

[0063] [ka] wherein R A and R 4 is as above, and 9,998≧c≧0. Alternatively, in formula (B2-3), subscript c may have a value from 0 to 2,000, alternatively from 0 to 1,000, alternatively from 50 to 2,000, alternatively from 50 to 1,000, alternatively from 80 to 800.

[0064] Alternatively, the polydiorganosiloxane of the unit formula (B2-1) may be a polydiorganosiloxane of the unit formula (B2-4): (R 4 2R A SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R A SiO 2 / 2 ) n , Unit formula (B2-5): (R 4 3SiO 1 / 2 )2(R4 2SiO 2 / 2 ) o (R 4 R A SiO 2 / 2 ) p or a combination of both (B2-4) and (B2-5).

[0065] In formulae (B2-4) and (B2-5), each R 4 and R A are as above. Subscript m may be 0 or a positive number. Alternatively, subscript m may be at least 2. Alternatively, subscript m may be from 2 to 2,000. Subscript n may be 0 or a positive number. Alternatively, subscript n may be from 0 to 2000. Subscript o may be 0 or a positive number. Alternatively, subscript o may be from 0 to 2000. Subscript p is at least 2. Alternatively, subscript p may be from 2 to 2000.

[0066] Alternatively, the starting material (B2) may be i) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), iii) bis-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), v) bis-trimethylsiloxy-terminated polymethylvinylsiloxane, vi) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane vii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane, x) bis-dimethylhexenylsiloxy terminated polydimethylsiloxane, xi) bis-dimethylhexenylsiloxy terminated poly(dimethylsiloxane / methyl xii) bis-dimethylhexenylsiloxy terminated polymethylhexenylsiloxane, xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) bis-trimethylsiloxy terminated polymethylhexenylsiloxane, xv) bis-dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methylhexenylsiloxane), xvi) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / xvii) bis-dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) bis-dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), xix) alpha-dimethyl(n-butyl)siloxy-omega-dimethylvinylsiloxy terminated poly(dimethylsiloxane), and xx) combinations of two or more of i)-xix).

[0067] Methods for preparing the above-mentioned linear alkenyl-functional polydiorganosiloxanes for starting material (B2), such as the hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or the equilibration of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Pat. Nos. 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of linear polydiorganosiloxanes having alkenyl groups are commercially available, for example, under the trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, DMS-V52, MCR-V21, MCR-V25, and MCR-41 from Gelest Inc. (Morrisville, Pennsylvania, USA).

[0068] (C) Hydroformylation reaction catalyst The starting material (C), which is a hydroformylation catalyst, comprises an active complex of rhodium with a closed-end bisphosphite ligand. The bisphosphite ligand can be symmetric or asymmetric. Alternatively, the bisphosphite ligand can be symmetric. The bisphosphite ligand has the formula (C1):

[0069] [ka] wherein R 6 and R 6’ are each independently selected from the group consisting of hydrogen, an alkyl group of at least one carbon atom, a cyano group, a halogen group, and an alkoxy group of at least one carbon atom; R 7 and R 7’ are each independently an alkyl group of at least 3 carbon atoms, and a group of the formula -SiR 17 3 groups, wherein each R17 is an independently selected monovalent hydrocarbon radical of 1 to 20 carbon atoms; R 8 , R 8’ , R 9 , and R 9’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R 10 , R 10’ , R 11 , and R 11’ are each independently selected from the group consisting of hydrogen and alkyl groups. 7 and R 7’ One of the groups may be hydrogen.

[0070] In formula (C1), R 6 and R 6’ R can be an alkyl group of at least 1 carbon atom, alternatively 1 to 20 carbon atoms. 6 and R 6’ Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 6 and R 6’ The alkyl groups for R may be selected from the group consisting of ethyl, propyl, and butyl, alternatively propyl and butyl. 6 and R 6’ The alkyl group for R can be butyl. 6 and R 6’ may be an alkoxy group, the alkoxy group being of the formula -OR 6’’ wherein R 6’’ is R 6 and R 6' is an alkyl group as described above.

[0071] Alternatively, in formula (C1), R 6 and R 6’ may be independently selected from alkyl groups of 1 to 6 carbon atoms and alkoxy groups of 1 to 6 carbon atoms. 6 and R 6’ can be an alkyl group of 2 to 4 carbon atoms. Alternatively, R 6 and R 6’ may be an alkoxy group of 1 to 4 carbon atoms. 6 and R 6’ may be a butyl group, alternatively a tert-butyl group. 6 and R 6’ can be a methoxy group.

[0072] In formula (C1), R 7 and R 7’ R can be an alkyl group of at least 3 carbon atoms, alternatively 3 to 20 carbon atoms. 7 and R 7’ Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 7 and R 7’ The alkyl group for R may be selected from the group consisting of propyl and butyl. 7 and R 7’ The alkyl group for can be butyl.

[0073] Alternatively, in formula (C1), R 7 and R 7’ is represented by the formula -SiR17 3 silyl groups, where each R 17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms. The monovalent hydrocarbon group is 6 and R 6 can be an alkyl group of 1 to 20 carbon atoms as described above.

[0074] Alternatively, in formula (C1), R 7 and R 7’ may each be an independently selected alkyl group, alternatively an alkyl group of 3 to 6 carbon atoms. Alternatively, R 7 and R 7’ can be an alkyl group of 3 to 4 carbon atoms. Alternatively, R 7 and R 7’ may be a butyl group, alternatively a tert-butyl group.

[0075] In formula (C1), R 8 , R 8’ , R 9 , R 9’ is R 6 and R 6’ may be an alkyl group of at least one carbon atom as described above. Alternatively, R 8 and R 8’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 8 and R 8’ Alternatively, in formula (C1), R 9 and R 9’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 9 and R 9’ can be hydrogen.

[0076] In formula (C1), R 10 and R 10’ R may be a hydrogen atom or an alkyl group of at least one carbon atom, alternatively from 1 to 20 carbon atoms. 10 and R 10’ The alkyl group of R 6 and R 6' may be as described above. Alternatively, R 10 and R 10’ Alternatively, R 10 and R 10’ can be hydrogen.

[0077] In formula (C1), R 11 and R 11’ R may be a hydrogen atom or an alkyl group of at least one carbon atom, alternatively from 1 to 20 carbon atoms. 11 and R 11’ The alkyl group for R 6 and R 6’ may be as described above for R. Alternatively, 11 and R 11’ can be hydrogen.

[0078] Alternatively, the ligand of formula (C1) may be selected from the group consisting of: (C1-1) 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine; (C1-2) 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine); and a combination of both (C1-1) and (C1-2).

[0079] Alternatively, the ligand may include 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine, as disclosed in column 11 of U.S. Pat. No. 10,023,516 (see also U.S. Pat. No. 7,446,231, which discloses this compound as Ligand D in column 22, and U.S. Pat. No. 5,727,893, which discloses this compound as Ligand F in column 20, lines 40-60).

[0080] Alternatively, the ligand may include biphephos, commercially available from Sigma Aldrich, and may be prepared as described in U.S. Patent No. 9,127,030. (See also U.S. Patent No. 7,446,231, column 21 for Ligand B, and U.S. Patent No. 5,727,893, column 20, lines 5-18 for Ligand D).

[0081] The rhodium / bisphosphite ligand complex catalyst, starting material (C), can be prepared by methods known in the art, such as those disclosed in U.S. Patent No. 4,769,498 to Billig et al., column 20, line 50 to column 21, line 40, and U.S. Patent No. 10,023,516 to Brammer et al., column 11, line 35 to column 12, line 12, by varying the appropriate starting materials. For example, the rhodium / bisphosphite ligand complex can be prepared by a process comprising combining a rhodium precursor with the above-described bisphosphite ligand (C1) under conditions to form a complex, which can then be introduced into a hydroformylation reaction medium containing one or both of the above-described starting materials (A) and / or (B). Alternatively, for in situ formation of the rhodium / bisphosphite ligand complex, the rhodium / bisphosphite ligand complex may be formed in situ by introducing a rhodium catalyst precursor to the reaction medium and (C1) introducing a bisphosphite ligand to the reaction medium (e.g., before, during, and / or after the introduction of the rhodium catalyst precursor). The rhodium / bisphosphite ligand complex may be activated by heating and / or exposure to starting material (A) to form (C) the rhodium / bisphosphite ligand complex catalyst. The rhodium catalyst precursor may be rhodium dicarbonyl acetylacetonate, RhO 3、 Rh4(CO) 12 , Rh6(CO) 16 , and Rh(NO3)3.

[0082] For example, the rhodium precursor, such as rhodium dicarbonyl acetylacetonate, optionally the starting material (D), the solvent, and (C1) the bisphosphite ligand can be combined by any convenient means, such as, for example, by mixing. The resulting rhodium / bisphosphite ligand complex can be introduced into a reactor, optionally with an excess of the bisphosphite ligand. Alternatively, the rhodium precursor, (D) the solvent, and the bisphosphite ligand can be combined with the starting material (A) and / or (B), the alkenyl functional polyorganosiloxane, in the reactor, and the rhodium / bisphosphite ligand complex can be formed in situ. The relative amounts of the bisphosphite ligand and the rhodium precursor are sufficient to provide a molar ratio of bisphosphite ligand / Rh of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, alternatively 2.5 / 1 to 1.5 / 1. In addition to the rhodium / bisphosphite ligand complex, excess (e.g., uncomplexed) bisphosphite ligand may be present in the reaction mixture. The excess bisphosphite ligand may be the same as or different from the bisphosphite ligand in the complex.

[0083] The amount of (C) rhodium / bisphosphite ligand complex catalyst (catalyst) is sufficient to catalyze the hydroformylation of (B) alkenyl-functional polyorganosiloxane. The exact amount of catalyst will depend on various factors, including the type of alkenyl-functional polyorganosiloxane selected for starting material (B), its exact alkenyl content, and reaction conditions such as temperature and pressure of starting material (A). However, the amount of (C) catalyst may be sufficient to provide a rhodium metal concentration of at least 0.1 ppm, alternatively 0.15 ppm, alternatively 0.2 ppm, alternatively 0.25 ppm, alternatively 0.5 ppm, based on the weight of (B) alkenyl-functional polyorganosiloxane. At the same time, the amount of (C) catalyst may be sufficient to provide a rhodium metal concentration of up to 300 ppm, alternatively up to 100 ppm, alternatively up to 20 ppm, alternatively up to 5 ppm, on the same basis. Alternatively, the amount of (C) catalyst may be sufficient to provide from 0.1 ppm to 300 ppm, alternatively from 0.2 ppm to 100 ppm, alternatively from 0.25 ppm to 20 ppm, alternatively from 0.5 ppm to 5 ppm, based on the weight of the (B) alkenyl-functional polyorganosiloxane.

[0084] (D) Solvents (suitable for use in the hydroformylation reaction) The hydroformylation reaction may be carried out without additional solvent. Alternatively, the hydroformylation reaction may be carried out with (D) a solvent suitable for use in the hydroformylation reaction to facilitate mixing and / or feeding of one or more of the above starting materials, such as (C) catalyst and / or starting material (B), when a solvent such as an alkenyl-functional polyorganosilicate resin is selected for the starting material (B). Solvents are exemplified by aliphatic or aromatic hydrocarbons capable of dissolving the starting materials, such as toluene, xylene, benzene, hexane, heptane, decane, cyclohexane, or combinations of two or more of these. Additional solvents include tetrahydrofuran (THF), dibutyl ether, diglyme, and texanol. Without wishing to be bound by theory, it is believed that a solvent may be used to reduce the viscosity of the starting materials. The amount of solvent is not critical, but if present, the amount of solvent may be 5% to 70% based on the weight of the starting material (B), which is an alkenyl-functional polyorganosiloxane.

[0085] Hydrogenation The process for making the macromonomer described herein may further include 3) preparing the carboxy-functional polyorganosiloxane by a process comprising combining starting materials including the above-mentioned (E) aldehyde-functional polyorganosiloxane, (F) oxygen source, optionally (G) oxidation reaction catalyst, and optionally (H) (second) solvent (suitable for use in the oxidation reaction) under conditions in which an oxidation reaction is carried out, thereby forming an oxidation reaction product including (I) carboxy-functional polyorganosiloxane. Alternatively, in addition to the steps cited above, the process may further include optionally drying one or more of the starting materials (E), (F), (G), and (H) before the oxidation reaction in step 3). The process may further include optionally 4) recovering the carboxy-functional polyorganosiloxane from the oxidation reaction product. Step 4) may be carried out during and / or after step 3).

[0086] (E) Aldehyde-functional polyorganosiloxane The starting material (E) is an aldehyde-functional polyorganosiloxane having at least one aldehyde functional group covalently bonded to silicon per molecule. Alternatively, the aldehyde-functional organosilicon compound may have two or more aldehyde functional groups covalently bonded to silicon per molecule. The aldehyde functional group covalently bonded to silicon is represented by the formula:

[0087] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms, as defined above.

[0088] The aldehyde-functional polyorganosiloxane can be branched, for example, a branched oligomer. The branched oligomer can be represented by the general formula (E1-1): R Ald SiR 12 3, where R Ald But, the formula

[0089] [ka] and each R 12 But R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, where each R 14 But R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3, wherein each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 16 is R 13 and -[OSiR13 2] ii OSiR 13 3, where the subscript ii has a value such that 0≦ii≦100. 12 At least two of -OSi(R 14 ) 3. Alternatively, R 12 All three of the -OSi(R 14 )3.

[0090] Alternatively, in formula (E1-1), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure (E1-2):

[0091] [ka] -OSi(R 15 ) 3 moieties, where R Ald and R 15 Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0092] Alternatively, in formula (E1-1), each R 12 -OSi(R 14 )3, then one R 14 is each R 12 -OSiR 13 (R 14 )2 for each -OSi(R 14 )3 in R 13 Alternatively, -OSiR 13 (R 14 )2 R's 14 each of which is a branched aldehyde-functional polyorganosiloxane oligomer having the following structure (E1-3):

[0093] [ka] -OSi(R 15 ) three parts, In the formula, R Ald , R 13 , and R 15 Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0094] Alternatively, in formula (E1-1), one R 12 is R 13 R 12 Two of them are -OSi(R 14 )3. R 12 Two of them are -OSi(R 14 )3, then one R 14 Each -OSi(R 14 )3 in R 13 Therefore, R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (E1-4):

[0095] [ka] -OSi(R 15 )3, wherein R Ald , R 13 , and R 15 Alternatively, each R 15 is R 13 Each R 13can be methyl. Alternatively, the aldehyde-functional branched polyorganosiloxane can have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule, alternatively 7 to 16 silicon atoms per molecule, alternatively 7 to 10 silicon atoms per molecule, alternatively 10 to 16 silicon atoms per molecule. Examples of aldehyde-functional branched polyorganosiloxane oligomers include those having the formula (E1-5):

[0096] [ka] 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal (which may also be referred to as propyl-aldehyde-tris(trimethylsiloxy)silane), Formula (E1-6):

[0097] [ka] 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propanal (which can also be referred to as methyl-(propyl-aldehyde)-di((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)silane), having the formula (E1-7):

[0098] [ka] and 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propanal (which may also be referred to as (propyl-aldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane), having the formula (E1-8):

[0099] [ka] and 7-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)heptanal (which can also be referred to as (heptyl-aldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane).

[0100] Alternatively, the (E) aldehyde-functional polyorganosiloxane may comprise a linear polydiorganosiloxane having at least one aldehyde functional group, alternatively at least two aldehyde functional groups, per (E2) molecule. For example, the polydiorganosiloxane may have the unit formula (E2-1): (R 4 3SiO 1 / 2 ) a (R Ald R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R Ald R 4 SiO 2 / 2 ) d wherein R Ald is as described above for formula (E1-1), and R 4 is as defined above for formula (B1-1) and the subscripts a, b, c, and d are as defined above for unit formula (B2-1).

[0101] Alternatively, the polydiorganosiloxane of the unit formula (E2-1) has the formula (E2-2):

[0102] [ka] wherein each R 2’ But independently, R 4 and R Ald with the proviso that at least one R2 per molecule is selected from the group consisting of R Ald And each R Ald is as described above for formula (E1-1), and each R 4 is as defined above for formula (B1-1) and the subscript zz is as defined above for formula (B2-2).

[0103] Alternatively, the polydiorganosiloxane may contain two different end groups, i.e., when subscript a = 1 and subscript b = 1. Alternatively, the polydiorganosiloxane may be monofunctional, having one aldehyde functional group per molecule, for example, when subscript a = 1, b = 1, and d = 0 in the unit formula (E2-1). The polydiorganosiloxane may be represented by the formula (E2-3):

[0104] [ka] wherein R Ald is as described above for formula (E1-1), and each R 4 is as defined above for formula (B1-1) and subscript c is as defined above for formula (B2-3).

[0105] Alternatively, the linear aldehyde-functional polydiorganosiloxane of the unit formula (E2-1) may be represented by the unit formula (E2-4): (R 4 2R Ald SiO 1 / 2 )2(R4 2SiO 2 / 2 ) m (R 4 R Ald SiO 2 / 2 ) n , Unit formula (E2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R Ald SiO 2 / 2 ) p or a combination of both (E2-4) and (E2-5). In formulas (E2-4) and (E2-5), each R Ald is as described above for formula (E1-1), and R 4 is as described above for formula (B1-1), and the subscripts m, n, o, and p are as described above for formulas (B2-4) and (B2-5).

[0106] The starting material (E2) is i) bis-dimethyl(propyl-aldehyde)siloxy terminated polydimethylsiloxane, ii) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methyl(propyl-aldehyde)siloxane), iii) bis-dimethyl(propyl-aldehyde)siloxy terminated polymethyl(propyl-aldehyde)siloxane, iv) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(propyl-aldehyde)siloxane), v) bis-trimethylsiloxy terminated polymethyl(propyl-aldehyde ) siloxane, vi) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(propyl-aldehyde)siloxane), vii) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, (propyl-aldehyde)-siloxy terminated polydimethylsiloxane, x) bis-dimethyl ) bis-dimethyl(heptyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xii) bis-dimethyl(heptyl-aldehyde)siloxy terminated polymethyl(heptyl-aldehyde)siloxane), xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xiv) bis-trimethylsiloxy terminated polymethyl(heptyl-aldehyde)siloxane, xv) bis- dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(heptyl-aldehyde)siloxane), xvi) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xvii) bis-dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) bis-dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane),xix) aldehyde-functional polydiorganosiloxanes such as alpha-dimethyl(n-butyl)siloxy-omega-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane); and xx) combinations of two or more of i) through xix).

[0107] (F) Oxygen source Oxygen sources are known in the art and readily available. For example, the oxygen source may be ambient air containing 21% oxygen. Alternatively, the oxygen source may be any gas stream having concentrated or purified oxygen, e.g., 21% to 100% oxygen. Pure or nearly pure (purity >99%) oxygen is known in the art and is commercially available from a variety of sources, e.g., Air Products (Allentown, Pennsylvania, USA). Alternatively, the oxygen source may include a peroxide compound (i.e., a compound having at least one -OO- group per molecule). Suitable peroxide compounds include organic hydroperoxides, such as alkyl hydroperoxides (e.g., tert-butyl hydroperoxide), dialkyl peroxides (e.g., di-tert-butyl peroxide), peroxyacids (e.g., 3-chloroperbenzoic acid), or combinations thereof. The oxygen source can be used in an amount sufficient to provide a superstoichiometric amount of oxygen relative to the aldehyde functionality of the starting material (E) which is the above-mentioned aldehyde-functional polyorganosiloxane. The amount of oxygen source (and reaction conditions) is sufficient to allow at least one of the aldehyde functional groups per molecule of aldehyde-functional polyorganosiloxane to be oxidized. Alternatively, a portion of the aldehyde functional group can be converted to a carboxylic acid group. Alternatively, complete conversion of the aldehyde functional group to a carboxylic acid functional group can be performed.

[0108] (G) Oxidation reaction catalyst The oxidation catalyst used in the process for preparing the carboxy-functional polyorganosiloxane (step 3)) can be a heterogeneous oxidation catalyst, a homogeneous oxidation catalyst, or a combination thereof.

[0109] Exemplary oxidation catalysts may include metal complexes or compounds. Metal complexes or compounds may include metals selected from the group consisting of cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), rhodium (Rh), selenium (Se), and tungsten (W), and combinations of two or more thereof. For example, manganese acetate (Mn(OAc)2) may be used. Non-metallic catalysts such as those described in RSC Adv., 2013, 3, 18931-18937 may also be suitable. The metal complex may further include a ligand such as acetate. Alternatively, the oxidation catalyst may include Rh. Without wishing to be bound by theory, it is believed that when the above hydroformylation process is used to make an aldehyde-functional polyorganosiloxane and (C) a Rh complex is present to be used as a hydroformylation catalyst, the Rh complex may function as an oxidation catalyst. Alternatively, (G) the oxidation catalyst may comprise an organic catalyst containing an N-hydroxy functional group. Exemplary organic catalysts include N-hydroxyphthalimide or 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). Suitable oxidation catalysts are known in the art and commercially available. For example, N-hydroxyphthalimide and TEMPO are available from various sources, including Sigma-Aldrich, Inc. (St. Louis, Missouri, USA).

[0110] The amount of (G) oxidation catalyst used in step 3) of the process depends on a variety of factors, including whether the process is run in batch or continuous mode, the selection of the aldehyde-functional polyorganosiloxane, whether a heterogeneous or homogeneous oxidation catalyst is selected, and reaction conditions such as temperature and pressure. However, the amount of catalyst (for batch or continuous processes using a homogeneous oxidation catalyst) can be from 0.001 mol% to 1 mol%, alternatively 0.005 mol% to 0.5 mol%, based on the number of moles of aldehyde functional groups in the starting (E) aldehyde-functional polyorganosiloxane. Alternatively, the amount of catalyst can be at least 0.001, alternatively at least 0.005, alternatively at least 0.01, alternatively at least 0.1 mol%, while at the same time, the amount of catalyst can be up to 1, alternatively up to 0.75, alternatively up to 0.5, alternatively up to 0.25, alternatively up to 0.1 mol%, on the same basis. Alternatively, when the oxidation reaction is carried out in a continuous mode, for example by packing the heterogeneous oxidation catalyst in a fixed bed reactor, the amount of the oxidation catalyst is -1 Reactor volume (filled with oxidation catalyst) to achieve a space-time of 1 m 2 It may be sufficient to provide sufficient catalyst surface area to achieve 8-10 kg / hr of substrate per sintered body.

[0111] (H) A second solvent (suitable for use in the oxidation reaction process) The solvent that may be optionally used in step 3) of the process to promote the oxidation reaction may be selected from those solvents that are neutral to the oxidation reaction. The following are specific examples of such solvents: ketones such as acetone and 3-pentanone; esters; carboxylic acids; aliphatic hydrocarbons such as hexane, heptane, and paraffinic solvents; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. These solvents may be used individually or in combination of two or more. This second solvent is the starting material (H) and may be the same or different from the starting material (D) when the above hydroformylation process is used to prepare the aldehyde-functional polyorganosiloxane used as starting material (E).

[0112] Oxidation reaction conditions The oxidation reaction in step 3) can be carried out using a pressurized oxygen source. The partial pressure of oxygen can be 3 psia (20 kPa) to 100 psia (690 kPa), alternatively 3 psia (20 kPa) to 15 psia (104 kPa). The reaction can be carried out at a temperature of 0 to 200°C. The temperature in step 3) can depend on various factors, such as the pressure selected, the aldehyde-functional polyorganosiloxane selected, and the reactor configuration. Without wishing to be bound by theory, it is believed that the oxidation reaction rate can increase with increasing temperature, but the oxygen solubility in the aldehyde-functional polyorganosiloxane can decrease with increasing temperature, and therefore the temperature can be selected to have sufficient oxygen solubility to allow the oxidation reaction to proceed while maximizing the reaction rate. The temperature can be, for example, 0 to 100°C. Alternatively, temperatures of 23°C to 100°C, alternatively 20°C to 50°C, can be suitable. Alternatively, the oxygen source partial pressure used may be at least 3, alternatively at least 4, alternatively at least 6, alternatively at least 8, alternatively at least 10 psig, while the pressure may be up to 100, alternatively up to 75, alternatively up to 50, alternatively up to 25, alternatively up to 15 psig. The temperature for the oxidation reaction may be at least 20, alternatively at least 25, alternatively at least 30°C, while the temperature may be up to 100, alternatively up to 95, alternatively up to 90°C.

[0113] The oxidation reaction can be carried out in batch or continuous mode. In batch mode, step 3) of the process described herein can be carried out for 1 minute to 250 hours, although the reaction time depends on various factors including the amount of catalyst and the reaction temperature. Alternatively, the oxidation reaction can be carried out for at least 1 minute, alternatively at least 2 minutes, alternatively at least 1 hour, alternatively at least 2.5 hours, alternatively at least 3 hours, alternatively at least 3.3 hours, alternatively at least 3.7 hours, alternatively at least 4 hours, alternatively at least 4.4 hours, alternatively at least 5.5 hours, while the oxidation reaction can be carried out for up to 250 hours, alternatively 200 hours, alternatively up to 175 hours, alternatively up to 150 hours, alternatively up to 125 hours, alternatively up to 100 hours, alternatively up to 75 hours.

[0114] Alternatively, in batch mode, the end point of the oxidation reaction may be considered to be the time when a decrease in the oxygen source pressure is no longer observed after continuing the reaction for an additional 1-2 hours. If the oxygen source pressure decreases during the course of the reaction, it may be desirable to repeat the introduction of the oxygen source and maintain it under a higher pressure to shorten the reaction time. Alternatively, the reactor can be repressurized with the oxygen source one or more times to achieve a sufficient supply of oxygen for the reaction of the aldehyde while maintaining a reasonable reactor pressure. When repressurizing the reactor to terminate the oxidation of the aldehyde, the same oxygen source or a different oxygen source (e.g., more concentrated in O2) can be used.

[0115] The oxidation reaction in step 3) may optionally further comprise irradiating the reaction mixture with ultra-violet (UV) radiation. The UV radiation may have a peak wavelength of 285 nm and may be provided by any convenient means such as an LED or other lamp. Alternatively, UV radiation having a wavelength of 200 nm to 460 nm, alternatively 250 nm to 350 nm, alternatively 265 nm to 315 nm may be used. The exposure dose depends on various factors including the wavelength selected and other reaction conditions. For example, 9 μW / cm 2A UV dose of about 1000 nm can be used. Without wishing to be bound by theory, it is believed that UV irradiation can increase the rate of the oxidation reaction in step 3).

[0116] After the oxidation reaction, the oxidation reaction catalyst may be separated in a pressurized atmosphere by any convenient means, such as, for example, filtration or adsorption using diatomaceous earth or activated carbon, sedimentation, centrifugation, by maintaining the oxidation reaction catalyst in a structured packing or other fixed structure, or by a combination of these (e.g., step 4)).

[0117] The carboxy-functional polyorganosiloxanes prepared as described above have at least one carboxy-functional group covalently bonded to silicon per molecule. Alternatively, the carboxy-functional polyorganosiloxanes may have more than one carboxy-functional group covalently bonded to silicon per molecule. The carboxy-functional group R covalently bonded to silicon Car is the expression:

[0118] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms, as described and exemplified above. Car are independently -(C2H4)C(=O)OH, -(C3H6)C(=O)OH, and -(C6H 12 The carboxy-functional polyorganosiloxane may have any one of the formulas shown above for the aldehyde-functional polyorganosiloxane, except that one or more of R Ald But R Car is replaced by

[0119] Transvinylation The process for preparing the vinyl ester functional siloxane macromonomer described herein comprises, under conditions for effecting a transvinylation reaction, (I) the carboxy-functional polyorganosiloxane described above; (J) formula

[0120] [ka] wherein R 3 is 1 to 6 alkyl groups; (K) a transvinylation reaction catalyst; optionally (L) a (third) solvent; combining the starting materials, optionally including (X) an inhibitor, This involves preparing a reaction mixture that includes a vinyl-ester functional macromonomer.

[0121] A transvinylation reaction can be carried out in step 5) when a process including a hydroformylation reaction and an oxidation reaction as described above is used to prepare (I) the carboxy-functional polyorganosiloxane.

[0122] The transvinylation reaction (e.g., step 5)) can be carried out at ambient pressure. The transvinylation reaction can be carried out at a temperature of 0 to 150°C. The temperature for the transvinylation reaction can depend on a variety of factors including the carboxy-functional organosilicon compound selected and the reactor configuration. The temperature can be, for example, 0°C to 150°C. Alternatively, temperatures of 23°C to 100°C, alternatively 30°C to 80°C, alternatively 40°C to 70°C, alternatively 50°C to 60°C can be suitable.

[0123] The transvinylation reaction can be carried out in batch or continuous mode. In batch mode, the transvinylation reaction can be carried out for 1 minute to 250 hours, although the reaction time depends on various factors including the amount of transvinylation reaction catalyst and the reaction temperature. Alternatively, the oxidation reaction can be carried out for at least 1 minute, alternatively at least 2 minutes, alternatively at least 1 hour, alternatively at least 2.5 hours, alternatively at least 3 hours, alternatively at least 3.3 hours, alternatively at least 3.7 hours, alternatively at least 4 hours, alternatively at least 4.4 hours, alternatively at least 5.5 hours, while the transvinylation reaction can be carried out for up to 250 hours, alternatively 200 hours, alternatively up to 175 hours, alternatively up to 150 hours, alternatively up to 125 hours, alternatively up to 100 hours, alternatively up to 75 hours.

[0124] The process for preparing the vinyl ester functional siloxane macromonomer may optionally further comprise recovering the vinyl-ester functional macromonomer. This may be carried out in step 6) when a process comprising a hydroformylation reaction and an oxidation reaction is used to prepare the above carboxy-functional polyorganosiloxane. Recovering the macromonomer may be carried out by any convenient means, such as stripping and / or distillation, optionally under heating and / or reduced pressure.

[0125] (I) Carboxy-functional polyorganosiloxane The starting material (I) in the process for preparing the vinyl-ester functional macromonomer is a carboxy-functional polyorganosiloxane. In addition to or instead of the carboxy-functional polyorganosiloxane prepared by the process including hydroformylation and oxidation reactions described above, commercially available carboxy-functional organosilicon compounds can be used. For example, MCR-B12 is a mono-carboxy-undecanoate terminated, monobutyl terminated polydimethylsiloxane having a molecular weight of 1500 g / mol, commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA). Other carboxyalkyl terminated polydimethylsiloxanes include bis-carboxypropyl terminated polydimethylsiloxanes and bis-carboxydecyl terminated polydimethylsiloxanes having molecular weights ranging from 1,000 to 28,000, also from Gelest under the trade names DMS-B12, DMS-B25, and DMS-B31.

[0126] Alternatively, (I) the carboxy-functional polyorganosiloxane may be branched. (I1) The branched carboxy-functional polyorganosiloxane may be represented by the general formula (I1-1): R Car SiR 12 3, where R Car But, the formula

[0127] [ka] wherein G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms as described above for starting material (E), and each R 12 But R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, where each R 14 But R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 133, wherein each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 16 is R 13 and -[OSiR 13 2] ii OSiR 13 3, where the subscript ii has a value such that 0≦ii≦100. 12 At least two of -OSi(R 14 ) 3. Alternatively, R 12 All three of the -OSi(R 14 )3.

[0128] Alternatively, in formula (I1-1), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure (I1-2):

[0129] [ka] -OSi(R 15 ) 3 moieties, where R Car and R 15 is as described above. Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0130] Alternatively, in formula (I1-1), each R 12 -OSi(R 14 )3, then one R 14 is each R 12 -OSiR 13 (R 14 )2 for each -OSi(R 14 )3 in R 13 Alternatively, -OSiR 13(R 14 )2 R's 14 each of which is a branched carboxy-functional polyorganosiloxane oligomer having the following structure (I1-3):

[0131] [ka] -OSi(R 15 ) three parts, In the formula, R Car , R 13 , and R 15 is as described above. Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0132] Alternatively, in formula (I1-1), one R 12 is R 13 R 12 Two of them are -OSi(R 14 )3. R 12 Two of them are -OSi(R 14 )3, then one R 14 Each -OSi(R 14 )3 in R 13 Therefore, R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 )2 for each R 14 is a branched polyorganosiloxane oligomer having the following structure (I1-4):

[0133] [ka] -OSi(R 15 )3, wherein R Car , R 13 , and R 15 is as described above. Alternatively, each R 15 is R13 Each R 13 can be methyl. Alternatively, the carboxy-functional polyorganosiloxane can have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule, alternatively 7 to 16 silicon atoms per molecule, alternatively 7 to 10 silicon atoms per molecule, alternatively 10 to 16 silicon atoms per molecule. Examples of carboxy-functional polyorganosiloxane oligomers include those represented by the formula (I1-5):

[0134] [ka] 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanoic acid, having the formula (I1-6):

[0135] [ka] 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propanoic acid, having the formula (I1-7):

[0136] [ka] and 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propanoic acid (Sil0Pr-acid), having the formula (I1-8):

[0137] [ka] and 7-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)heptanoic acid (Sil0Hep-acid).

[0138] Alternatively, the carboxy-functional polyorganosiloxane (I) may comprise a linear polydiorganosiloxane having at least one carboxy-functional group, alternatively at least two carboxy-functional groups, per molecule (I2). For example, the polydiorganosiloxane may be represented by the unit formula (I2-1): (R 4 3SiO 1 / 2 ) a (R Car R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R Car R 4 SiO 2 / 2 ) d wherein R Car is as defined above for formula (I1-1), and each R 4 is as described above for starting material (B1-1) and the subscripts a, b, c, and d are as described above for unit formula (B2-1).

[0139] Alternatively, the polydiorganosiloxane of the unit formula (I2-3) is represented by the formula (I2-2):

[0140] [ka] wherein each R 2” But independently, R 4 and R Car with the proviso that at least one R 2” But R Car And each R Car is as defined above for formula (I1-1), and each R 4is as defined above for formula (B1-1) and the subscript zz is as defined above for formula (B2-2).

[0141] Alternatively, the polydiorganosiloxane may contain two different end groups, i.e., when subscript a = 1 and subscript b = 1. Alternatively, the polydiorganosiloxane may be monofunctional, having one carboxy functional group per molecule, for example, when subscript a = 1, b = 1, and d = 0 in the unit formula (I2-1). The polydiorganosiloxane may be represented by the formula (I2-3):

[0142] [ka] wherein R Car is as defined above for formula (I1-1), and each R 4 is as defined above for formula (B1-1) and subscript c is as defined above for formula (B2-3).

[0143] Alternatively, the linear carboxy-functional polydiorganosiloxane of the unit formula (I2-1) may be represented by the unit formula (I2-4): (R 4 2R Car SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R Car SiO 2 / 2 ) n , Unit formula (I2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R Car SiO 2 / 2 ) p In formulae (I2-4) and (I2-5), each R Car is as described above for formula (I1-1), and each R4 is as described above for formula (B1-1), and the subscripts m, n, o, and p are as described above for formulas (B2-4) and (B2-5).

[0144] The starting material (I2) is i) bis-dimethyl(propanoic acid)siloxy terminated polydimethylsiloxane, ii) bis-dimethyl(propanoic acid)siloxy terminated poly(dimethylsiloxane / methyl(propanoic acid)siloxane), iii) bis-dimethyl(propanoic acid)siloxy terminated polymethyl(propanoic acid)siloxane, iv) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(propanoic acid)siloxane), v) bis-trimethylsiloxy terminated polymethyl(propanoic acid)siloxane, vi) bis-dimethyl(propanoic acid)siloxy terminated poly (dimethylsiloxane / methylphenylsiloxane / methyl(propanoic)siloxane), vii) bis-dimethyl(propanoic)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethyl(propanoic)siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, (propanoic)-siloxy terminated polydimethylsiloxane, x) bis-dimethyl(heptanoic)siloxy terminated polydimethylsiloxane, xi) bis-dimethyl(heptanoic)siloxy terminated poly(dimethylsiloxane xii) bis-dimethyl(heptanoic acid)siloxy terminated polymethyl(heptanoic acid)siloxane), xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(heptanoic acid)siloxane), xiv) bis-trimethylsiloxy terminated polymethyl(heptanoic acid)siloxane, xv) bis-dimethyl(heptanoic acid)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(heptanoic acid)siloxane), xvi) bis-dimethyl(propanoic acid)siloxy terminated poly(di xvii) bis-dimethyl(heptanoic acid)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane); xviii) bis-dimethyl(heptanoic acid)-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane); xix) alpha-dimethyl(n-butyl)siloxy-omega-dimethyl(propanoic acid)siloxy terminated poly(dimethylsiloxane); and xx) combinations of two or more of i)-xix).

[0145] The starting material (I) can be any one of the carboxy-functional organosilicon compounds described above. Alternatively, the starting material (I) can include a mixture of two or more of the carboxy-functional organosilicon compounds.

[0146] (J) Vinyl acetate functional compounds In the process for preparing a vinyl ester-functional polyorganosiloxane, the starting material (J) is a vinyl acetate-functional compound. The vinyl acetate-functional compound is represented by the formula formula

[0147] [ka] wherein R 3 is an alkyl group having 1 to 6 carbon atoms. 3 Suitable alkyl groups for include methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n-butyl, isobutyl, sec-butyl, and t-butyl), pentyl and hexyl, as well as branched isomers of 5 or 6 carbon atoms. Alternatively, starting material (J) can be vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl laurate, and combinations of two or more of these. Alternatively, R 3 can be methyl. These vinyl acetate functional compounds are known in the art and are commercially available from a variety of sources, such as Sigma Aldrich, Inc. (St. Louis, Missouri, USA). Alternatively, the starting material (J) can include vinyl acetate.

[0148] The amount of (J) the vinyl acetate functional compound can be from 0.1 molar equivalents to 20 molar equivalents based on the carboxy functionality content of (I) the carboxy functional polyorganosiloxane.

[0149] (K) Transvinylation reaction catalyst The transvinylation reaction catalyst used herein may include a metal-ligand complex. The metal may be cobalt (Co), iron (Fe), iridium (Ir), nickel (Ni), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), or ruthenium (Ru). Suitable metal-ligand complexes are described, for example, in Biomacromolecules 2019,20,4-26. Alternatively, the transvinylation reaction catalyst may be a palladium-ligand complex. The ligand may be a phenanthroline. For example, the transvinylation reaction catalyst may be prepared by a process that includes combining a palladium catalyst precursor with a phenanthroline ligand under conditions to form a complex, which may then be introduced into a transvinylation reaction medium that includes one or both of the starting materials (I) and / or (J) described above. The palladium catalyst precursor may be any Pd(II) compound. Alternatively, for in situ formation of the palladium / phenanthroline ligand complex, the palladium / phenanthroline complex may be formed in situ by introducing a palladium catalyst precursor into the reaction medium and introducing a phenanthroline ligand into the reaction medium (e.g., before, during, and / or after introduction of the palladium catalyst precursor). The palladium / phenanthroline ligand complex may be activated by heating to form the (K) transvinylation reaction catalyst. The palladium catalyst precursor is exemplified by palladium acetate.

[0150] The palladium catalyst precursor, e.g., palladium acetate, optionally the starting material (L), the (third) solvent, and the phenanthroline ligand may be combined by any convenient means, e.g., by mixing. The resulting palladium / phenanthroline ligand complex may be introduced into the reactor, optionally with an excess of the phenanthroline ligand. Alternatively, the palladium catalyst precursor, (L) solvent, and the phenanthroline ligand may be combined with the starting materials (I) and / or (J) in the reactor, and the (K) transvinylation reactant may be formed in situ. The relative amounts of the phenanthroline ligand and the palladium catalyst precursor are sufficient to provide a molar ratio of phenanthroline ligand / Pd of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, alternatively 2.5 / 1 to 1.5 / 1.

[0151] The amount of (K) transvinylation catalyst is sufficient to catalyze the transvinylation reaction under the conditions described above, and may be from 0.0001 mole % to 10 mole % of (K) transvinylation catalyst, based on the carboxy functionality of (I) the carboxy-functional polyorganosiloxane.

[0152] (L) A (third) solvent suitable for use in the transvinylation reaction The starting material (L) is a solvent that can be used in the transvinylation reaction in the process described herein. The solvent can be used to provide the starting material and / or to facilitate the transvinylation reaction. The solvent used in the transvinylation reaction can be aprotic. The solvent used in the transvinylation reaction can be an aliphatic hydrocarbon, such as hexane. The amount of the (L) solvent suitable for use in the transvinylation reaction is not particularly limited and can be, for example, 0 to 95% by weight, based on the total weight of the (I) carboxy-functional polyorganosiloxane, (J) vinyl acetate-functional compound, and (K) transvinylation reaction catalyst.

[0153] (X) Inhibitor Starting material (X) is optionally an inhibitor that may be added during the transvinylation reaction to minimize or prevent polymerization of vinyl ester functional groups. The inhibitor may include a phenolic compound, a quinone or hydroquinone compound, an N-oxyl compound, a phenothiazine compound, a hindered amine compound, or a combination thereof.

[0154] Examples of phenolic compounds include phenol, alkylphenols, aminophenols (e.g., p-aminophenol), nitrosophenols, and alkoxyphenols. Specific examples of such phenolic compounds include o-, m-, and p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, or are 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-oxybiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, pyrocatechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohex-1'-yl)-4,6-dimethylphenol, 2- or 4-(1'-phenylethyl-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, phenol, 2,6-di-tert-butylphenol, nonylphenol, octylphenol, 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy 4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5,-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate or pentaerythrityl tetrakis[p-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-sec-butyl-2,4-dinitrophenol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis[(3',5'- di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine 1,1-methanediaminebis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid hydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionic acid hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohex-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen- 1-yl) sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris-[1'-(3Δ,5”-di-tert-butyl-4”-hydroxyphen-1”-yl)methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane and tert-butylcatechol, p- Nitrosophenols, p-nitroso-o-cresol, methoxyphenols (guaiacol, pyrocatechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether, MEHQ), mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxyphenyl hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillone), eugenol, dihydroeugenol, isoeugenol, tocopherols, such as α-, β-, γ-, δ-, and ε-tocopherol, tocol, α-tocopherol hydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), and combinations thereof.

[0155] Suitable quinones and hydroquinones include hydroquinone, hydroquinone monomethyl ether (4-methoxyphenol), methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methylpyrocatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, tetramethyl-p-benzoquinone, phenyl-p-benzoquinone, 2,5-dimethyl-3-benzyl-p-benzoquinone, 2-isopropyl-5-methyl-p-benzoquinone (thymoquinone), 2, 6-Diisopropyl-p-benzoquinone, 2,5-Dimethyl-3-hydroxy-p-benzoquinone, 2,5-Dihydroxy-p-benzoquinone, Embelin, Tetrahydroxy-p-benzoquinone, 2,5-Dimethoxy-1,4-benzoquinone, 2-Amino-5-methyl-p-benzoquinone, 2,5-Bisphenylamino-1,4-benzoquinone, 5,8-Dihydroxy-1,4-naphthoquinone, 2-Anilino-1, 4-naphthoquinone, anthraquinone, N,N-dimethylindoaniline, N,N-diphenyl-p-benzoquinone diimine, 1,4-benzoquinone dioxime, 3,3'-di-tert-butyl-5,5'-dimethyldiphenoquinone, p-rosolic acid (aurin), 2,6-di-tert-butyl-4-benzylidenebenzoquinone, 2,5-di-tert-amylhydroquinone, and combinations thereof.

[0156] Suitable N-oxyl compounds (i.e., nitroxyl or N-oxyl groups) include compounds having at least one NO group, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl (tetramethylpiperidin-N-oxyl, T EMPO), 4,4',4"-tris(2,2,6,6-tetramethylpiperidine-N-oxyl)phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, bis(2,2,6,6-tetramethylpiperidin-1-yl)oxyl sebacate, 1-oxy 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl (4-tert-butyl)benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,10-decane dioate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butyl malonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]triazine, N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-bisformyl-1,6-diaminohexane, 4,4'-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one) and combinations thereof.

[0157] Other compounds suitable for use in or as an inhibitor include phenothiazine (PTZ) and compounds having a similar structure, such as phenoxazine, promazine, N,N'-dimethylphenazine, carbazole, N-ethylcarbazole, N-benzylphenothiazine, N-(1-phenylethyl)phenothiazine, N-alkylated phenothiazine derivatives such as N-benzylphenothiazine and N-(1-phenylethyl)phenothiazine. Alternatively, the inhibitor may be selected from the group consisting of 4-methoxyphenol (MEHQ), (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), 4-hydroxy(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4HT), bis(2,2,6,6-tetramethylpiperidin-1-yl)oxyl sebacate (Bis-TEMPO), polymer-bound TEMPO, or combinations thereof.

[0158] Inhibitors may be used to inhibit polymerization of vinyl ester functional groups prior to use of a starting material (e.g., starting material (J)) and / or during and / or after the transvinylation reaction. The amount of (X) inhibitor will depend on a variety of factors, including the type and amount of (J) vinyl acetate functional compound, but the (X) inhibitor may be present in an amount of from 10 ppm to 10,000 ppm, alternatively from 50 ppm to 1,000 ppm, based on the weight of (J) vinyl acetate functional compound and / or based on the weight of (M1) vinyl ester functional siloxane macromonomer (e.g., if added after the transvinylation reaction).

[0159] The transvinylation reaction process described above can be used to produce vinyl ester functional siloxane macromonomers useful as starting material M1) (above) in the process for making the copolymers described herein. Starting material M1) is used in a mixture with monomers M2) alkenyl esters of aliphatic fatty acids and optional M3) additional monomers introduced above and described in detail below.

[0160] Starting material M2) vinyl esters of aliphatic fatty acids The starting material M2) used in the process for preparing the silicone-vinyl ester copolymer is a vinyl ester of an aliphatic fatty acid. The starting material M2) has the formula:

[0161] [ka] wherein R 24 is hydrogen or an alkyl group having 1 to 14 carbon atoms. 24The alkyl group for R may be linear or branched. For example, the alkyl group may be methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, isobutyl, sec-butyl, and / or tert-butyl), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl (and saturated branched isomers having 5 to 14 carbon atoms). Alternatively, R 24 Alternatively, the starting material M2) may include vinyl acetate, which is commercially available from Sigma-Aldrich, Inc. (St. Louis, Missouri, USA).

[0162] The amount of M2) vinyl ester of an aliphatic fatty acid in the mixture of monomers will depend on a variety of factors, including the selection and amount of each of the other monomers in the mixture, as well as the desired end use of the copolymer. However, the amount of M2) vinyl ester of an aliphatic fatty acid can be from 1% to 99%, alternatively 40% to 70%, based on the total weight of all monomers in the mixture of monomers (e.g., based on the total weight of M1), M2), and M3) as described herein).

[0163] Starting Material M3) Optional Additional Monomers The mixture of monomers described above may optionally further comprise an additional ethylenically unsaturated monomer different from the starting materials M1) and M2) described above, but capable of copolymerizing with the starting materials M1) and M2). The optional additional monomer may be of the formula:

[0164] [ka] wherein R 18 is hydrogen or a methyl group, R 19 is hydrogen or an alkyl group of 1 to 22 carbon atoms, and the alkyl group can be linear or branched. 19Alkyl groups for are exemplified by methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, isobutyl, tert-butyl, and sec-butyl), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl (and branched alkyl groups of 5 to 14 carbon atoms). 18 can be hydrogen. Alternatively, R 19 can be an alkyl group of 1 to 14 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.

[0165] Alternatively, the optional additional monomer may be a cyclic ketene acetal monomer. The cyclic ketene acetal monomer may be one described in U.S. Patent Application Publication No. 2020 / 0325261 to Carter et al. The cyclic ketene acetal monomer may be a monomer having the formula:

[0166] [ka] where the subscript jj is 0, 1, or 2; 20 is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R 21 and R 22 are each independently selected from hydrogen, an alkyl group of 1 to 12 carbon atoms, phenyl, or vinyl, with the proviso that R 21 and R 22 together with the carbon atom to which they are attached form a fused benzene ring or a fused alicyclic ring having 3 to 7 carbon atoms; R 21’ and R 22’ are each independently selected from hydrogen or an alkyl group of 1 to 12 carbon atoms, with the proviso that R 21 and R 21’ and / or R 22 and R 22’provided that the exocyclic double bond can be formed. Examples of cyclic ketene acetal monomers where jj=2 in the above formula include 4,7-dimethyl-1,2-methylene-1,3-dioxepane, 2-methylene-1,3-dioxepane (MDO), 2-methylene-4,7-dihydro-1,3-dioxepine, and 3-methylene-1,5-dihydrobenzo[e][1,3]dioxepine, and combinations thereof. Examples of cyclic ketene acetal monomers where jj=1 in the above formula include 4-methyl-2-methylene-1,3-dioxane, 4,6-dimethyl-2-methylene-1.3-dioxane, 5,5-dimethyl-2-methylene-1.3-dioxane, 2-methylene-1,3-dioxane, 2-methylene-4-phenyl-1,3-dioxane, 3,9-dimethylene-2,4,8,10-tetraoxaspiro[5.5]undecane, and combinations thereof. Examples of cyclic ketene acetal monomers where jj=0 in the above formula include 2-methylene-1,3-dioxolane, 4-methyl-2-methylene-1,3-dioxolane, 4-hexyl-2-methylene-1,3-dioxolane, 4-decyl-2-methylene-1,3-dioxolane, 4,5-dimethyl-2-methylene-1,3-dioxolane, 2-methylenehexahydrobenzo[d][1,3]dioxole, and combinations thereof.

[0167] Alternatively, M3) optional additional monomers may be selected from the group consisting of acrylic acid, MDO, and combinations thereof. Suitable additional monomers are known in the art and commercially available, for example, from Sigma-Aldrich, Inc.

[0168] The amount of M3) additional monomer that may optionally be included in the mixture of monomers depends on a variety of factors, including the selection and amount of other monomers in the mixture, as well as the desired end use of the copolymer. However, the amount of M3) additional monomer may be from 0 to 20%, alternatively from 0 to 10%, based on the total weight of all monomers in the mixture of monomers (e.g., based on the total weight of M1), M2), and M3) as described herein).

[0169] Methods for preparing copolymers Silicone-vinyl ester copolymers (introduced above) may be prepared by a process comprising: I) combining starting materials comprising a mixture of monomers comprising M1), M2), and optionally M3) above, N) a radical initiator, and optionally O) a (fourth) solvent (i.e., a solvent suitable for use in the copolymerization reaction of the mixture of monomers) under conditions for free radical polymerization, thereby forming a reaction mixture. The process may further comprise II) quenching the reaction mixture after step I). The process may further comprise, optionally, III) recovering the copolymer from the reaction mixture, and / or IV) dissolving the copolymer in a simple alcohol such as ethanol, and / or V) performing a solvent exchange to dissolve the copolymer in P) a carrier suitable for use in personal care compositions.

[0170] In step I), the mixture of monomers including M1), M2), and, if present, M3), as described above, can be copolymerized by mixing and heating to form a reaction mixture. The copolymerization can be carried out by free radical polymerization, and N) a radical initiator can be combined with the mixture of monomers in step I).

[0171] N) Radical initiator The starting material N) which is a radical initiator can be, for example, an azo-based compound, an organic peroxide, and combinations thereof. The radical initiator can include, for example, an azo-based compound such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methyl)butyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), and combinations of two or more thereof. Alternatively, the radical initiator can include organic peroxides such as, for example, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxypivalate, cyclohexanone peroxide, isopropyl cumyl hydroperoxide, di-tert-butyl peroxide, diisopropyl percarbonate, tert-butyl perbenzoate, tert-butyl peroctanoate, bis(3,5,5-trimethyl)hexanoyl peroxide, tert-butyl peroxypivalate, and combinations of two or more thereof. Radical initiators are known in the art and are commercially available. For example, organic peroxides such as peroxydicarbonate, diacyl peroxide, dialkyl peroxide, and peroxyether are available from Arkema Inc. (King of Prussia, Pennsylvania, USA) under the trade name LUPEROX™. Tert-amyl peroxypivalate is available from AkzoNobel under the trade name TRIGONOX™. The amount of radical initiator may be from 0.1 to 5 parts by weight per 100 parts by weight of the mixture of monomers used in step I).Other examples of suitable initiators for the free radical polymerization of these vinyl ester monomers can be found in the product brochure entitled "Initiators for acrylics manufacturing" by AkzoNobel, published in 2018, and the product brochure entitled "azo polymerization initiators comprehensive catalog" by Wako Pure Chemical Industries, Ltd.

[0172] The copolymerization in step I) may be a solution polymerization, and O) a solvent suitable for use in radical polymerization reactions may be added in step I). One or more of the starting materials (e.g., N) that are radical initiators, and / or a mixture of M1) macromonomers, M2) alkenyl esters of aliphatic fatty acids, and optionally M3) may be provided in a solvent. For example, the radical initiator may be provided in mineral spirits. The solvent for solution polymerization may be in addition to or instead of the solvent for providing the starting materials. The solvent in step I) may be a solvent of formula R 2 OH, where R 2 is a monovalent hydrocarbon group of 1 to 4 carbon atoms, alternatively an alkyl group of 1 to 4 carbon atoms. The simple alcohol is exemplified by ethanol, n-propanol, isopropanol, n-butanol, t-butanol, or a combination thereof. The simple alcohol may include ethanol. Alternatively, the simple alcohol may be selected from ethanol, isopropanol, or a combination thereof. Alternatively, the solvent in step I) is a carboxylic acid having the formula R 2 O(CO)R 5 wherein R 2 is as defined above, and R 5 is hydrogen or an alkyl group having 1 to 14 carbon atoms (R 3 As described above for (a) above). Alternatively, the simple aliphatic ester may be ethyl acetate. Alternatively, the solvent in step I) may be a compound of formula R 2 OH and one or more simple alcohols of formula R2 O(CO)R 5 with one or more simple aliphatic esters of the above.

[0173] Step I) can be carried out in batch, semi-batch or continuous mode, for example at a temperature of >30°C, alternatively 50°C to 150°C, for a period of 3 to 20 hours. In semi-batch mode, fractions of the reagents can be dosed to the reactor (e.g., radical initiator, mixture of monomers, and / or solvent in which the mixture of radical initiator and monomers is fed), and the remaining reagents are metered into the reactor over a target feed time, typically 1 to 20 hours. In continuous mode, the reagents are continuously metered into the reactor and the reaction mixture containing the copolymer is continuously removed from the reactor. The starting materials used in step I) can be free of acid.

[0174] In step II), the quenching may be carried out by cooling the reaction mixture to 25±5° C.

[0175] The method may optionally further comprise step III) recovering the copolymer from the reaction mixture. The recovery of the copolymer may be carried out by any convenient means. For example, if any one or more unreacted monomers are present and / or if a solvent is used, these may be removed, for example, by heating, optionally with reduced pressure. For example, stripping and / or distillation may be used to purify the copolymer. Alternatively, the unreacted monomer may be reduced by a chemical chase in which additional radical initiator is added to consume the unreacted monomer and reduce its level to a sufficiently low level (for example, <500 ppm) that the unreacted monomer does not need to be removed.

[0176] The method may optionally further comprise, for example if no solvent is used in step I), IV) dissolving the copolymer in a simple alcohol such as ethanol.

[0177] Alternatively, the method may optionally further comprise step V) solvent exchange after II), if present, or after step III), or after step IV).If a different carrier for the P) copolymer is desired, the above O) solvent may be removed and replaced with a different carrier, such as a carrier suitable for personal care. Alternatively, the P) carrier may be a monohydric alcohol such as ethanol, isopropyl alcohol, n-propanol, tert-butanol, and sec-butanol; a dihydric alcohol such as 1,3-propanediol, 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, and octylene glycol; a trihydric alcohol such as trimethylolpropane and 1,2,6-hexanetriol; a tetrahydric or higher alcohol such as pentaerythritol and xylitol; an alcohol including a sugar alcohol such as sorbitol; acetone and methyl ethyl ketone; The organic solvent may be selected from the group consisting of ketones including ketones, fatty esters including isopropyl myristate and isopropyl palmitate, natural oils including sunflower seed oil, caprylic / capric triglyceride, coconut oil, castor oil, argan oil, and jojoba oil, hydrocarbon oils including isododecane, isohexadecane, paraffin, isoparaffin, squalane, and squalene, and alkanes of 9 to 11 carbon atoms, siloxane or silicone oils such as decamethylcyclopentasiloxane (D5) and linear low viscosity polydimethylsiloxane (PDMS) (e.g., having a viscosity of 1.5 cSt to 6 cSt at 25° C. by rotational viscometer using a Brookfield viscometer), glycerin, glycerol, or a combination of two or more thereof. Such organics are commercially available. For example, D5 and linear polydimethylsiloxanes having the above viscosities are available from Dow Silicones Corporation, Midland, Michigan, USA.

[0178] Copolymer The copolymers prepared as above may comprise the following unit formula:

[0179] [ka] In the formula, R 12 , G, and R 3 is as above, and subscripts z1, z2, and z3 represent weight fractions, z1 is 0.01 to 0.99, z2 is 0.01 to 0.99, and z3 is 0 to 0.2, with the proviso that the quantity (z1+z2+z3)=1, U represents units derived from the starting material M3), and E is an end-blocking moiety. Alternatively, z1 can be 0.3 to 0.6. Alternatively, z3 can be 0.4 to 0.7. Alternatively, z3 can be 0 to 0.1.

[0180] The units derived from the starting material M3) when the above (meth)acrylic monomers are used have the formula:

[0181] [ka] In this formula, R 18 and R 19 is as described above for the (meth)acrylic monomers. Subscript z4 may also be equal to z3 if no other additional monomers are used as starting materials M3).

[0182] Alternatively, the units derived from the starting material M3) when a cyclic ketene acetal monomer is used have the formula:

[0183] [ka] In this formula, R 20 , R 21 , R 21’ , R 22 , R 22’ , R23 , R 23’ and subscript jj are as described above for the cyclic ketene acetal monomers, and subscript z5 may be equal to z3 if no other additional monomers are used as starting materials M3).

[0184] The copolymer further comprises a terminal unit. The terminal unit of the copolymer is a fragment of an initiator and / or a hydrogen atom. Examples of suitable initiators are as described above and include t-amyl peroxypivalate (commercially available as Trigonox 125-C75 initiator), t-butyl peroxypivalate (commercially available as Trigonox 25-C75), t-amyl peroxy-2-ethylhexanoate, 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionate).

[0185] The copolymers described herein may have a glass transition temperature (measured by DSC as described in the Examples below) that varies depending on a variety of factors including the amount of each of the starting materials M1) and M2), and whether additional monomer M3) is present, but the glass transition temperature may be from -20°C to 25°C, alternatively from 0°C to 20°C, alternatively from 3°C to 19°C, alternatively from 0°C to 5°C.

[0186] The molecular weight and polydispersity of the copolymers described herein depend on a variety of factors, including the number of silicon atoms per molecule in the M1) macromonomer, the amount of each of M1) and M2) vinyl ester of an aliphatic fatty acid, and whether M3) additional monomers are present. However, the molecular weight (i.e., number average molecular weight and weight average molecular weight) can be measured by GPC, as described in the examples below. The copolymers can have Mn of 4 kg / mol to 20 kg / mol, alternatively 5 kg / mol to 18 kg / mol, alternatively 6 kg / mol to 16 kg / mol. The copolymers can have Mw of 15 kg / mol to 100 kg / mol, alternatively 16 kg / mol to 75 kg / mol, alternatively 17 kg / mol to 70 kg / mol, alternatively 18 kg / mol to 55 kg / mol.

[0187] How to use The copolymer prepared as described herein can be added to a personal care composition. For example, the copolymer can act as a film former in the personal care composition. The personal care composition is not particularly limited, but the personal care composition can be a leave-on product suitable for application to the skin, such as skin care, sunscreen, and color cosmetic products (e.g., foundation). The copolymer or the solution of the copolymer prepared as described above can be added to the personal care composition by any convenient means, such as mixing. The personal care composition can include the copolymer in any amount, such as at least 1%, alternatively at least 2%, alternatively at least 5%, alternatively at least 10%, alternatively at least 20%, and alternatively at least 30%, based on the weight of all components of the personal care composition (excluding the carrier for supplying the copolymer). At the same time, the personal care composition may contain the copolymer in an amount of up to 99%, alternatively up to 90%, alternatively up to 80%, alternatively up to 70%, alternatively up to 50%, alternatively up to 10%, alternatively up to 8%, alternatively up to 6%, based on the weight of all components of the personal care composition (excluding the carrier for supplying the copolymer). The exact amount of copolymer used depends on various factors such as the type of personal care composition to be formulated. Alternatively, the personal care composition may contain the copolymer in an amount of 1% to 99% by weight, alternatively 5% to 95%, alternatively 1% to 10%, alternatively 2% to 8%, alternatively 4% to 6%, based on the weight of all components of the personal care composition (excluding the carrier for supplying the copolymer).

[0188] The copolymers prepared as described above can be used to replace different copolymers in personal care compositions known in the art, such as those disclosed in U.S. Patent No. 7,488,492 to Furukawa et al., U.S. Patent No. 9,670,301 to Furukawa et al., U.S. Patent No. 10,047,199 to Iimura et al., U.S. Patent No. 10,172,779 to Hori et al., and U.S. Patent Application Publication No. 2020 / 0222300 to Souda et al. Alternatively, the copolymers described herein can be formulated in sunscreens and cosmetics described in U.S. Patent Application Publication No. 2019 / 0201317 to Konishi et al. in place of the organosiloxane-grafted polyvinyl alcohol polymers described therein. Alternatively, the copolymers described herein can be used in cosmetic ingredients in U.S. Patent No. 6,280,748 to Morita et al. in place of the (meth)acrylate-functional carbosiloxane dendrimers disclosed therein. Alternatively, the copolymers described herein can be incorporated in the sun care and cosmetic compositions of Iida et al., U.S. Patent No. 8,541,009, in place of (meth)acrylate-based polymers having carbosiloxane dendrimer structures in their side chains. Alternatively, the copolymers described herein can be incorporated in the makeup and / or care compositions for keratin materials of Arnaud et al., U.S. Patent No. 8,828,372, in place of vinyl polymers containing units derived from carbosiloxane dendrimers. EXAMPLES

[0189] These examples are intended to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials used in these examples are listed in Table 1.

[0190] [Table 1-1]

[0191] [Table 1-2]

[0192] Example 1 - Hydroformylation of Si10-Hexenyl In this Example 1, hydroformylation of SilO-hexenyl branched oligomers was carried out as follows: In a nitrogen-filled glovebox, Rh(acac)(CO)2 (25.5 mg, 0.0984 mmol), Ligand 1 (122.3 mg, 0.1457 mmol), and toluene (5.0 g) were added to a 30 mL vial equipped with a magnetic stir bar. The mixture was mixed on a magnetic stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and removed from the glovebox. In a fume hood, SilO-hexenyl (100.0 g, 121.6 mmol) was added to a Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (690 kPa) with nitrogen via a dip tube and carefully released three times through the headspace. After pressure testing, the catalyst solution was added to the reactor. The reactor was pressurized with syngas to 100 psi, then released three times and then pressurized to 80 psig via a dip tube. Stirring and heating were started. Once the reaction reached 110°C, an intermediate cylinder containing syngas was connected to the reactor. The pressure of the intermediate cylinder was monitored by a data logger. After the reaction was complete, the reactor was purged with nitrogen three times and the material was transferred to a glass container as a colorless liquid that turned pale yellow over time. The product was crude (M2T)3T heptaldehyde (Si10HeptAld).

[0193] Example 2 - Oxidation of Si10-heptanaldehyde In Example 2, oxidation of (M2T)3T heptanealdehyde was carried out as follows: Crude (M2T)3T heptanealdehyde (100 g) containing approximately 5 wt. % toluene (as prepared in Example 1) was charged to a single-neck round-bottom flask equipped with a PTFE-coated stir bar and a septum cap. The liquid was stirred at 1150 rpm on a magnetic stir plate while air was sparged below the surface through a needle. The mixture was stirred until complete. 1The reaction mixture was analyzed by H NMR. After 24 hours, the reaction was stopped and the (M2T)3T-heptanoic acid product (Si10heptanoic acid) was collected as a clear orange liquid.

[0194] Example 3 - Transvinylation of Si10-heptanoic acid In this Example 3, a three-neck round bottom flask equipped with a thermometer, a condenser with a bubbler on top, and a rubber septum was used for this synthesis. A heating mantle with a J-Kem controller was used to control the heating. A magnetic stir bar, (M2T)3T-heptanoic acid product (176.0 g, 0.2026 mol) prepared as described in Example 2 above, and vinyl acetate (186.0 g, 2.163 mol) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle under vigorous stirring for 5 minutes. Palladium acetate (0.2390 g, 0.001067 mol) and phenanthroline (0.4070 g, 0.002258 mol) were added through the septum port. After stirring the mixture for 10 minutes, the reaction mixture was heated to 60° C. overnight. After the reaction was complete, the material was evaporated on a rotary evaporator with a bath temperature of 40 °C (500-10 mbar). 200 mL of hexane was added to the flask. The mixture was filtered through a disposable filter with 7 g of silica. The filtrate was concentrated under rotary evaporator to obtain a yellow viscous liquid (165.0 g, 96% purity). MEHQ (60.3 mg) was added to the material. The resulting material was Si10HepVE, which was stored in an amber bottle until further use.

[0195] Example 4 - Hydroformylation of Si10Vi In Example 4, in a nitrogen filled glove box, Rh(acac)(CO)2 (15.8 mg, 0.0610 mmol), Ligand 1 (75.1 mg, 0.0895 mmol), and toluene (7.5 g) were added to a 30 mL vial equipped with a magnetic stir bar. The mixture was mixed on a magnetic stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and removed from the glove box. In a fume hood, Si10Vi (142.4 g, 185.8 mmol) was added to a Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen via a dip tube and carefully depressurized through the headspace three times. After pressure testing, the catalyst solution was added to the reactor. The reactor was pressurized to 100 psi with syngas and then depressurized three times before being pressurized to 80 psig via a dip tube. Stirring and heating were started. Once the reaction reached 100°C, an intermediate cylinder containing synthesis gas was connected to the reactor. The pressure of the intermediate cylinder was monitored by a data logger. After the reaction was completed, the reactor was purged with nitrogen three times and the material was transferred to a glass container as a colorless liquid that turned pale yellow over time. This material was named crude Si10PrAld.

[0196] Example 5 - Oxidation of Si10-propanaldehyde In this Example 5, crude Si10PrAld (51.92 g) prepared as above in Example 4 containing approximately 5 wt. % toluene was charged to an 8 oz. narrow-mouth glass bottle equipped with a PTFE-coated stir bar and a septum cap. The liquid was stirred at 900 rpm on a magnetic stir plate while air was sparged subsurface through a needle at 100 cc / min. The mixture was stirred until complete. 1 The reaction mixture was analyzed by H NMR. After 24 hours, the reaction was stopped and the resulting Si10PrAcid product was collected as a clear, pale yellow liquid (50.5 g).

[0197] Example 6 - Transvinylation of Si10-propanoic acid In this Example 6, a three-neck round bottom flask equipped with a thermometer, a condenser with a bubbler on top, and a rubber septum was used for this synthesis. A heating mantle with a J-Kem controller was used to control the heating. A magnetic stir bar, Si10PrAcid (110.0 g, 0.1354 mol) prepared as above in Example 5, and vinyl acetate (129.1 g, 1.501 mol) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle under vigorous stirring for 5 minutes. Palladium acetate (0.3406 g, 0.001520 mol) and phenanthroline (0.4273 g, 0.002371 mol) were added through the septum port. After stirring the mixture for 10 minutes, the reaction mixture was heated to 60° C. overnight. After the reaction was completed, the material was transferred to a round-bottom flask and evaporated on a rotary evaporator with a bath temperature of 40 °C (500-10 mbar). 200 mL of hexane was added to the flask. The mixture was filtered through a disposable filter with 7 g of silica. The filtrate was concentrated under rotary evaporator to obtain a yellow viscous liquid. The macromonomer prepared by this Example 6 was named Si10PrVi.

[0198] Comparative Example 7 - Synthesis of solution polymer by free radical polymerization In this Comparative Example 7, a polymer designated CE P1 was prepared via solution polymerization in a thermal semi-batch process. The polymer backbone was made of 100% vinylacetate (Vac). A 500 mL round bottom flask was equipped with a glass rod propeller connected to a half-moon Teflon blade, a condenser, and a thermocouple. The propeller was driven by an overhead mechanical stirrer, and the thermocouple was connected to a J-KEM temperature controller, the input of which was provided to a pneumatic pot lifter to obtain the desired temperature. The flask was first charged with 45.0 g of EtOAc and heated to 65° C. A N2 blanket was applied to remove entrained air, and the stirring speed was started at 120 rpm. A separate 8 oz glass bottle was charged with 60.0 g of VAc monomer. A co-feed initiator was prepared by diluting 0.80 g of Trigonox 125-C75 with 22.50 g of EtOAc. When the reactor temperature reached 50° C., 12 g of VAc monomer was transferred to the reactor and heat was continued. When the reactor temperature reached 65° C., the remainder of the VAc monomer and the cofeed initiator were started to be metered in at rates of 0.40 g / min and 0.19 g / min, respectively. The target feed time was 120 minutes. Moderate heat was continued to maintain a polymerization temperature of 65° C. When the monomer feeds were completed, 6.00 g of EtOAc was added to the monomer bottle and rinsed into the reactor. The batch was held at 65° C. for 30 minutes. Then, two chemical chases of 1.20 g of Trigonox 125-C75 in 4.50 g of EtOAc were metered in over 30 minutes each at a rate of 0.19 g / min with a 15 minute hold in between. During the chemical chase, the temperature increased to 70° C. The batch was held for an additional 60 minutes before the reaction was quenched by cooling to ambient temperature.

[0199] The resulting polyvinyl acetate polymer was 40 wt. % dissolved solids in EtOAc. Residual VAc was 1 It was below the detection limit by H NMR spectroscopy (typically taken as 200 ppm). n , M wThe molecular weight and dispersity were 19.3 kg / mol, 84.3 kg / mol, and 4.37, respectively (relative to polystyrene (PS) standards). THF with 0.1 wt% formic acid was the mobile phase for GPC. g was 16.7° C. by DSC using a second heat at a rate of 20° C. / min.

[0200] Example 8 - Copolymer synthesis using the macromonomer of Example 6 In this Example 8, a copolymer designated as IE P2 was synthesized. The copolymer backbone was made of 60 VAc / 40 Si10PrVi by weight. A three-necked 250 mL round-bottom flask was equipped with a condenser, a thermocouple, and a Y-shaped glass adapter for two polyethylene feed lines. The flask was first charged with an egg-shaped Teflon-coated magnetic stir bar and 13.50 g of ethyl acetate. The flask was placed on an Opti-chem™ hotplate stirrer and the temperature was increased to 65° C. A nitrogen blanket was applied to remove entrained air, and the stirring speed was 300 rpm. In a separate 60 mL glass bottle, 10.80 g of VAc and 7.20 g of the macromonomer prepared according to Example 6 were charged in sequence to form a homogenous monomer mixture. The co-feed initiator was 0.24 g of Trigonox 125-C75 in 6.75 g of EtOAc. When the reactor temperature reached 65°C, 3.60g of the homogenous monomer mixture was charged to the reactor. After a few minutes, the remainder of the homogenous monomer mixture and the co-feed initiator were started to be metered in at rates of 0.12g / min and 0.0583g / min, respectively. The target feed time was 120 minutes. When the monomer feed was completed, 1.80g of EtOAc was added to the monomer syringe and rinsed into the reactor. The batch was held at 65°C for 15 minutes. Then, two chemical chases of 0.36g of Trigonox 125-C75 in 1.35g of EtOAc were metered in at a rate of 0.057g / min over 30 minutes with a 15 minute hold in between. The batch was held for an additional 30 minutes before being quenched by air cooling. The final product was analyzed for monomer conversion at 0.057g / min and 0.0583g / min. 1H NMR spectroscopy, GPC for molecular weight and dispersity, glass transition temperature (T g ) was analyzed by DSC.

[0201] Characterization of the final product showed copolymer solids: 40 wt.%. Residual VAc: 1 The residual macromonomer content (for Example 6) was 240 ppm by H NMR spectroscopy. 1 The M of the copolymer was below the detection limit by H NMR spectroscopy (typically taken as 1000 ppm). n , M w , and dispersity were 16.0 kg / mol, 54.8 kg / mol, and 3.42, respectively (relative to PS standard). g was 3.0° C. by DSC using a second heat at a rate of 20° C. / min.

[0202] Additional copolymers were made following the procedure of Example 8, but varying the amounts of monomers in the monomer mixture and the types of macromonomers, the amounts and selections being shown in Table 2 below.

[0203] Example 9 - Copolymer synthesis using the macromonomer of Example 6 In this Example 9, a copolymer designated as IE P5 was prepared as described below. The copolymer backbone was made of 50 VAc / 40 Sil0PrVi / 10 MDO by weight. A three-necked 250 mL round-bottom flask was equipped with a condenser, a thermocouple, and a Y-shaped glass adapter for two polyethylene feed lines. The flask was first charged with an egg-shaped Teflon-coated magnetic stir bar and 13.50 g of ethyl acetate. The flask was placed on an Opti-chem™ hotplate stirrer and the temperature was increased to 65° C. A nitrogen blanket was applied to remove entrained air, and the stirring speed was 300 rpm. In a separate 60 mL glass bottle, 9.00 g VAc, 7.20 g Sil0PrVi (macromonomer prepared according to Example 6), and 1.80 g MDO were charged in order to form a homogenous monomer mixture. The co-feed initiator was 0.24 g Trigonox 125-C75 in 6.75 g EtOAc. When the reactor temperature reached 65° C., 3.60 g of the homogenous monomer mixture was charged to the reactor. After a few minutes, the remainder of the homogenous monomer mixture and the co-feed initiator began to be metered in via syringe pumps at rates of 0.12 g / min and 0.0583 g / min, respectively. The target feed time was 120 minutes. When the monomer feed was completed, 1.80 g EtOAc was added to the monomer syringe and rinsed into the reactor. The batch was held at 65° C. for 15 minutes. Then, two chemical chases of 0.36 g Trigonox 125-C75 in 1.35 g EtOAc were metered in at a rate of 0.057 g / min over 30 minutes with 15 minutes of hold in between. The batch was then held for an additional 30 minutes before being quenched by air cooling.

[0204] Characterization of the final product: Solids: 40 wt.%. Residual VAc, Si10PrVi, and MDO contents: 1 It was below the detection limit by H NMR spectroscopy (typically taken as 1000 ppm). n , M w , and dispersity were 6.1 kg / mol, 35.9 kg / mol, and 5.88, respectively (relative to PS standard). gwas found to be −19.4° C. by DSC using a second heat at a rate of 20° C. / min.

[0205] Additional copolymers were made following the procedure of Example 9, but varying the amounts and types of monomers in the monomer mixture, the amounts and selections being shown in Table 2 below.

[0206] Example 10 - Copolymer synthesis using the macromonomer of Example 6 In this Example 10, a copolymer designated as IE P4 was prepared as described below. The copolymer backbone was made of 56 wt% VAc / 40 wt% Si10PrVi / 4 wt% AA. A three-necked 250 mL round-bottom flask was equipped with a condenser, a thermocouple, and a Y-shaped glass adapter for two polyethylene feed lines. The flask was first charged with a Teflon-coated magnetic stir bar and a mixture of 10.13 g ethyl acetate and 3.38 g ethanol. The flask was placed on an Opti-chem™ hotplate stirrer and the temperature was increased to 65° C. A nitrogen blanket was applied to remove entrained air, and the stirring speed was 300 rpm. In a separate 60 mL glass bottle, 10.08 g VAc, 7.20 g Si10PrVi (macromonomer prepared according to Example 6), and 0.72 g AA were charged in order to form a homogenous monomer mixture. The co-feed initiator was 0.24 g Trigonox 125-C75 in a mixture of 5.06 g ethyl acetate and 1.69 g ethanol. When the reactor temperature reached 65° C., 3.60 g of the homogenous monomer mixture was charged to the reactor. After a few minutes, the remainder of the homogenous monomer mixture and the co-feed initiator began to be metered via syringe pump at rates of 0.12 g / min and 0.0583 g / min, respectively. The target feed time was 120 minutes. The reaction mixture became opaque during the feeds. A first charge of 1.69 g ethanol was added to the reactor about 45 minutes after the start of the feeds, and a second charge of 1.69 g ethanol was added to the reactor about 90 minutes after the start of the feeds. When the monomer feeds were completed, a mixture of 1.35 g ethyl acetate and 0.45 g ethanol was added to the monomer syringe and rinsed into the reactor. The batch was held at 65° C. for 15 minutes. Two chemical chases of 0.48 g Trigonox 125-C75 in a mixture of 1.35 g ethyl acetate and 0.45 g ethanol were then metered in at a rate of 0.076 g / min over 30 minutes with a 15 minute hold in between. The batch was then held for an additional 30 minutes before being quenched by air cooling.

[0207] Example 11 - Synthesis of MCR-V21-aldehyde In this Example 11, the hydroformylation of MCR-V21 was carried out as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.0023 g), Ligand 1 (0.0147 g), and toluene (3.0 g) were added to a vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous catalyst solution was formed. The catalyst solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, MCR-V21 (90.0 g, 0.015 mol) was charged to a 300 mL Parr reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen via a dip tube and carefully released through a valve connected to the headspace. Pressurization / venting cycles with nitrogen were repeated three times. A pressure test was then performed by pressurizing the reactor to 300 psig (2086 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample charge port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then evacuated three times before pressurizing to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 70°C. The heater and agitation were turned on. The reaction was run at 100 psig (689 kPa) syngas pressure. 1 A 99.5% conversion of the vinyl groups was observed after 5.5 h reaction time as monitored by H NMR. The reactor was evacuated and purged with nitrogen three times, after which the product (MCR-V21-aldehyde) was collected and evaporated under vacuum.

[0208] Example 12 - Synthesis of MCR-V21-acid In this Example 12, the oxidation of MCR-V21-aldehyde (prepared as described in Synthesis Example 11) was carried out as follows: Crude MCR-V21-aldehyde (90 g) containing approximately 5 wt. % toluene was charged to a single-neck round-bottom flask equipped with a PTFE-coated stir bar and a septum cap. The liquid was stirred at 1150 rpm on a magnetic stir plate while air was sparged below the surface through a needle. The mixture was stirred until complete. 1The reaction mixture was analyzed by H NMR. After 24 h the reaction was stopped and the MCR-V21-acid product was collected as a clear orange liquid.

[0209] Example 13 - Synthesis of MCR-V21-vinyl ester In this Example 13, a linear vinyl ester functional polydimethylsiloxane was prepared using as starting material a carboxy functional polydimethylsiloxane prepared from hydroformylation of MCR-V21 from Gelest. A three-neck round bottom flask equipped with a thermometer, a condenser with a bubbler on top, and a rubber septum was used for this synthesis. A heating mantle with a J-Kem controller was used to control the heating. A magnetic stir bar, MCR-V21-aldehyde (75.8 g), prepared as above in Example 11, and vinyl acetate (26.1 g, 0.302 mol) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle under vigorous stirring for 5 minutes. Palladium acetate (0.172 g, 0.000766 mol), phenanthroline (0.21 g, 0.0012 mol), and MEHQ (0.023 g, 0.00018 mol) were added through the septum port. After stirring the mixture for 10 min, the reaction mixture was heated to 60 °C overnight. After the reaction was complete, the material was transferred to a round-bottom flask and evaporated on a rotary evaporator with a bath temperature of 40 °C (500-10 mbar). 200 mL of hexane was added to the flask. The mixture was filtered through a disposable filter with 7 g of silica. The filtrate was concentrated under rotary evaporator to give 72.1 g of a brown liquid.

[0210] Example 14 - Synthesis of Si4-aldehyde In this Example 14, the hydroformylation of 1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)-3-vinyltrisiloxane (Si4Vi) was carried out as follows: In a nitrogen-filled glovebox, Rh(acac)(CO)2 (0.0023 g), Ligand 1 (0.0147 g), and toluene (3.0 g) were added to a vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous catalyst solution was formed. The catalyst solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, Si4Vi (177.8 g, 0.055 mol) was charged to a 300 mL Parr reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen via a dip tube and carefully released through a valve connected to the headspace. Pressurization / vent cycles with nitrogen were repeated three times. A pressure test was then performed by pressurizing the reactor to 300 psig (2086 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample charge port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then evacuated three times before pressurizing to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 70°C. The heater and agitation were turned on. The reaction was run at 100 psig (689 kPa) syngas pressure. 1 A 99.5% conversion of the vinyl groups was observed after 5.5 h reaction time as monitored by H NMR. After evacuating the reactor and purging with nitrogen three times, the product 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanal was collected and evaporated under vacuum.

[0211] Example 15 - Synthesis of Si4-acid In this Example 15, the oxidation of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanal (Si4-aldehyde) (prepared as described in Example 14X) was carried out as follows: Si4-aldehyde (90 g) containing approximately 5% by weight toluene was charged to a single-neck round-bottom flask equipped with a PTFE-coated stir bar and septum cap. The liquid was stirred at 1150 rpm on a magnetic stir plate while air was sparged below the surface through a needle. The mixture was stirred until complete. 1 The reaction mixture was analyzed by H NMR. After 24 hours, the reaction was stopped and the 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanoic acid (Si4-acid) product was collected as a clear orange liquid.

[0212] Example 16-Synthesis of Si4-vinyl ester In this Example 16, vinyl 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanoate (Si4-VE) was prepared using Si4-acid as the starting material. A three-neck round bottom flask equipped with a thermometer, a condenser with a bubbler on top, and a rubber septum was used for this synthesis. A heating mantle with a J-Kem controller was used to control the heating. A magnetic stir bar, Si4-acid (27.8 g, 0.0759 mol), and vinyl acetate (136.1 g, 1.58 mol) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle under vigorous stirring for 5 minutes. Palladium acetate (0.214 g, 0.000955 mol), phenanthroline (0.214 g, 0.0012 mol), and MEHQ (0.036 g, 0.00029 mol) were added through the septum port. After stirring the mixture for 10 min, the reaction mixture was heated to 60 °C overnight. After the reaction was complete, the material was transferred to a round-bottom flask and evaporated on a rotary evaporator with a bath temperature of 40 °C (500-10 mbar). 200 mL of hexane was added to the flask. The mixture was filtered through a disposable filter with 7 g of silica. The filtrate was concentrated under rotary evaporator to give 27.6 g of a clear oil.

[0213] Characterization of the final product: Solids: 35.4 wt%. Conversion of VAc was 99.8% by 1H NMR spectroscopy, with residual Si10PrVi and AA contents below the detection limit by 1H NMR spectroscopy (typically taken as 1000 ppm). Mn, Mw, and dispersity were 4.5 kg / mol, 18.6 kg / mol, and 4.17, respectively (relative to PS standard). Tg was 6.6°C by DSC using a second heating at a rate of 20°C / min.

[0214] [Table 2]

[0215] In the above Table 2, the solids content refers to the amount of (co)polymer dissolved in the carrier. The theoretical biodegradable content of the (co)polymers in Table 2 was calculated using Equation 1 below.

[0216]

number

[0217] [Table 3]

[0218] The polymers (Comparative Example CE P1) and copolymers prepared as above in Table 2 were characterized using the test methods described below. Number average molecular weight (M) as measured by GPC n ), weight average molecular weight (M w ), and dispersity (M w / M n ) and the glass transition temperature (T g ) are reported in Table 4.

[0219] [Table 4]

[0220] The data in Table 4 show that silicone-vinyl ester copolymers can be prepared with various amounts of starting materials M1) and M2) under the conditions of Examples 8 and 9. In addition, copolymers containing starting material M3) were also successfully prepared (in IE P4 and IE P5).

[0221] Samples of polymer (CE P1) and copolymers (IE P1-IE P11) prepared as described in Examples 7-10 were analyzed for water and sebum contact angles according to the following test methods. Comparative commercial silicone-acrylate copolymer compositions were also tested (CE P2 and CE P3). Neat film contact angles (CA) to assess the inherent water and sebum repellency of the (co)polymer compositions are shown in Table 5. As noted, higher contact angle values ​​indicate either higher water or sebum repellency.

[0222] [Table 5]

[0223] Five measurements were made for each film. The averages and standard deviations are reported in Table 5. * " indicates that the copolymer sample was prepared using the macromonomer prepared above in Example 3 instead of the macromonomer prepared above in Example 6. ** " indicates the use of 4% acrylic acid (AA) instead of 10% MDO as M3) additional monomer in the preparation of copolymer IE P4 by the method of Example 9. Comparative Examples 2 and 3 (CE2 and CE3) in the above table represent commercially available silicone-acrylate copolymers.

[0224] Copolymers IE P1-IE P11 demonstrated that the process described herein can be used to successfully synthesize copolymers with varying levels of M1) vinyl ester functional siloxane macromonomer and M2) vinyl ester of aliphatic fatty acid. Samples IE P1-IE P11 showed an advantage over CE P1 in that the water contact angle and sebum contact angle remained consistent over 200 seconds, while sample CE P1 showed a significant decrease in sebum contact angle over time (i.e., sebum contact angle decreased from 16.6 to 6.8 after 200 seconds). This attribute suggests superior hydrophobicity and low water absorption of the copolymers of the present invention, thus holding the potential for better durability of formulated personal care products after application to keratinous surfaces, such as skin. In contrast, copolymers containing 10% to 50% vinyl ester functional siloxane macromonomer prepared as described herein had more consistent sebum contact angles over time, suggesting that an advantage of the copolymers described herein is that they may provide sebum resistance that can be maintained over time.

[0225] In addition, copolymers IE P1-IE P8 showed advantages over vinyl acetate homopolymer in sample CE P1. CE P1 showed an initial water contact angle of 57.8°. Copolymers IE P1-IE P8 showed initial water contact angles of 90-110°, with these examples showing essentially the same water contact angles after 200 seconds. These results demonstrated the superior water repellency of copolymers IE P1-IE P8. Surprisingly, certain copolymers (e.g., IE P2, IE P3, IE P4, and IE P5) showed higher water contact angles than commercial silicone-acrylate compositions (CE P5 and P6).

[0226] A similar composition / performance relationship was observed in the sebum contact angle measurements. Comparative polymer CE P1 exhibited an initial sebum contact angle of 16.6°. In comparison, copolymers IE P1-IE P11 all exhibited higher initial sebum contact angles than CE P1. These copolymers also exhibited sebum contact angles an order of magnitude higher after 200 seconds than the 6.8° sebum contact angle of polymer CE P1. These results demonstrated the excellent sebum repellency of the copolymers prepared as described herein. Surprisingly, certain copolymers (e.g., IE P1, IE P2, IE P3, IE P4, and IE P5) also exhibited higher sebum contact angles than comparative commercial silicone-acrylate compositions (CE 2 and CE 3).

[0227] Preparation of Cosmetic Foundation Formulations The copolymers described in Table 2 were tested in cosmetic foundation formulations. A foundation for color cosmetics was prepared using the formulations shown in Table 6 according to the following general procedure: Starting materials 1-5 were first added to a plastic cup and homogenized in a FlackTeck speed mixer at a centrifugal speed of 2000 rpm for 1 minute. Starting materials 6 and 7 were added to the same cup and the mixture was homogenized for another minute at the same centrifugal speed to obtain phase A. Starting materials 8-11 were prepared in a separate vessel and homogenized at 500-800 rpm with an overhead mixer until a homogenous mixture of phase B was obtained. The mixture of phase B was then slowly added to the mixture of phase A while mixing with an overhead mixer operating at 500-800 rpm. Phase C was then introduced to the mixture of phases A and B under the same mixing conditions until a homogenous mixture was obtained. Finally, phase D was added under the same mixing conditions until a homogenous mixture was obtained.

[0228] [Table 6]

[0229] The foundation formulations described in Table 6 were cast into thin films and allowed to dry. Three tests were performed as follows: Visual evaluation of film quality ○Contact angle of water and sebum ○ Rub-off resistance The test methods are described below, and the results are shown in Table 7.

[0230] [Table 7] Film Evaluation Criteria: 5-Fine, smooth, shiny and without obvious defects 4 - Very fine and smooth, but slightly uneven in thickness or color 3-Very fine and smooth, some pinholes or uneven color 2 - No cracks, continuous polymer film, no grains but no noticeable pinholes or uneven color 1 - Continuous polymer film without cracks, but grainy, noticeable pinholes or uneven color 0 - Cracks and no longer form a continuous film

[0231] Certain copolymers prepared as described herein provide excellent film quality in foundation formulations tested under the above conditions.These data indicate the excellent film-forming ability of the copolymers, especially when the copolymers contain more than 20% of the vinyl ester functional siloxane macromonomers described herein.

[0232] Foundation films prepared as above from the foundation formulations in Table 6 were also tested for water and sebum contact angles, and the results are shown in Table 8.

[0233] [Table 8]

[0234] Five measurements were taken for each film. The average and standard deviation are reported. The data in Table 8 showed that IE F3 and IE F4 showed higher initial sebum contact angles than all other samples tested. Without wishing to be bound by theory, this result is believed to be due to the heptanoate group from the macromonomer used to prepare the copolymer, which may provide an additional advantage in sebum resistance compared to the propanoate group used to prepare the other copolymers in the foundation formulations tested.

[0235] The foundation films prepared above were also evaluated for rub off according to the following test method, with the results being in Table 9.

[0236] [Table 9]

[0237] In Table 9, ten measurements were made for each film. The average and one standard deviation are reported. The lower the Delta E value, the better the rub-off resistance. The results in Table 9 suggest that the copolymers prepared as described herein have comparable or better rub-off resistance than vinyl ester homopolymers (CE P1 in Foundation Example CE F2) and commercial silicone-acrylate compositions (CE P2 and CE P3 in Samples CE F3 and CE F4, respectively).

[0238] Preparation of Oil-in-Water Sunscreen Formulations Oil-in-water (O / W) sunscreen formulations were then prepared using the copolymers as described above in Table 2 using the types and amounts of starting materials shown in Table 10 below according to the following procedure. The ingredients of Phase A were combined in a suitable sized vessel and mixed while heating to 75° C. to obtain a homogeneous mixture. In a separate vessel, the ingredients of Phase B were combined and mixed while heating to 75° C. until completely dissolved. Phase B was added to Phase A while mixing at a moderate speed. After all of Phase B had been added, the batch was maintained at 75° C. while mixing at a moderate speed. Phase C was added to the batch and mixed until a homogeneous mixture was obtained. Phase D was preheated to 75° C., added to the batch and mixed until a homogeneous mixture was obtained. The ethyl acetate in each original copolymer solution was removed by distillation and the resulting dry copolymer was reconstituted as a 40% by weight solution in either isododecane or C12-15 alkyl benzoate. The batch was then cooled and mixed at moderate speed. When the batch temperature was below 45° C., Phase E was added and mixed at moderate speed until the batch reached room temperature.

[0239] [Table 10]

[0240] Procedure for preparing water-in-oil sunscreen formulations: Water-in-oil (W / O) sunscreen formulations were then prepared using the copolymers as described above in Table 2 using the types and amounts of starting materials shown in Table 11 below according to the following procedure. The ingredients of Phase A were combined and mixed until a homogenous mixture was obtained. In a suitable size vessel, the ingredients of Phase B were combined and mixed at moderate speed. Phase B was then heated to 75°C and mixed until all ingredients were dissolved and a homogenous mixture was obtained. The ethyl acetate in the original silicone-vinyl ester copolymer solution was removed by distillation and the dried copolymer was reconstituted as a 40 wt% solution in either isododecane or C12-15 alkyl benzoate. Phase A was slowly added to Phase B under homogenization at 4000 rpm. After all Phase A was added, homogenization was continued for 3 minutes at 4000 rpm. The batch was transferred and stirred at moderate speed under an overhead mixer. When the batch temperature was below 45°C, Phase C was added and mixed at moderate speed until the batch reached room temperature.

[0241] [Table 11]

[0242] Both O / W and W / O sunscreen formulations were cast into uniform thin films and allowed to dry. The initial SPF values ​​were measured to evaluate the SPF boosting effect. Three measurements were made for each formulation. The average and one standard deviation are reported. The in vitro SPF results of the O / W sunscreen formulations are shown below in Table 12. The in vitro SPF results of the W / O sunscreen formulations are shown below in Table 13.

[0243] [Table 12]

[0244] All of the copolymers prepared as described herein and tested in O / W sunscreens had SPF-enhancing effects, with in vitro SPF values ​​higher than a control without the copolymer and a comparative O / W formulation containing a commercial silicone-acrylate copolymer.

[0245] [Table 13]

[0246] Water-in-oil sunscreen formulations containing copolymers IE P3 and IE P5 showed some SPF enhancement.

[0247] Test methods used in the examples 1 H nuclear magnetic resonance (NMR) spectroscopy Small amounts (50–100 mg) of solution polymer samples were dissolved in approximately 1.0 mL of deuterated chloroform and analyzed on a Bruker AVANCE III HD 500 spectrometer equipped with a 5 mm PRODIGY CryoProbe. 1 H spectra were acquired with a zg30 pulse sequence, a relaxation delay of 60 seconds, and 64 scans. Spectra were analyzed using MestReNova software (version 12) from Mestrelab Research. Residual monomer was quantified by comparing the signal from the vinyl regions of the monomer to the signal from the solvent.

[0248] Gel-permeation chromatography (GPC) The solution polymers were diluted with tetrahydrofuran to a concentration of approximately 2.0 mg / mL and analyzed by GPC consisting of an Agilent 1260 Infinity II Model isocratic pump and an Agilent 1260 Infinity II refractive index detector. Tetrahydrofuran was the mobile phase, the elution rate was 1.0 mL / min, and separation was enabled by two PLgel Mixed A columns (300 x 7.5 mm i.d.) and a guard column (50 x 7.5 mm i.d.). A first-order fit calibration curve was constructed using ten narrow polystyrene standards in the range of 580 g / mol to 6,800,000 g / mol. Data was processed using Agilent GPC / SEC software version A.02.01.

[0249] Glass transition temperature (T g ) A small amount of the solution polymer was transferred to an aluminum pan. The solution polymer was first dried at ambient temperature and then dried at 60°C under house vacuum until a constant mass was achieved. The mass of the dried polymer was typically 3-10 mg. The aluminum pan was sealed and analyzed on a TA Instruments Q1000 Differential Scanning Calorimeter. Two heating scans were applied between -90°C and 150°C at a rate of 20°C / min. Values ​​from the second scan were reported.

[0250] Preparation of polymer neat films and contact angle measurements Thin films of the solution polymer were prepared by hand using a 6 mil doctor blade on a LENETA black plastic chart. The films were allowed to dry at 23°C in a fume hood for at least 72 hours.

[0251] Contact angle data was collected from the surface of each film using both water and sebum on a Kruss DSA100 instrument. Data was collected as soon as possible (0 seconds) and after approximately 200 seconds for the same drop. Five drops were applied to the same piece of film and the average and standard deviation values ​​are reported.

[0252] Rub-off test of cured foundation films The foundation samples were each coated onto a black vinyl chart (available from Leneta) using a doctor blade film applicator with the gap set at 6 mil (0.1524 mm) and allowed to dry at 22° C. for at least 48 hours. The color readings of each sample were then measured by a colorimeter (Ocean Optics). The abrasion resistance of the deposited films of the color cosmetic formulations was characterized by the change (ΔE) before and after abrasion on a pre-cut bath towel (55 mm×45 mm). The bath towel was fixed to the moving part of a robot that periodically moved back and forth at a constant speed. The film was abraded by three abrasion cycles with the bath towel under a pressure of about 600 Pa. Readings were taken from 10 points of each deposited film.

[0253] In vitro SPF measurement In vitro SPF measurements were performed using a LABSHPERE UV 2000S spectrometer. First, approximately 0.0325 g of each formulation was weighed onto a HELIOPLATE HD6 PMMA substrate. The formulation was then spread evenly using an index finger covered with a rubber finger cot. The samples were allowed to dry for 20-30 minutes at ambient conditions. UV absorbance between 290 nm and 400 nm was measured at nine locations on the dried samples. Selection of the nine locations was guided by positioning marks on the instrument sample stage assembly. In vitro SPF values ​​were generated and recorded at the end of each measurement. Each formulation was measured three times, and the in vitro SPF value of each formulation was calculated as the average of the three measurements.

[0254] Industrial Applicability The above examples show that M1) vinyl ester functional siloxane macromonomer (macromonomer) was successfully synthesized and copolymerized with M2) vinyl ester of aliphatic fatty acid to form silicone-vinyl ester copolymer (copolymer). Copolymers with various amounts of macromonomer and vinyl ester of aliphatic fatty acid were successfully synthesized. Additional monomer M3) was also successfully included in some copolymer samples. The copolymers are useful in different personal care compositions, such as cosmetic foundations and sunscreens. By varying the type and amount of M1) macromonomer and M2) vinyl ester of aliphatic fatty acid, and by adding M3) optional additional monomer, the desired properties of the copolymer, such as biodegradation potential, or water resistance and / or sebum resistance in different personal care formulations, can be adjusted.

[0255] Definitions and Use of Terms All amounts, ratios, and percentages are by weight unless otherwise specified. The amounts of all starting materials in the composition total 100% by weight. The Summary and Abstract are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more, unless otherwise indicated by the context of the specification. The singular includes the plural unless otherwise indicated. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in Sections §2111.03 I., II., and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. Abbreviations used herein have the definitions in Table Z.

[0256] [Table 14]

[0257] The following test methods were used herein: 29 Si NMR: The alkenyl content of the alkenyl-functional polyorganosiloxanes described herein can be measured by techniques described in "The Analytical Chemistry of Silicones," edited by A. Lee Smith, Vol. 112 of Chemical Analysis, John Wiley & Sons, Inc. (1991). Viscosity: Viscosity can be measured, for example, for polymers having a viscosity of 120 mPa·s to 250,000 mPa·s (such as certain alkenyl-functional polyorganosiloxanes, aldehyde-functional polyorganosiloxanes, carboxy-functional polyorganosiloxanes, and vinyl ester-functional siloxane macromonomers) with a Brookfield DV-III cone & plate viscometer equipped with a #CP-52 spindle at 25°C and 0.1 to 50 RPM. One skilled in the art will recognize that as the viscosity increases, the rotation speed decreases and that an appropriate spindle and rotation speed can be selected.

Claims

1. 1. A method for making a silicone-vinyl ester functional copolymer, the method comprising: I) under conditions conducive to free radical polymerization, M1) a vinyl ester functional siloxane macromonomer; M2) vinyl esters of aliphatic fatty acids; optionally M3) an additional alkenyl-functional monomer; N) a free radical initiator; and optionally O) an organic carrier, thereby forming a reaction mixture comprising said silicone-vinyl ester functional copolymer; II) quenching the reaction mixture after step I); Optionally, III) recovering said silicone-vinyl ester functional copolymer from said reaction mixture; and Optionally, IV) dissolving the silicone-vinyl ester functional copolymer in a simple alcohol; and optionally V) performing a solvent exchange after II), or after step III) or after step IV) if step III) or step IV) is present.

2. M1) the vinyl ester functional siloxane macromonomer is used in an amount of 1% to 99% by weight; M2) the vinyl ester of the aliphatic fatty acid is used in an amount of 1% to 99% by weight; M3) the additional alkenyl functional monomer is used in an amount of 0-20 wt.%; 2. The method of claim 1, each based on the combined weight of M1), M2), and M3).

3. M1) a vinyl ester functional siloxane macromonomer having the formula 【Chemistry 1】 wherein G is a divalent hydrocarbon group free of aliphatic unsaturation, and each R １２ are independently -OSi(R １４ ) ３ and R １３ wherein each R １３ is a monovalent hydrocarbon group, wherein each R １４ But, R １３ , -OSi(R １５ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ wherein each R １５ But, R １３ , -OSi(R １６ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ wherein each R １６ But, R １３ and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ wherein each subscript ii independently has a value such that 0≦ii≦100, with the proviso that R １２ At least two of the groups are -OSi(R １４ ) ３ and wherein the vinyl ester functional polyorganosiloxane has from 4 to 16 silicon atoms per molecule.

4. M1) The vinyl ester functional siloxane macromonomer has the formula: 【Chemistry 2】 wherein G and R １５ The method of claim 3, wherein:

5. M1) The vinyl ester functional siloxane macromonomer has the formula: 【Chemistry 3】 wherein G, R １３ , and R １５ The method of claim 3, wherein:

6. M1) The vinyl ester functional siloxane macromonomer has the formula: 【Chemistry 4】 wherein G, R １３ , and R １５ The method of claim 3, wherein:

7. M1) the vinyl ester functional siloxane macromonomer is 【Chemistry 5】 The method of claim 3 , comprising one or more of:

8. M1) the vinyl ester functional siloxane macromonomer is 5) combining starting materials comprising (I) a carboxy-functional polyorganosiloxane, (J) an alkenyl acetate, (K) a transvinylation catalyst, optionally (L) a third solvent, and optionally (M) an inhibitor, under conditions conducive to a transvinylation reaction, thereby producing (M1) a transvinylation reaction product comprising said vinyl ester functional siloxane macromonomer; and optionally 6) recovering (M1) said vinyl ester functional siloxane macromonomer.

9. (I) the carboxy-functional polyorganosiloxane is Under the conditions in which the oxidation reaction takes place, (E) an aldehyde-functional polyorganosiloxane; and (F) a source of oxygen, (I) forming an oxidation reaction product comprising the carboxy-functional polyorganosiloxane; 9. The method of claim 8, wherein the carboxy-functional polyorganosiloxane is prepared by a process comprising:

10. (E) the aldehyde-functional polyorganosiloxane is Under conditions that catalyze the hydroformylation reaction, (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional polyorganosiloxane; and (C) A rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand has the formula 【Chemistry 6】 wherein R ６ and R ６’ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 20 carbon atoms, a cyano group, a halogen group, and an alkoxy group of 1 to 20 carbon atoms; R ７ and R ７’ each independently represents an alkyl group of 3 to 20 carbon atoms, and a group of the formula -SiR １７ ３ wherein each R １７ is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms; R ８ , R ８’ , R ９ , and R ９’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R １０ , R １０’ , R １１ , and R １１’ are each independently selected from the group consisting of hydrogen or and alkyl groups, thereby forming a hydroformylation reaction product comprising said aldehyde-functional polyorganosiloxane; and combining the starting materials, optionally including (D) a solvent; thereby forming (E) a hydroformylation reaction product comprising the aldehyde-functional polyorganosiloxane; and 10. The method of claim 9, wherein the aldehyde-functional branched polyorganosiloxane oligomer is prepared by a process comprising the steps of:

11. M2) The vinyl ester of the aliphatic fatty acid has the formula: 【Chemistry 7】 wherein R ３ The method of any one of claims 1 to 10, wherein is hydrogen or an alkyl group of 1 to 14 carbon atoms.

12. 12. The method of claim 10 or 11, wherein M2) the vinyl ester of the aliphatic fatty acid comprises vinyl acetate.

13. M1) the vinyl ester functional siloxane macromonomer is used in an amount of 30% to 60% by weight; M2) the vinyl ester of the aliphatic fatty acid is used in an amount of 40% to 70% by weight; M3) the additional alkenyl functional monomer is used in an amount of 0-20 wt.%; 13. The method of any one of claims 1 to 12, each based on the combined weight of M1), M2), and M3).

14. 14. Use of the silicone-vinyl ester copolymer prepared by the method of claim 13 in a personal care composition.

15. A silicone-vinyl ester copolymer prepared by the method of any one of claims 1 to 13.

16. M1) a vinyl ester functional siloxane macromonomer having the unit formula: (R ４ ３ SiO １／２ ) ａ (R ＶＥ R ４ ２ SiO １／２ ) ｂ (R ４ ２ SiO ２／２ ) ｃ (R ＶＥ R ４ SiO ２／２ ) ｄ wherein R ＶＥ but, 【Chemistry 8】 wherein G is a divalent hydrocarbon group free of aliphatic unsaturation, and each R ４ are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and subscripts a, b, c, and d represent the average number of each unit in said formula, with subscript a having a value such that subscript b is 0, 1, or 2, subscript c > 0, and subscript d > 0, with the proviso that the quantity (b+d) > 1, the quantity (a+b) = 2, and the quantity (a+b+c+d) > 2.

17. M1) The vinyl ester functional siloxane macromonomer has the formula: 【Chemistry 9】 wherein each R ２’’’ But independently, R ４ and R ＶＥ with the proviso that at least one R ２’’’ But, R ＶＥ and each R ４ is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; ＶＥ but, 【Chemistry 10】 17. The method of claim 16, wherein G is a divalent hydrocarbon group free of aliphatic unsaturation and the subscript zz = the quantity (c + d).

18. M1) The vinyl ester functional siloxane macromonomer has the formula: 【Chemistry 11】 wherein each R ４ is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; ＶＥ but, 【Chemistry 12】 17. The method of claim 16, wherein G is a divalent hydrocarbon group free of aliphatic unsaturation and subscript c is 0 to 2,000.

19. M1) the vinyl ester functional siloxane macromonomer is used in an amount of 30% to 60% by weight; M2) the vinyl ester of the aliphatic fatty acid is used in an amount of 40% to 70% by weight; M3) the additional alkenyl functional monomer is used in an amount of 0-20 wt.%; 19. The method of any one of claims 16 to 18, each based on the combined weight of M1), M2), and M3).

20. 20. Use of the silicone-vinyl ester copolymer prepared by the method of claim 19 in a personal care composition.

21. A silicone-vinyl ester copolymer prepared by the method of any one of claims 16 to 19.

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