Preparation of organosilicon compounds containing vinyl ester functionality

Abstract

Preparation of vinyl ester functional organosilicon compounds. Vinyl ester functional organosilicon compounds can be prepared by a process that includes hydroformylating an alkenyl functional organosilicon compound to produce an aldehyde functional organosilicon compound, oxidizing the aldehyde functional organosilicon compound to produce a carboxy functional organosilicon compound, and vinylexchanging the carboxy functional organosilicon compound to produce a vinyl ester functional organosilicon compound.

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 / 330,503, filed April 13, 2022. U.S. Provisional Application No. 63 / 330,503 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION A process for preparing vinyl ester functional organosilicon compounds is disclosed. The process for preparing vinyl ester functional organosilicon compounds can be carried out by hydroformylating an alkenyl functional organosilicon compound with carbon monoxide and hydrogen to form an aldehyde functional organosilicon compound, oxidizing to produce a carboxy functional organosilicon compound, followed by vinyl exchange. [Background technology]

[0003] Introduction Organic vinyl ester monomers are important for use in polymer synthesis. Polyvinyl ester polymers can be hydrolyzed to poly(vinyl alcohol), which is known to be highly biodegradable. To this end, the introduction of vinyl ester functionality into siloxane materials provides an opportunity to generate vinyl ester-functional siloxanes. However, vinyl ester-functionalized siloxanes have been rarely studied. Traditional methods of making carboxylic acid derivatives, such as hydrosilylation, are difficult to use to make vinyl esters, since the vinyl ester group can be hydrosilylated under similar conditions as the vinyl group, thereby destroying the vinyl ester functionality during the process. Summary of the Invention

[0004] The process for preparing a vinyl ester functional organosilicon compound comprises combining starting materials comprising a carboxy functional organosilicon compound, a vinyl acetate functional compound, and a transvinylation catalyst under conditions conducive to a transvinylation reaction, thereby forming a transvinylation reaction product comprising a vinyl ester functional organosilicon compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] Alternatively, the process presented above can be 1) Under conditions which catalyze the hydroformylation reaction, (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional organosilicon compound; and (C) A rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand has the formula:

[0006] [ka] 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’ are each independently an alkyl group having 3 to 20 carbon atoms, and a group of the formula -SiR 17 3 (in the formula, each R 17 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 or alkyl groups; (D) a solvent; mixing starting materials comprising thereby forming a hydroformylation reaction product comprising (E) an aldehyde-functional organosilicon compound; and Optionally, 2) recovering (E) the aldehyde-functional organosilicon compound; and 3) Under conditions in which an oxidation reaction occurs, (E) an aldehyde-functional organosilicon compound; and (F) an oxygen source; Optionally, (G) an oxidation reaction catalyst; Optionally, (H) a second solvent; and mixing the starting materials including (I) forming an oxidation reaction product comprising a carboxy-functional organosilicon compound; and optionally, 4) (I) recovering the carboxy-functional organosilicon compound; and 5) under conditions conducive to a vinyl exchange reaction; (I) a carboxy-functional organosilicon compound; (J) formula

[0007] [ka] wherein R 3 is an alkyl group having 1 to 6 carbon atoms, and (K) a vinyl exchange reaction catalyst; mixing the starting materials, optionally including (L) a solvent; thereby preparing a reaction mixture comprising (M) a vinyl ester functional organosilicon compound; Optionally, the method may further comprise: 6) recovering the (M) vinyl ester functional organosilicon compound.

[0008] Aldehyde-functional organosilicon compounds Aldehyde functional organosilicon compounds suitable for use in the process for preparing vinyl ester functional organosilicon compounds are known and may be made by known methods such as those described in U.S. Pat. No. 4,424,392 to Petty, U.S. Pat. No. 5,021,601 to Frances et al., U.S. Pat. No. 5,739,246 to Graiver et al., U.S. Pat. No. 7,696,294 to Asirvatham, and U.S. Pat. No. 7,999,053 to Sutton et al., European Patent Application Publication No. 0392948(A1) to Frances, and International Patent Application Publication No. WO2006027074 to Kuhnle et al.

[0009] Alternatively, the aldehyde-functional organosilicon compound can be prepared by a hydroformylation process, which comprises: 1) mixing starting materials including (A) a gas containing hydrogen and carbon monoxide, (B) an alkenyl-functional organosilicon compound, and (C) a hydroformylation reaction catalyst, such as a rhodium / bisphosphite ligand complex catalyst, under conditions that catalyze the hydroformylation reaction, thereby forming a hydroformylation reaction product that includes the aldehyde-functional organosilicon compound.

[0010] The hydroformylation process described herein employs starting materials comprising (A) a gas comprising hydrogen and carbon monoxide, (B) an alkenyl-functional organosilicon compound, and (C) a rhodium / bisphosphite ligand catalyst. The starting materials may optionally further comprise (D) a solvent.

[0011] (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. Syngas 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.

[0012] (B) Alkenyl-functional organosilicon compounds The alkenyl-functional organosilicon compound has at least one alkenyl group covalently bonded to silicon per molecule. Alternatively, the alkenyl-functional organosilicon compound can have one or more alkenyl groups covalently bonded to silicon per molecule. The starting material (B) can be one alkenyl-functional organosilicon compound. Alternatively, the starting material (B) can comprise two or more alkenyl-functional organosilicon compounds that are different from each other. For example, the alkenyl-functional organosilicon compound can comprise one or both of (B1) silane and (B2) polyorganosiloxane.

[0013] The starting material (B1), an alkenyl-functional silane, has the formula (B1-1): R A x SiR 4 (4-x)wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, 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, and the subscript x is 1 to 4. Alternatively, the subscript x can be 1 or 2, alternatively 2, alternatively 1. Alternatively, each R 4 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.

[0014] R A The alkenyl group of R may have a terminal alkenyl functionality, e.g., A is the formula

[0015] [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 may be independently selected from the group consisting of vinyl and hexenyl. Alternatively, each R A Alternatively, each R A Alternatively, each R A can be hexenyl.

[0016] R 4Suitable 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 group of R may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl or ethyl. 4 The alkyl group in may be methyl.

[0017] R 4 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.

[0018] Suitable alkenyl-functional silanes are exemplified by alkenyl-functional trialkylsilanes such as vinyltrimethylsilane, vinyltriethylsilane, and allyltrimethylsilane. All of these alkenyl-functional silanes are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA). Additionally, alkenyl-functional silanes can be prepared by known methods such as those disclosed in U.S. Patent No. 4,898,961 to Baile et al. and U.S. Patent No. 5,756,796 to Davern et al.

[0019] Alternatively, (B) the alkenyl-functional organosilicon compound may comprise (B2) an alkenyl-functional polyorganosiloxane. The polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The polyorganosiloxane may have a unit formula (B2-1): (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein R A and R 4 is as defined above, and each Z is independently selected from a hydrogen atom and R 4 (R 4 is an alkyl or aryl group as defined above), the subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, and subscript g≧0, the quantity (a+b+c+d+e+f+g)≧2 and the quantity (b+d+f)≧1, and the subscript h is 0 ≦ h / (e+f+g) ≦ 1.5. If e=f=g=0, then h≧0. At the same time, the quantity (a+b+c+d+e+f+g) can be ≦10,000. Alternatively, each Z can be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z can be hydrogen.

[0020] Alternatively, the alkenyl-functional polyorganosiloxane (B2) may comprise a linear polydiorganosiloxane having at least one alkenyl group per molecule (B2-2), alternatively at least two alkenyl groups (e.g., when subscripts e=f=g=0 in formula (B2-1) above). For example, the polydiorganosiloxane may have the unit formula (B2-3): (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 (B2-3), 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 (B2-3), 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 (B2-3), 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 (B2-3) 4 can be an alkyl group, alternatively, each R 4 can be methyl.

[0021] Alternatively, the polydiorganosiloxane of the unit formula (B2-3) may be a polydiorganosiloxane of the unit formula (B2-4): (R 4 2R A SiO 1 / 2 )2(R 4 2SiO2 / 2 ) m (R 4 R A SiO 2 / 2 ) n , Unit formula (B2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R A SiO 2 / 2 ) p 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.

[0022] Alternatively, the polydiorganosiloxane of the unit formula (B2-3) is represented by the formula (B2-3a)

[0023] [ka] wherein R 4 is as above, and R 2 is the above R A and R 4 with the proviso that at least one R 2 is R A where the subscript zz=the amount (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, or alternatively from 80 to 800.

[0024] 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 subscripts a = 1, b = 1, and d = 0 in the unit formula (B2-3). The polydiorganosiloxane may be represented by the formula (B2-3b):

[0025] [ka] wherein R A and R 4 is as defined above, and 9,998≧c≧0. Alternatively, in formula (B2-3b), 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 from 80 to 800.

[0026] The starting material (B2) is 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 / methylvinylsiloxane), ) bis-phenyl, methyl, vinyl-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), vii) 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 / methylhex 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-dimethylhexenylsiloxy terminated poly(dimethylsiloxane / diphenylsiloxane), xix) alpha-dimethyl(n-butyl)siloxy-omega-dimethylvinylsiloxy terminated poly(dimethylsiloxane), and xx) combinations of two or more of i) through xix).

[0027] Methods for preparing the above-mentioned linear alkenyl-functional polydiorganosiloxanes for starting material (B2), such as hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or equilibration of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Patent 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.

[0028] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be cyclic, for example, where in the unit formula (B2-1), the subscripts a=b=c=e=f=g=h=0. Cyclic alkenyl-functional polydiorganosiloxanes are represented by the unit formula (B2-7): (R 4 R A SiO 2 / 2 ) d wherein R A and R 4is as above, and subscript d can be 3 to 12, alternatively 3 to 6, alternatively 4 to 5. Examples of cyclic alkenyl functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexavinyl-cyclohexasiloxane. These cyclic alkenyl-functional polydiorganosiloxanes are known in the art and are commercially available, for example, from Sigma-Aldrich (St. Louis, Missouri, USA), Milliken (Spartanburg, South Carolina, USA), and other vendors.

[0029] Alternatively, the cyclic alkenyl-functional polydiorganosiloxane may be represented by the unit formula (B2-8): (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d wherein R 4 and R A is as above, and subscript c is >0 to 6, and subscript d is 3 to 12. Alternatively, in formula (B2-8), c can be 3 to 6, and d can be 3 to 6.

[0030] Alternatively, (B2) the alkenyl-functional polyorganosiloxane may be an oligomer, for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (B2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer may be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as the starting material (B2-6).

[0031] An example of a linear alkenyl-functional polyorganosiloxane oligomer is represented by the formula (B2-10):

[0032] [ka] wherein R 4 is as above, and each R 2 are independently 4 and R A with the proviso that at least one R 2 is R A with the proviso that the subscript z is 0 to 48. Examples of linear alkenyl-functional polyorganosiloxane oligomers can include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-vinyl-disiloxane, 1,1,1,3,5,5,5-heptamethyl-3-vinyl-trisiloxane, all of which are commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA) or Sigma-Aldrich (St. Louis, Missouri, USA).

[0033] Alternatively, the alkenyl-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (B2-11): R A SiR 12 3, wherein R A is as above, and each R 12 is R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR13 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.

[0034] Each R 13 R is an independently selected monovalent hydrocarbon group. 13 The monovalent hydrocarbon groups 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 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 group of R may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl or ethyl. 13 The alkyl group in may be methyl.

[0035] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure:

[0036] [ka] (In the formula, R A and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 As above, R 13 Each R may be 13 can be methyl.

[0037] Alternatively, in formula (B2-11), 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 polyorganosiloxane oligomer having the following structure:

[0038] [ka] (In the formula, R A , R 13 , and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0039] Alternatively, in formula (B2-11), one R 12 is R 13 R 12 Two of them are -OSi(R 14 )3. R 12 Two of them are -OSi(R14 )3 and one R 14 Each -OSi(R 14 )R in 3 13 If R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 )2 in each R 14 The branched polyorganosiloxane oligomer has the following structure:

[0040] [ka] (In the formula, R A , R 13 , and R 15 is as described above) 15 ) 3. 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. Exemplary alkenyl functional branched polyorganosiloxane oligomers include those having the formula:

[0041] [ka] vinyl-tris(trimethylsiloxy)silane having the formula

[0042] [ka] (1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane), and

[0043] [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 the formula (Si10 Vi),

[0044] [ka] (Si10 Hex) 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. The branched alkenyl-functional polyorganosiloxane oligomers 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, (Copyright) The Royal Society of Chemistry 2010.

[0045] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be branched, such as the branched oligomers described above, and / or branched alkenyl-functional polyorganosiloxanes that may have, for example, more alkenyl groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (B2-1), the quantity (a+b+c+d+e+f+g)>50). The branched alkenyl-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide the branched alkenyl-functional polyorganosiloxane (in formula (B2-1)) with greater than 0 to 5 mole percent trifunctional and / or tetrafunctional units.

[0046] For example, the branched alkenyl-functional polyorganosiloxane may be represented by the unit formula (B2-13): (R 4 3SiO 1 / 2 ) q (R 4 2R A SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t In one embodiment, the Q-type branched polyorganosiloxane is represented by the formula: 4 and R A is as above, and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the branched polyorganosiloxane a viscosity of greater than 170 mPa·s as measured by a rotational viscometer (described below along with the test method). Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, alternatively greater than 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, alternatively 190 mPa·s to 420 mPa·s. Q-type branched polyorganosiloxanes suitable for the starting material (B2-12) are known in the art and can be made by known methods, exemplified by those disclosed in U.S. Pat. No. 6,806,339 to Cray et al. and U.S. Patent Application Publication No. 2007 / 0289495 to Cray et al.

[0047] Alternatively, the branched alkenyl-functional polyorganosiloxane may be represented by the formula (B2-14): [R A R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w wherein R A and R 4 is as above, and the subscripts v, w, and x have values ​​such that 200 ≧ v ≧ 1, 2 ≧ w ≧ 0, and 200 ≧ x ≧ 1. Alternatively, in this formula (B2-14), each R 4 is independently selected from the group consisting of methyl and phenyl; A is independently selected from the group consisting of vinyl, allyl, and hexenyl. Suitable branched polyorganosiloxanes for the starting material (B2-14) can be prepared by known methods such as by heating a mixture containing a polyorganosilicate resin and a cyclic or linear polydiorganosiloxane in the presence of a catalyst such as an acid or a phosphazene base, followed by neutralization of the catalyst.

[0048] Alternatively, the branched alkenyl-functional polyorganosiloxane for the starting material (B2-11) may have the unit formula (B2-15): (R 4 3SiO 1 / 2 ) aa (R A R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R A R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd In addition, the polyorganosiloxane may include a T-branched polyorganosiloxane (silsesquioxane) of the formula: 4 and R Ais as above, with subscript aa≧0, subscript bb>0, subscript cc is from 15 to 995, subscript dd>0, and subscript ee≧0. Subscript aa may be from 0 to 10. Alternatively, subscript aa may have a value such that 12≧aa≧0, alternatively 10≧aa≧0, alternatively 7≧aa≧0, alternatively 5≧aa≧0, alternatively 3≧aa≧0. Alternatively, subscript bb≧1. Alternatively, subscript bb≧3. Alternatively, subscript bb may have a value such that 12≧bb>0, alternatively 12≧bb≧3, alternatively 10≧bb>0, alternatively 7≧bb>1, alternatively 5≧bb≧2, alternatively 7≧bb≧3. Alternatively, the subscript cc may have a value such that 800≧cc≧15, alternatively 400≧cc≧15. Alternatively, the subscript ee may have a value such that 800≧ee≧0, 800≧ee≧15, alternatively 400≧ee≧15. Alternatively, the subscript ee may be 0. Alternatively, the quantity (cc+ee) may have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd may be 1 to 10. Alternatively, the subscript dd may have a value such that 10≧dd>0, alternatively 5≧dd>0, alternatively dd=1. Alternatively, the subscript dd may be 1 to 10, alternatively the subscript dd may be 1 or 2. Alternatively, when subscript dd=1, subscript bb can be 3 and subscript cc can be 0. The value of subscript bb can be sufficient to provide a silsesquioxane of formula (B2-15) having an alkenyl content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane. Suitable T-branched polyorganosiloxanes (silsesquioxanes) for the starting material (B2-15) are exemplified by those disclosed in U.S. Patent No. 4,374,967 to Brown et al., U.S. Patent No. 6,001,943 to Enami et al., U.S. Patent No. 8,546,508 to Nabeta et al., and U.S. Patent No. 10,155,852 to Enami.

[0049] Alternatively, (B2) the alkenyl-functional polyorganosiloxane may be represented by the formula R M 3SiO 1 / 2 and monofunctional units ("M" units) of formula SiO 4 / 2 In some embodiments, the alkenyl-functional polyorganosilicate resin may include tetrafunctional silicate units ("Q" units) of the formula: M are independently selected monovalent hydrocarbon radicals, and each R M are independently R as above 4 and R A Alternatively, each R M may be selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, each R M may be selected from methyl, vinyl, and phenyl. Alternatively, R M At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M units are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2ViSiO 1 / 2 The polyorganosilicate resins are soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0050] When prepared, the polyorganosilicate resin contains the M and Q units described above, and the polyorganosiloxane contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M 3) may contain 4 neopentamers, where R M is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M and Q units, expressed as {M(resin)} / {Q(resin)}, excluding the M and Q units from the neopentamer. The M / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M:Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0051] The Mn of the polyorganosilicate resin is determined by the R M The Mn of the polyorganosilicate resin depends on various factors including the type of hydrocarbon group represented by. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively greater than 3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0052] U.S. Patent No. 8,580,073, column 3, line 5 to column 4, line 31, and U.S. Patent Application Publication No. 2016 / 0376482, paragraphs

[0023] to

[0026] are incorporated herein by reference to disclose MQ resins, which are suitable polyorganosilicate resins for use as starting material (B2). The polyorganosilicate resins can be prepared by any suitable method, such as cohydrolysis of the corresponding silanes, or by a silica hydrosol capping method. The polyorganosilicate resins can be prepared by a silica hydrogel capping process, such as those disclosed in U.S. Patent No. 2,676,182 to Daudt et al., U.S. Patent No. 4,611,042 to Rivers-Farrell et al., and U.S. Patent No. 4,774,310 to Butler et al. The method of Daudt et al., supra, involves reacting a silica hydrosol with a hydrolyzable triorganosilane, such as trimethylchlorosilane, a siloxane, such as hexamethyldisiloxane, or mixtures thereof, under acidic conditions, and recovering a copolymer having M and Q units. The resulting copolymer generally contains 2-5 weight percent hydroxyl groups.

[0053] The intermediates used to prepare the polyorganosilicate resins can be triorganosilanes and silanes or alkali metal silicates containing four hydrolyzable substituents. The triorganosilanes are represented by the formula R M 3SiX, where R M is as defined above, and X is a hydroxyl group or, for example, a group represented by the formula (ZO 1 / 2 ) represents a hydrolyzable substituent of the formula SiX. 2 4, wherein each X 2 is independently selected from the group consisting of halogen, alkoxy, and hydroxyl. Suitable alkali metal silicates include sodium silicate.

[0054] The polyorganosilicate resins prepared as described above typically have the formula, for example, HOSiO 3 / 2of silicon-bonded hydroxyl groups. The polyorganosilicate resin may contain up to 3.5% silicon-bonded hydroxyl groups as measured by FTIR spectroscopy and / or NMR spectroscopy, as described above. In certain applications, it may be desirable for the amount of silicon-bonded hydroxyl groups to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane, or disilazane containing the appropriate end group. The silane containing the hydrolyzable group can be added in a molar excess over the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0055] Alternatively, the polyorganosilicate resin has no more than 2%, alternatively no more than 0.7%, alternatively no more than 0.3%, alternatively between 0.3% and 0.8% hydroxyl groups, e.g., of the formula XSiO 3 / 2 (In the formula, R M wherein X represents a hydrolyzable substituent, e.g., OH. The concentration of silanol groups (wherein X=OH) present in the polyorganosilicate resin can be determined using FTIR spectroscopy and / or NMR, as described above.

[0056] For use herein, polyorganosilicate resins further comprise one or more terminal alkenyl groups per molecule. Polyorganosilicate resins having terminal alkenyl groups can be prepared by reacting the product of Daudt et al. with an alkenyl-containing endblocking agent and an endblocking agent free of aliphatic unsaturation in an amount sufficient to provide 3 to 30 mole percent alkenyl groups in the final product. Examples of endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and are exemplified in U.S. Patents 4,584,355 to Blizzard et al., 4,591,622 to Blizzard et al., and 4,585,836 to Homan et al. A single endblocking agent or a mixture of such agents can be used to prepare such resins.

[0057] Alternatively, the polyorganosilicate resin may be represented by the unit formula (B2-17): (R 4 3SiO 1 / 2 ) mm (R 4 2R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h wherein Z, R 4 , and R A , and subscript h are as above, and the subscripts mm, nn, and oo have average values ​​such that mm≧0, nn>0, oo>0, and 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively, 0.7≦(mm+nn) / oo≦4, alternatively, 0.8≦(mm+nn) / oo≦4.

[0058] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be (B2-18) an alkenyl-functional silsesquioxane resin, i.e., a polyorganosiloxane having the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h may contain a resin containing trifunctional (T) units of the formula, where R 4 and R A are as defined above, subscript f > 1, 2 < (e + f) < 10,000, 0 < (a + b) / (e + f) < 3, 0 < (c + d) / (e + f) < 3, and 0 < h / (e + f) < 1.5. Alternatively, the alkenyl-functional silsesquioxane resin may contain the unit formula (B2-19): (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h , where R 4 , R A , Z, and subscripts h, e, and f are as defined above. Alternatively, in addition to the above T units, the alkenyl-functional silsesquioxane resin may further contain difunctional (D) units of the formula (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d , i.e., a DT resin, where subscripts c and d are as defined above. Alternatively, the alkenyl-functional silsesquioxane resin has the formula (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) bwhere the subscripts a and b are as defined above for unit formula (B2-1).

[0059] Alkenyl-functional silsesquioxane resins are commercially available, for example, of the formula (B2-20): (Me2ViSiO 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 RMS-310, which includes D-units, is commercially available from Dow Silicones Corporation (Midland, Michigan, USA). Alkenyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trialkoxysilanes or mixtures using methods such as those described in "Chemistry and Technology of Silicone" by Noll, Academic Press, 1968, chapter 5, p190-245. Alternatively, alkenyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trichlorosilanes using methods described in U.S. Pat. No. 6,281,285 to Becker et al. and U.S. Pat. No. 5,010,159 to Bank et al. Alkenyl-functional silsesquioxane resins containing D units can be prepared by known methods such as those disclosed in U.S. Patent Application Publication No. 2020 / 0140619 to Swier et al. and WO 2018 / 204068 to Swier et al.

[0060] The starting material (B) can be any one of the alkenyl-functional organosilicon compounds described above. Alternatively, the starting material (B) can include a mixture of two or more of the alkenyl-functional organosilicon compounds.

[0061] (C) Hydroformylation reaction catalyst The starting material (C), which is a hydroformylation catalyst for use herein, 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):

[0062] [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 (in the formula, each R 17 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.

[0063] 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 group of R may be selected from the group consisting of ethyl, propyl, and butyl, alternatively propyl and butyl. 6 and R 6’ The alkyl group in R may 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 for

[0064] 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.

[0065] 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 of R may be selected from the group consisting of propyl and butyl. 7 and R 7’ The alkyl group can be butyl.

[0066] Alternatively, in formula (C1), R 7 and R 7’ is represented by the formula -SiR 17 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.

[0067] 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.

[0068] In formula (C1), R 8 , R8’ , 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.

[0069] 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, each R 10 and R 10’ Alternatively, each R 10 and R 10’ can be hydrogen.

[0070] 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 of R 6 and R 6’ may be as described above for each R. Alternatively, 11 and R 11’ can be hydrogen.

[0071] 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).

[0072] 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).

[0073] 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).

[0074] The rhodium / bisphosphite ligand complex catalyst, starting material (C), can be prepared by varying the appropriate starting materials in a manner 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. For example, the rhodium / bisphosphite ligand complex can be prepared by a process comprising mixing 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.

[0075] 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 materials (A) and / or (B), the alkenyl functional organosilicon compound, 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.

[0076] The amount of (C) rhodium / bisphosphite ligand complex catalyst (catalyst) is sufficient to catalyze the hydroformylation of (B) alkenyl-functional organosilicon compound. The exact amount of catalyst depends on various factors, including the type of alkenyl-functional organosilicon compound 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 organosilicon compound. 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 organosilicon compound.

[0077] (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 a solvent to facilitate mixing and / or delivery 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 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 material. The amount of solvent is not critical, but if present, the amount of solvent may be 5% to 70% based on the weight of starting material (B), which is an alkenyl-functional organosilicon compound.

[0078] Hydroformylation reaction conditions In the process described herein, the hydroformylation reaction of step 1) is carried out at a relatively low temperature. For example, the hydroformylation reaction of 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 of the hydroformylation reaction can be up to 150°C. Alternatively, it can be up to 100°C, alternatively up to 90°C, alternatively up to 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.

[0079] In the process described herein, the hydroformylation reaction of 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 1,000 kPa, alternatively 344 kPa to 689 kPa. Without wishing to be bound by theory, it is believed that it may be beneficial to use a relatively low pressure, for example, less than 6,895 kPa, in the hydroformylation reaction step of the process herein, and the ligand described herein has the advantage of enabling low pressure hydroformylation reaction, which has the advantage of being less costly and more safe than high pressure hydroformylation reaction.Furthermore, the hydroformylation reaction used in the process herein has the advantage of being robust in that it can convert a wide variety of alkenyl functional organosilicon compounds into aldehyde functional organosilicon compounds (silane to polyorganosiloxane resin), as shown in the following examples.

[0080] The hydroformylation reaction of the process may be carried out in batch, semi-batch, or continuous mode using one or more suitable reactors, such as fixed bed reactors, fluidized bed reactors, continuous stirred tank reactors (CSTRs), or slurry reactors. (B) The alkenyl-functional organosilicon compound 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 and achieving high catalyst selectivity, activity, life, and ease of operation, as well as the reactivity of the particular starting material and the reaction conditions selected, and the desired products.

[0081] Alternatively, the hydroformylation reaction can be carried out in a continuous manner.For example, the hydroformylation reaction 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 organosilicon compound and (C) the rhodium / bisphosphite ligand complex catalyst described herein, respectively.

[0082] Step 1) of the process forms a hydroformylation reaction product comprising (E) an aldehyde-functional organosilicon compound. 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 organosilicon compound, 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.

[0083] The process may further include one or more additional steps, such as 2) recovering the aldehyde-functional organosilicon compound (E) from the hydroformylation reaction product. This can be done by separating the rhodium / bisphosphite ligand complex catalyst (C) from the hydroformylation reaction product. Separating the rhodium / bisphosphite ligand complex catalyst (C) can 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.

[0084] 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 organosilicon compound produced by the process may be stable even if the hydroformylation catalyst is not removed.Furthermore, without being bound by theory, it is believed that (C) hydroformylation catalyst may also catalyze the oxidation reaction of the aldehyde-functional organosilicon compound, as described herein below.Therefore, alternatively, the above hydroformylation process may be carried out without removing the hydroformylation catalyst in step 2).

[0085] Alternatively, optional step 2) of the process may include purification of the hydroformylation reaction product.For example, the aldehyde-functional organosilicon compound may be isolated from the above-mentioned additional materials by any convenient means, such as stripping and / or distillation, optionally using reduced pressure.Alternatively, step 2) may be omitted, leaving (C) the hydroformylation reaction catalyst in the hydroformylation reaction product, for example, containing the aldehyde-functional organosilicon compound.

[0086] Aldehyde-functional organosilicon compounds are useful as starting materials in the above process for preparing vinyl ester-functional organosilicon compounds. The starting material (E) is an aldehyde-functional organosilicon compound having at least one aldehyde functional group covalently bonded to silicon per molecule. Alternatively, the aldehyde-functional organosilicon compound may have one 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. G can be linear or branched. Examples of divalent hydrocarbyl groups for G include those having the empirical formula -C r H 2r -, where the subscript r is 2 to 8. The alkane-diyl group can be a linear alkane-diyl, for example, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane-diyl, for example,

[0088] [ka] Alternatively, each G can be an alkane-diyl group of 2 to 6 carbon atoms, alternatively 2, 3, or 6 carbon atoms. The aldehyde-functional organosilicon compound can be one aldehyde-functional organosilicon compound. Alternatively, two or more aldehyde-functional organosilicon compounds different from each other can be used in the process described herein. For example, the aldehyde-functional organosilicon compound can include one or both of an aldehyde-functional silane and an aldehyde-functional polyorganosiloxane.

[0089] Alternatively, the aldehyde-functional organosilicon compound may include (E1) an aldehyde-functional silane. The aldehyde-functional organosilicon compound may be represented by the formula (E1-1): R Ald x SiR 4 (4-x) wherein each R Ald are independently selected formulas as above

[0090] [ka] is a group of R 4 and subscript x is as defined above for formula (B1-1).

[0091] Suitable aldehyde-functional silanes are exemplified by aldehyde-functional trialkylsilanes such as (propyl-aldehyde)-trimethylsilane, (propyl-aldehyde)-triethylsilane, and (butyl-aldehyde)trimethylsilane.

[0092] Alternatively, the aldehyde-functional organosilicon compound may comprise (E2) an aldehyde-functional polyorganosiloxane. The aldehyde-functional organosilicon compound may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The aldehyde-functional polyorganosiloxane may be represented by the unit formula (E2-1): (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein each R I are independently selected formulas as described above for formula (E1-1).

[0093] [ka] is an aldehyde group, and R 4 is as defined above for formula (B1-1), and Z, and the subscripts a, b, c, d, e, f, g, and h are as defined above for formula (B2-1).

[0094] Alternatively, the (E2) aldehyde-functional polyorganosiloxane may comprise (E2-2) a linear polydiorganosiloxane having at least one aldehyde functional group per molecule, alternatively at least two aldehyde functional groups (e.g., where subscripts e=f=g=0 in formula (E2-1) for the aldehyde-functional polyorganosiloxane above). For example, the polydiorganosiloxane may comprise a unit of formula (E2-3): (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 are as defined above for formula (B1-1) and the subscripts a, b, c, and d are as defined above for unit formula (B2-3).

[0095] Alternatively, the linear aldehyde-functional polydiorganosiloxane of the unit formula (E2-3) may be represented by the unit formula (E2-4): (R 4 2R Ald SiO 1 / 2 )2(R 4 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 Aldis as described above for formula (E1-1), and each 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).

[0096] Alternatively, the polydiorganosiloxane of the unit formula (E2-3) is represented by the formula (E2-3a):

[0097] [ka] wherein each R 2’ are independently 4 and R Ald with the proviso that at least one R 2’ is R Ald And each R Ald is as described above for formula (E1-1), and each R 4 is as described above for formula (B1-1) and the subscript zz is as described above for formula (B2-3a).

[0098] 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 (E2-3). The polydiorganosiloxane may be represented by the formula (E2-3b):

[0099] [ka] wherein R Ald is as described above for formula (E1-1), and each R 4 is as described above for formula (B1-1) and subscript c is as described above for formula (B2-3b).

[0100] 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 (heptyl-aldehyde)siloxy terminated polydimethylsiloxane, xi) 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-di 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 α-dimethyl(n-butyl)siloxy-ω-dimethyl(propylaldehyde)siloxy terminated poly(dimethylsiloxane); and xx) combinations of two or more of i) through xix).

[0101] Alternatively, (E2) the aldehyde-functional polyorganosiloxane may be cyclic, for example, in the unit formula (E2-1), the subscripts a=b=c=e=f=g=h=0. (E2-6) The cyclic aldehyde-functional polydiorganosiloxane may be represented by the unit formula (E2-7): (R 4 R Ald SiO 2 / 2 ) d wherein each R Ald is as described above for formula (E1-1), and each R 4 is as described above for formula (B1-1) and subscript d is as described above for unit formula (B2-7). Examples of cyclic aldehyde-functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-tri(propyl-aldehyde)-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra(propyl-aldehyde)-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-penta(propyl-aldehyde)-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexa(propyl-aldehyde)-cyclohexasiloxane.

[0102] Alternatively, the (E2-6) cyclic aldehyde-functional polydiorganosiloxane may be represented by the unit formula (E2-8): (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d wherein each R Ald is as described above for formula (E1-1), and each R 4is as defined above for formula (B1-1), and the subscripts c and d are as defined above for unit formula (B2-8).

[0103] Alternatively, (E2) aldehyde-functional polyorganosiloxane may be (E2-9) oligomer, for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (E2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer may be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as starting material (E2-6).

[0104] An example of a linear aldehyde-functional polyorganosiloxane oligomer is represented by the formula (E2-10):

[0105] [ka] wherein each R 4 is as described above for formula (B1-1), and each R 2’ is R 4 and R Ald with the proviso that at least one R 2’ is RAld, and each R Ald is as described above for formula (E1-1), and subscript z is 0 to 48. Examples of linear aldehyde-functional polyorganosiloxane oligomers include 1,3-di(propyl-aldehyde)-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-(propyl-aldehyde)-disiloxane, and 1,1,1,3,5,5,5-heptamethyl-3-(propyl-aldehyde)-trisiloxane.

[0106] Alternatively, the aldehyde-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (E2-11): R Ald SiR 123, where R Ald is as described above for formula (E1-1), and each R 12 is R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and 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.

[0107] Alternatively, in formula (E2-11), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure:

[0108] [ka] (In the formula, R Ald and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0109] Alternatively, in formula (E2-11), 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:

[0110] [ka] (In the formula, R Ald , R 13 , and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0111] Alternatively, in formula (E2-11), 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 and one R 14 Each -OSi(R 14 )R in 3 13 If 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:

[0112] [ka] (In the formula, R Ald , R 13 , and R 15 is as described above) 15 ) 3. Alternatively, each R 15 is R 13 Each R 13 can 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. Exemplary aldehyde functional branched polyorganosiloxane oligomers include those having the formula:

[0113] [ka] 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal (which may be referred to as propylaldehyde-tris(trimethylsiloxy)silane), having the formula

[0114] [ka] 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propanal (which may also be referred to as methyl-(propylaldehyde)-di((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-silane), having the formula

[0115] [ka] 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

[0116] [ka] and 7-(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)heptanal (which may also be referred to as (heptylaldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-silane), having the formula:

[0117] Alternatively, the (E2) aldehyde-functional polyorganosiloxane may be branched, such as the branched oligomers described above, and / or branched aldehyde-functional polyorganosiloxanes that may have, for example, more aldehyde groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (E2-1), the quantity (a+b+c+d+e+f+g)>50). The branched aldehyde-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide the branched aldehyde-functional polyorganosiloxane (in formula (E2-1)) with greater than 0 to 5 mole percent trifunctional and / or tetrafunctional units.

[0118] For example, the branched aldehyde-functional polyorganosiloxane may be represented by the unit formula (E2-13): 4 3SiO 1 / 2 ) q (R 4 2R Ald SiO 1 / 2 )r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t wherein each R 4 is as described above for formula (B1-1), and each R Ald is as described above for formula (E1-1), and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) have a value sufficient for the branched polyorganosiloxane to have a viscosity greater than 170 mPa·s as measured by rotational viscometry (described below along with the test method). Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, alternatively greater than 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, alternatively 190 mPa·s to 420 mPa·s.

[0119] Alternatively, the branched aldehyde-functional polyorganosiloxane may be represented by the formula (E2-14): [R Ald R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w wherein each R 4 is as described above for formula (B1-1), and each R Ald are as defined above for formula (E1-1). The subscripts v, w and x are as defined above for formula (B2-14).

[0120] Alternatively, the branched aldehyde-functional polyorganosiloxane for the starting material (E2-11) may have the unit formula (E2-15): (R 4 3SiO 1 / 2 ) aa (R Ald R 4 2SiO 1 / 2 ) bb (R 4 2SiO2 / 2 ) cc (R Ald R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd In the formula, each R 4 is as described above for formula (B1-1), and each R Ald are as described above for formula (E1-1), and the subscripts aa, bb, cc, dd, and ee are as described above for formula (B2-15). Alternatively, the value of subscript bb may be sufficient to provide a silsesquioxane of formula (E2-15) having an aldehyde content of from 0.1% to 1%, alternatively from 0.2% to 0.6%, based on the weight of the silsesquioxane.

[0121] Alternatively, (E2) the aldehyde-functional polyorganosiloxane may comprise an aldehyde-functional polyorganosiloxane resin, such as an aldehyde-functional polyorganosilicate resin and / or an aldehyde-functional silsesquioxane resin. Such resins may be prepared, for example, by hydroformylating an alkenyl-functional polyorganosiloxane resin, as described above. The aldehyde-functional polyorganosilicate resin may be represented by the formula R M’ 3SiO 1 / 2 and monofunctional units ("M" units) of formula SiO 4 / 2 "R" is a tetrafunctional silicate unit ("Q" unit) of the formula M’ are independently R as above 4 and R Ald Alternatively, each R M’ may be selected from the group consisting of alkyl groups, aldehyde functional groups of the formula shown above, and aryl groups. Alternatively, each R M’ may be selected from methyl, propylaldehyde, heptylaldehyde and phenyl. Alternatively, R M’ At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M' units are (MeSiO 1 / 2), (Me2PhSiO 1 / 2 ), and (MeR Ald SiO 1 / 2 The polyorganosilicate resins are soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0122] When prepared, the polyorganosilicate resin contains the M' and Q units described above, and the polyorganosilicate resin contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M’ 3) may contain 4 neopentamers, where R M’ is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M' and Q units, expressed as {M'(resin)} / {Q(resin)}, excluding the M' and Q units from the neopentamer. The M' / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M' units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M' / Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0123] The Mn of the polyorganosilicate resin is determined by the R M’The Mn of the polyorganosilicate resin depends on various factors including the type of group represented by. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively greater than 3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0124] Alternatively, the polyorganosilicate resin may be represented by the unit formula (E2-17): 4 3SiO 1 / 2 ) mm (R 4 2R Ald SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R Ald is as defined above for formula (E1-1), each Z is as defined above for unit formula (B2-1), and the subscripts mm, nn and oo are as defined above for unit formula (B2-17).

[0125] Alternatively, (E2) the aldehyde-functional polyorganosiloxane may include (E2-18) an aldehyde-functional silsesquioxane resin, i.e., a resin including trifunctional units, the aldehyde-functional silsesquioxane resin being represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 )e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R Ald is as described above for formula (E1-1), each Z is as described above for unit formula (B2-1), and the subscripts a, b, c, d, e, f, and h are as described above for formula (B2-18). Alternatively, the aldehyde-functional silsesquioxane resin can be represented by a unit formula (E2-19): (R 4 SiO 3 / 2e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R Ald is as described above for formula (E1-1), each Z is as described above for unit formula (B2-1), and subscripts e, f, and h are as described above for formula (B2-19). Alternatively, the aldehyde-functional silsesquioxane resin may contain, in addition to the T units described above, units of the formula (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d where subscripts c and d are as defined above. Alternatively, the aldehyde-functional silsesquioxane resin may further comprise a difunctional (D') unit of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b , ie, an M'D'T' resin, where the subscripts a and b are as defined above.

[0126] The starting material (E) can be any one of the aldehyde-functional organosilicon compounds described above. Alternatively, the starting material (E) can include a mixture of two or more of the aldehyde-functional organosilicon compounds.

[0127] Carboxy-functional organosilicon compounds The process described herein comprises reacting (I) a carboxy-functional organosilicon compound with 3) Under conditions in which an oxidation reaction occurs, (E) an aldehyde-functional organosilicon compound as described above; and (F) an oxygen source; Optionally, (G) an oxidation reaction catalyst; Optionally, the method may further include preparing the reaction product by a process that includes mixing the starting materials with a second solvent (suitable for use in the oxidation reaction), thereby forming an oxidation reaction product that includes (I) a carboxy-functional organosilicon compound.

[0128] Alternatively, in addition to the above steps, the process may optionally further comprise drying one or more of the starting materials (E), (F), (G), and (H) prior to the oxidation reaction, e.g., in step 3).

[0129] The process may optionally further comprise 4) recovering the carboxy-functional organosilicon compound from the oxidation reaction product. Step 4) may be carried out during and / or after step 3).

[0130] (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 (>99% purity) 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 to the aldehyde functionality of the starting material (E) above-mentioned aldehyde-functional organosilicon compound. The amount of oxygen source (and reaction conditions) is sufficient to allow at least one aldehyde functionality per molecule of aldehyde-functional organosilicon compound to be oxidized. Alternatively, a portion of the aldehyde functionality can be converted to a carboxylic acid functionality. Alternatively, complete conversion of the aldehyde functionality to a carboxylic acid functionality can be performed.

[0131] (G) Oxidation reaction catalyst The oxidation catalyst used in the process for preparing the carboxy-functional organosilicon compound (Step 3) can be a heterogeneous oxidation catalyst, a homogeneous oxidation catalyst, or a combination thereof.

[0132] 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 RSCAdv., 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 being bound by theory, it is believed that when the above hydroformylation process is used to make an aldehyde-functional organosilicon compound, 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).

[0133] 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 organosilicon compound, 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) may be from 0.001 mol% to 1 mol%, alternatively from 0.005 mol% to 0.5 mol%, based on the number of moles of aldehyde functional groups in the starting (E) aldehyde-functional organosilicon compound. Alternatively, the amount of catalyst may 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 may 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, if the process is run in a continuous mode, for example by filling the reactor with a heterogeneous oxidation catalyst, the amount of oxidation catalyst may be increased by 10 h. -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.

[0134] (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 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 organosilicon compound used as starting material (E).

[0135] 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 organosilicon compound selected, and the reactor configuration. Without being bound by theory, it is believed that the oxidation reaction rate can increase with increasing temperature, but the oxygen solubility in the aldehyde-functional organosilicon compound 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.

[0136] The oxidation reaction can be carried out in batch mode 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.

[0137] Alternatively, in batch mode, the end point of the oxidation reaction may be considered to be the time when a decrease in the hydrogen 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.

[0138] The oxidation reaction in step 3) may optionally further comprise irradiating the reaction mixture with ultraviolet (UV) light. The UV light 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 light 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 2Without being bound by theory, it is believed that UV irradiation may increase the rate of the oxidation reaction in step 3).

[0139] 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 in a structured packing or other fixed structure, or by a combination of these (e.g., step 4).

[0140] The carboxy-functional organosilicon compounds prepared as above have at least one carboxy-functional group covalently bonded to silicon per molecule. Alternatively, the carboxy-functional organosilicon compounds may have more than one carboxy-functional group covalently bonded to silicon per molecule. R, the carboxy-functional group covalently bonded to silicon, Car is the expression:

[0141] [ka] where G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms as described and exemplified above for the (E) aldehyde-functional organosilicon compounds. Alternatively, each R Car are independently -(C2H4)C(=O)OH, -(C3H6)C(=O)OH, and -(C6H 12 The carboxy functional organosilicon compound may have any of the formulas shown above for the (E) aldehyde functional organosilicon compound, except that R Ald At least one instance of R Car or alternatively R Ald All of the cases are R Car can be replaced with.

[0142] Process for preparing vinyl ester functional organosilicon compounds The process for preparing the vinyl ester functional organosilicon compounds described herein includes: reacting a compound selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, (I) a carboxy-functional organosilicon compound as described above; (J) formula

[0143] [ka] wherein R 3 is an alkyl group having 1 to 6 carbon atoms, vinyl acetate functional compound (K) vinyl exchange reaction catalyst, optionally (L) a (third) solvent, and Optionally, mixing starting materials including (X) an inhibitor; thereby preparing a reaction mixture comprising a vinyl ester functional organosilicon compound.

[0144] When a process including hydroformylation and oxidation reactions as described above is used to prepare the carboxy-functional organosilicon compound (I), a vinyl exchange reaction can be carried out in step 5).

[0145] The vinylation reaction (e.g., step 5)) can be carried out at ambient pressure. The vinylation reaction can be carried out at a temperature of 0 to 150°C. The temperature of the vinylation 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 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.

[0146] The vinyl exchange reaction can be carried out in batch or continuous mode. In batch mode, the vinyl exchange reaction can be carried out for 1 minute to 250 hours, although the reaction time depends on various factors including the amount of vinyl exchange 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 vinyl exchange 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.

[0147] The process for preparing vinyl ester functional organosilicon compounds may optionally further comprise recovering the vinyl ester functional organosilicon compounds. This may be carried out in step 6) when a process comprising hydroformylation and oxidation reactions is used to prepare the above carboxy functional organosilicon compounds. Recovering the vinyl ester functional organosilicon compounds may be carried out by any convenient means, such as filtration, stripping and / or distillation, optionally under heating and / or reduced pressure.

[0148] (I) Carboxy-functional organosilicon compounds The starting material (I) in the preparation process of vinyl ester functional organosilicon compounds is a carboxy functional organosilicon compound. In addition to or instead of the carboxy functional organosilicon compounds 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 with a molecular weight of 1500 g / mol, commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA). Other carboxyalkyl terminated polydimethylsiloxanes include biscarboxypropyl and biscarboxydecyl terminated polydimethylsiloxanes (also from Gelest under the trade names DMS-B12, DMS-B25, and DMS-B31) with molecular weights ranging from 1,000 to 28,000.

[0149] The carboxy-functional organosilicon compound is represented by the formula (I1) (I1-1): Car x SiR 4 (4-x) wherein each R Car are independently selected expressions

[0150] [ka] where 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 4 is as described above for starting material (B1-1) and the subscript x is as described above for starting material (B1-1).

[0151] Alternatively, the carboxy-functional organosilicon compound may comprise (I2) a carboxy-functional polyorganosiloxane. The carboxy-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The carboxy-functional organosilicon compound may have the unit formula (I2-1): (R 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Car SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein R Car is as described above for formula (I1-1), and R 4 is as described above for formula (B1-1), and Z and subscripts a, b, c, d, e, f, g, and h are as described above for formula (B2-1).

[0152] Alternatively, (I2) the carboxy-functional polyorganosiloxane compound may comprise (I2-2), a linear polydiorganosiloxane having at least one carboxy-functional group per molecule, or alternatively at least two carboxy-functional groups (e.g., where subscripts e=f=g=0 in formula (I2-1) for the carboxy-functional polyorganosiloxane above). For example, the polydiorganosiloxane may have the unit formula (I2-3): (R 4 3SiO 1 / 2 ) a (R Car R 4 2SiO 1 / 2 ) b (R 42SiO 2 / 2 ) c (R Car R 4 SiO 2 / 2 ) d wherein R Car is as described above for formula (I1-1), and R 4 are as defined above for formula (B1-1) and the subscripts a, b, c, and d are as defined above for unit formula (B2-3).

[0153] Alternatively, the linear carboxy-functional polydiorganosiloxane of the unit formula (I2-3) may be represented by the unit formula (I2-4): (R 4 2R Ald SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R Car SiO 2 / 2 ) n , Unit formula (I2-5): (R 4 3R Car SiO 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 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).

[0154] Alternatively, the polydiorganosiloxane of the unit formula (I2-3) is represented by the formula (I2-3a):

[0155] [ka] wherein each R 2’’are independently 4 and R Car with the proviso that at least one R 2’’ is R Car And each R Car is as described above for formula (I1-1), and each R 4 is as described above for formula (B1-1) and the subscript zz is as described above for formula (B2-3a).

[0156] 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 (I2-3). The polydiorganosiloxane may have the formula (I2-3b).

[0157] [ka] In the formula, R Car is as described above for formula (I1-1), and each R 4 is as described above for formula (B1-1) and subscript c is as described above for formula (B2-3b).

[0158] The starting material (I2) is i) bisdimethyl(propanoic acid)siloxy-terminated polydimethylsiloxane, ii) bisdimethyl(propanoic acid)siloxy-terminated poly(dimethylsiloxane / methyl(propanoic acid)siloxane), iii) bisdimethyl(propanoic acid)siloxy-terminated polymethyl(propanoic acid)siloxane, iv) bistrimethylsiloxy-terminated poly(dimethylsiloxane / methyl(propanoic acid)siloxane), v) bistrimethylsiloxy-terminated polymethyl(propanoic acid)siloxane, vi) bisdimethyl(propanoic acid)siloxy-terminated poly(dimethylsiloxane / methyl(propanoic acid)siloxane siloxane / 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( 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) through xix).

[0159] Alternatively, the carboxy-functional polyorganosiloxane may be, for example, the unit formula (I2-1) where the subscripts a=b=c=e=f=g=h=0. (I2-6) The cyclic carboxy-functional polydiorganosiloxane may be, for example, the unit formula (I2-7): (R 4 R Car SiO 2 / 2 ) d wherein R Car is as described above for formula (I1-1), and R 4 is as described above for formula (B1-1) and subscript d is as described above for formula (B2-7). Examples of cyclic aminopropyl-functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-tri(propanoic acid)-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra(propanoic acid)-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-penta(propanoic acid)-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexa(propanoic acid)-cyclohexasiloxane.

[0160] Alternatively, (I2-6) the cyclic carboxy-functional polydiorganosiloxane may be represented by the unit formula (I2-8): (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d wherein R Car is as described above for formula (I1-1), and R 4 is as defined above for formula (B1-1), and the subscripts c and d are as defined above for unit formula (B2-8).

[0161] Alternatively, (I2) the carboxy-functional polyorganosiloxane may be an oligomer (I2-9), for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (I2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer may be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as the starting material (I2-6).

[0162] An example of a linear carboxy-functional polyorganosiloxane oligomer is represented by the formula (I2-10):

[0163] [ka] wherein each R 4 is as described above for formula (B1-1), and each R 2’’ is R 4 and R Car with the proviso that at least one R 2’’ is R Car And each R Car is as described above for formula (I1-1), and subscript z is 0 to 48.

[0164] Alternatively, the carboxy-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (I2-11): R Car SiR 12 3, wherein R Car is as described above for formula (I1-1), and each R 12 is R 13 and -OSi(R14)3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 15is 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.

[0165] Alternatively, in formula (I2-11), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure:

[0166] [ka] (In the formula, R Car and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0167] Alternatively, in formula (I2-11), 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's14 each of which is a branched carboxy-functional polyorganosiloxane oligomer having the following structure:

[0168] [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.

[0169] Alternatively, in formula (I2-11), 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 and one R 14 Each -OSi(R 14 )R in 3 13 If 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:

[0170] [ka] (In the formula, R Car , R 13 , and R 15 is as described above) 15 ) 3. Alternatively, each R 15 is R 13 Each R 13may be methyl. Alternatively, the carboxy functional branched polyorganosiloxane may 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 branched polyorganosiloxane oligomers include those of the formula:

[0171] [ka] 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanoic acid, having the formula

[0172] [ka] and 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propanoic acid having the formula

[0173] [ka] (Si10Pr acid), 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 having the formula

[0174] [ka] (SilOHep acid), 7-(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)propyl methacrylate.

[0175] Alternatively, (I2) the carboxy-functional polyorganosiloxane may be branched, such as the branched oligomers described above, and / or branched carboxy-functional polyorganosiloxanes that may have, for example, more carboxy groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (I2-1), the quantity (a+b+c+d+e+f+g)>50). The branched carboxy-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide the branched carboxy-functional polyorganosiloxane (in formula (I2-1)) with greater than 0 to 5 mole percent trifunctional and / or tetrafunctional units.

[0176] For example, the branched carboxy-functional polyorganosiloxane may be represented by the unit formula (I2-13): 4 3SiO 1 / 2 ) q (R 4 2R Car SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t wherein each R 4 is as described above for formula (B1-1), and each R Caris as described above for formula (I1-1), and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) have a value sufficient for the branched polyorganosiloxane to have a viscosity greater than 170 mPa·s as measured by rotational viscometry (described below along with the test method). Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, alternatively greater than 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, alternatively 190 mPa·s to 420 mPa·s.

[0177] Alternatively, the branched carboxy-functional polyorganosiloxane may be represented by the formula (I2-14): [R Car R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w wherein each R 4 is as described above for formula (B1-1), and each R Car are as defined above for formula (I1-1). The subscripts v, w and x are as defined above for formula (B2-14).

[0178] Alternatively, the branched carboxy-functional polyorganosiloxane for (I2-11) may have the unit formula (I2-15): (R 4 3SiO 1 / 2 ) aa (R Car R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R Car R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd In the formula, each R4 is as described above for formula (B1-1), and each R Car are as described above for formula (I1-1), and the subscripts aa, bb, cc, dd, and ee are as described above for unit formula (B2-15). The value of subscript bb may be sufficient to provide the silsesquioxane of unit formula (I2-15) with from 0.1% to 1%, alternatively from 0.2% to 0.6%, of carboxy groups, based on the weight of the silsesquioxane.

[0179] Alternatively, (I2) the carboxy-functional polyorganosiloxane may comprise a carboxy-functional polyorganosiloxane resin, such as a carboxy-functional polyorganosilicate resin and / or a carboxy-functional silsesquioxane resin. The carboxy-functional polyorganosilicate resin may be represented by the formula R M’’ 3SiO 1 / 2 and monofunctional units ("M'' units) of formula SiO 4 / 2 "R" is a tetrafunctional silicate unit ("Q" unit) of the formula M’’ are independently R as above 4 and R Car Alternatively, each R M’’ may be selected from the group consisting of alkyl groups, carboxy functional groups of the formula shown above, and aryl groups. Alternatively, each R M’’ may be selected from methyl, (propanoic acid), (heptanoic acid), and phenyl. Alternatively, R M’’ At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M″ units are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (MeR Car SiO 1 / 2 The polyorganosilicate resins are soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0180] When prepared, the polyorganosilicate resin contains the M″ and Q units described above, and the polyorganosilicate resin contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M’’ 3) may contain 4 neopentamers, where R M’’ is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M″ and Q units, expressed as {M″(resin)} / {Q(resin)}, excluding the M″ and Q units from the neopentamer. The M″ / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M″ units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M″ / Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0181] The Mn of the polyorganosilicate resin is determined by the R M’’ The Mn of the polyorganosilicate resin depends on various factors including the type of group represented by. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively greater than 3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0182] Alternatively, the carboxy-functional polyorganosilicate resin may be represented by the unit formula (I2-17): 4 3SiO 1 / 2 ) mm (R 4 2R Car SiO 1 / 2 ) nn (SiO4 / 2 ) oo (ZO 1 / 2 ) h and each R 4 is as described above for formula (B1-1), and each R Car is as defined above for formula (I1-1), each Z is as defined above for unit formula (B2-1), and the subscripts mm, nn and oo are as defined above for unit formula (B2-17).

[0183] Alternatively, (I2) the carboxy-functional polyorganosiloxane may include a I2-18 carboxy-functional silsesquioxane resin, i.e., a resin containing trifunctional units. The carboxy-functional silsesquioxane resin is represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Car SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R Car is as defined above for formula (I1-1), each Z is as defined above for unit formula (B2-1), and the subscripts a, b, c, d, e, f, and h are as defined above for formula (B2-18).

[0184] Alternatively, the carboxy-functional silsesquioxane resin may be represented by the unit formula (I2-19): 4 SiO 3 / 2e (R Car SiO 3 / 2 ) f (ZO1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R Car is as described above for formula (I1-1), each Z is as described above for unit formula (B2-1), and subscripts e, f, and h are as described above for formula (B2-19). Alternatively, the carboxy-functional silsesquioxane resin may contain, in addition to the T units described above, units of the formula (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d where subscripts c and d are as defined above. Alternatively, the carboxy-functional silsesquioxane resin may further comprise a difunctional (D″) unit of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b , ie, M''D''T'' resins, where the subscripts a and b are as defined above.

[0185] 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.

[0186] (J) Vinyl acetate functional compounds In the process for preparing a vinyl ester functional organosilicon compound, the tarred material (J) is a vinyl acetate functional compound. The vinyl acetate functional compound may have the formula:

[0187] [ka] In the formula, R 3R 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) may be vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl laurate, and combinations of two or more thereof. Alternatively, R 3 can be methyl. These vinyl acetate functional compounds are known in the art and are commercially available from a variety of suppliers, such as Sigma-Aldrich, Inc. of St. Louis, Missouri, USA. Alternatively, the starting material (A) can include vinyl acetate.

[0188] The amount of (J) the vinyl acetate functional compound may be from 0.1 molar equivalents to 20 molar equivalents based on the carboxy functionality content of (I) the carboxy functional organosilicon compound.

[0189] (K) Transvinylation catalyst The vinylation catalyst used herein may comprise 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 vinylation catalyst may be a palladium-ligand complex. The ligand may be a phenanthroline. For example, the vinylation catalyst may be prepared by a process that includes mixing a palladium catalyst precursor with a phenanthroline ligand under conditions to form a complex, which complex may then be introduced into a vinylation 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, 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 the introduction of the palladium catalyst precursor) for the in situ formation of the palladium / phenanthroline ligand complex. The palladium / phenanthroline ligand complex can be activated by heating to form the (K) vinyl exchange reaction catalyst. The palladium catalyst precursor is exemplified by palladium acetate.

[0190] For example, the palladium catalyst precursor, such as palladium acetate, optionally the starting material (L), the (third) solvent, and the phenanthroline ligand can be combined by any convenient means, such as by mixing. The resulting palladium / phenanthroline ligand complex can be introduced into the reactor, optionally with an excess of the phenanthroline ligand. Alternatively, the palladium catalyst precursor, (L) the solvent, and the phenanthroline ligand can be combined with the starting materials (I) and / or (J) in the reactor, and (K) the vinyl exchange reaction can 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.

[0191] The amount of (K) transvinylation catalyst is an amount sufficient to catalyze the transvinylation reaction under the conditions described above, and may be from 0.0001 mol % to 10 mol % of (K) transvinylation catalyst, based on the carboxy functionality of (I) the carboxy-functional organosilicon compound.

[0192] (L) Solvents suitable for use in the (tertiary) vinyl exchange reaction The starting material (L) is a (third) solvent that may be used in the vinyl exchange reaction in the process described herein. The solvent may be used to deliver the starting material and / or to facilitate the vinyl exchange reaction. The solvent used in the vinyl exchange reaction may be aprotic. The solvent used in the vinyl exchange reaction may be an aliphatic hydrocarbon such as hexane. The amount of the solvent (L) suitable for use in the vinyl exchange reaction is not particularly limited, but may be, for example, 0 to 95% by weight based on the total weight of (I) the carboxy-functional organosilicon compound, (J) the vinyl acetate-functional compound, and (K) the vinyl exchange reaction catalyst.

[0193] (X) Inhibitor Starting material (X) is an inhibitor that may be optionally added during the vinyl exchange reaction to minimize or prevent polymerization of the vinyl ester functionality. Inhibitors (F) may include phenolic compounds, quinone or hydroquinone compounds, N-oxyl compounds, phenothiazine compounds, hindered amine compounds, or combinations thereof.

[0194] 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 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 -Nitrosophenol, 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.

[0195] 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.

[0196] 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 Sil-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-deca N,N'-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.

[0197] Other compounds suitable for use in or as the 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.

[0198] Inhibitors may be used to prevent polymerization of the vinyl ester functionality prior to use of the initiator (e.g., initiator (J)) and / or during and / or after the vinyl exchange 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 10 ppm to 10,000 ppm, alternatively 50 ppm to 1,000 ppm, based on the weight of the (J) vinyl acetate functional compound and / or based on the weight of the (M) vinyl ester functional organosilicon compound (e.g., if added after the vinyl exchange reaction).

[0199] Vinyl ester functional organosilicon compounds A vinyl ester functional organosilicon compound has at least one vinyl ester functional group per molecule. The vinyl ester functional group, R VE is the expression:

[0200] [ka] where G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, as described and exemplified above for the (E) aldehyde-functional organosilicon compounds. VE are independently -(C2H4)C(=O)O(CH=CH2), -(C3H6)C(=O)O(CH=CH2), and -(C6H 12 The vinyl ester functional organosilicon compound may have any one of the formulas shown above for (I) the carboxy functional organosilicon compound, except that one or more of R Car The example of R VE Alternatively, R Car All or substantially all of the cases are VE can be replaced by

[0201] The vinyl ester functional organosilicon compound is represented by the formula (VE1) (VE1-1): R VEx SiR 4 (4-x) wherein each R VE are independently selected expressions

[0202]

number

[0203] Alternatively, the vinyl ester functional organosilicon compound may comprise a (VE2) vinyl ester functional polyorganosiloxane. The vinyl ester functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The vinyl ester functional organosilicon compound may have the unit formula (VE2-1):(R 4 3SiO 1 / 2 ) a (R 4 2R VE SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R VE SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R VE SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein R VE is as described above for formula (VE1-1), and R 4 is as described above for formula (B1-1), and Z and subscripts a, b, c, d, e, f, g, and h are as described above for formula (B2-1).

[0204] Alternatively, the vinyl ester functional polyorganosiloxane compound (VE2) may comprise (VE2-2), a linear polydiorganosiloxane having at least one vinyl ester functional group per molecule, alternatively at least two vinyl ester functional groups (e.g., where subscripts e=f=g=0 in formula (VE2-1) for the vinyl ester functional polyorganosiloxane above). For example, the polydiorganosiloxane may comprise a unit of formula (VE2-3): (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 is as above for formula (VE1-1), and R 4 are as defined above for formula (B1-1) and the subscripts a, b, c, and d are as defined above for unit formula (B2-3).

[0205] Alternatively, the linear vinyl ester functional polydiorganosiloxane of the unit formula (VE2-3) may be represented by the unit formula (VE2-4): (R 4 2R VE SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R VE SiO 2 / 2 ) n , Unit formula (VE2-5):(R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R VE SiO 2 / 2 ) por a combination of both (VE2-4) and (VE2-5). In formulae (VE2-4) and (VE2-5), each R VE is as described above for formula (VE1-1), and each 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).

[0206] Alternatively, the polydiorganosiloxane of the unit formula (VE2-3) is represented by the formula (VE2-3a):

[0207] [ka] wherein each R 2’’’ are independently 4 and R VE with the proviso that at least one R 2’’’ is R VE And each R VE is as described above for formula (VE1-1), and each R 4 is as described above for formula (B1-1) and the subscript zz is as described above for formula (B2-3a).

[0208] 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 vinyl ester functional group per molecule, for example, when subscript a=1, b=1, and d=0 in the unit formula (VE2-3). The polydiorganosiloxane may have the formula (VE2-3b).

[0209] [ka] In the formula, R VE is as described above for formula (VE1-1), and each R 4is as described above for formula (B1-1) and subscript c is as described above for formula (B2-3b).

[0210] The starting material (VE2) is i) bisdimethyl(propanoate)siloxy terminated polydimethylsiloxane, ii) bisdimethyl(propanoate)siloxy terminated poly(dimethylsiloxane / methyl(propanoate)siloxane), iii) bisdimethyl(propanoate)siloxy terminated polymethyl(propanoate)siloxane, iv) bistrimethylsiloxy terminated poly(dimethylsiloxane / methyl(propanoate)siloxane), v) bistrimethylsiloxy terminated poly(dimethylsiloxane / methyl(propanoate)siloxane), ) 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 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) combinations of two or more of i) through xix).

[0211] Alternatively, the vinyl ester functional polyorganosiloxane is, for example, the unit formula (VE2-1) where the subscripts a=b=c=e=f=g=h=0. (VE2-6) Cyclic vinyl ester functional polydiorganosiloxane is, for example, the unit formula (VE2-7): (R 4 R VE SiO 2 / 2 ) d wherein R VE is as described above for formula (VE1-1), and R 4 is as described above for formula (B1-1) and the subscript d is as described above for formula (B2-7).

[0212] Alternatively, the (VE2-6) cyclic vinyl ester functional polydiorganosiloxane may be represented by the unit formula (VE2-8): (R 4 2SiO 2 / 2 ) c (R 4 R VE SiO 2 / 2 ) d wherein R VE is as described above for formula (VE1-1), and R 4 is as defined above for formula (B1-1), and the subscripts c and d are as defined above for unit formula (B2-8).

[0213] Alternatively, (VE2) vinyl ester functional polyorganosiloxane can be an oligomer (VE2-9), for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (VE2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer can be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as the starting material (VE2-6).

[0214] An example of a linear vinyl ester functional polyorganosiloxane oligomer has the formula (VE2-10):

[0215] [ka] where R and each R 4 is as described above for formula (B1-1), and each R 2’’’ is R 4 and R VE with the proviso that at least one R 2’’’ is R VE And each R VE is as described above for formula (VE1-1), and subscript z is 0 to 48.

[0216] Alternatively, the vinyl ester functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (VE2-11): R VE SiR 12 3, wherein R VE is as described above for formula (VE1-1), and each R 12 is R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and 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.

[0217] Alternatively, in formula (VE2-11), each R 12 -OSi(R 14 )3, then each R 14 The branched polyorganosiloxane oligomer has the following structure:

[0218] [ka] (R VE and R 15 is as described above),15 ) 3 moieties. Alternatively, each R 15 As above, R 13 Each R 13 can be methyl.

[0219] Alternatively, in formula (VE2-11), 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 vinyl ester functional polyorganosiloxane oligomer having the structure:

[0220] [ka] (In the formula, R VE , R 13 , and R 15 is as described above) 15 ) 3 moieties. Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0221] Alternatively, in formula (VE2-11), 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 and one R 14 Each -OSi(R 14 )R in 3 13 If 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:

[0222] [ka] (In the formula, R VE , R 13 , and R 15 is as described above) 15 ) 3. Alternatively, each R 15 is R 13 Each R 13 can be methyl. Alternatively, the vinyl ester 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. Exemplary vinyl ester functional branched polyorganosiloxane oligomers include those having the formula:

[0223] [ka] vinyl 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanoate having the formula

[0224] [ka] and vinyl 3-(1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propanoate having the formula

[0225] [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, having the formula

[0226] [ka] and vinyl 7-(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)heptanoate.

[0227] Alternatively, the vinyl ester functional polyorganosiloxane (VE2) may be branched, such as the branched oligomers described above, and / or branched vinyl ester functional polyorganosiloxanes that may have, for example, more vinyl ester groups and / or more polymer units per molecule than the branched oligomers described above (e.g., when the quantity (a+b+c+d+e+f+g)>50 in formula (VE2-1). The branched vinyl ester functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide the branched vinyl ester functional polyorganosiloxane (in formula (VE2-1)) with greater than 0 to 5 mole percent trifunctional and / or tetrafunctional units.

[0228] For example, the branched vinyl ester functional polyorganosiloxane may be represented by the unit formula (VE2-13): (R 4 3SiO 1 / 2 ) q (R 4 2R VE SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) twherein each R 4 is as described above for formula (B1-1), and each R VE is as described above for formula (VE1-1), and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) have a value sufficient for the branched polyorganosiloxane to have a viscosity greater than 170 mPa·s as measured by rotational viscometry (described below along with the test method). Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, alternatively greater than 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, alternatively 190 mPa·s to 420 mPa·s.

[0229] Alternatively, the branched vinyl ester functional polyorganosiloxane may be represented by the formula (VE2-14): [R VE R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w wherein each R 4 is as described above for formula (B1-1), and each R VE are as described above for formula (VE1-1). The subscripts v, w and x are as described above for formula (B2-14).

[0230] Alternatively, the branched vinyl ester functional polyorganosiloxane for the starting material (VE2-11) may have the unit formula (VE2-15): (R 4 3SiO 1 / 2 ) aa (R VE R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R VE R 4 SiO 2 / 2 )ee (R 4 SiO 3 / 2 ) dd In the formula, each R 4 is as described above for formula (B1-1), and each R VE are as described above for formula (VE1-1), and the subscripts aa, bb, cc, dd, and ee are as described above for unit formula (B2-15). The value of subscript bb may be sufficient to provide a silsesquioxane of unit formula (VE2-15) having a vinyl ester group content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane.

[0231] Alternatively, (VE2) the vinyl ester functional polyorganosiloxane may comprise a vinyl ester functional polyorganosiloxane resin, such as a vinyl ester functional polyorganosilicate resin and / or a vinyl ester functional silsesquioxane resin. The vinyl ester functional polyorganosilicate resin may be represented by the formula R M’’’ 3SiO 1 / 2 and monofunctional units ("M'' units) of formula SiO 4 / 2 "R" is a tetrafunctional silicate unit ("Q" unit) of the formula M’’’ are independently R as above 4 and R VE Alternatively, each R M’’’ may be selected from the group consisting of alkyl groups, vinyl ester functional groups of the formula shown above, and aryl groups. Alternatively, each R M’’’ may be selected from methyl, propanoate, heptanoate, and phenyl. Alternatively, R M’’’ At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M"' units are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (MeR VE SiO 1 / 2The polyorganosilicate resins are soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0232] When prepared, the polyorganosilicate resin contains M''' and Q units as described above, and the polyorganosilicate resin contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) as described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M’’ 3) may contain 4 neopentamers, where R M’’’ is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M''' and Q units, expressed as {M'''resin) / {Q(resin)}, excluding the M'' and Q units from the neopentamer. The M'' / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M'' units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M'' / Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0233] The Mn of the polyorganosilicate resin is determined by the R M’’’ The Mn of the polyorganosilicate resin depends on various factors including the type of group represented by. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively greater than 3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0234] Alternatively, the vinyl ester functional polyorganosilicate resin may comprise the unit formula (VE2-17): (R 4 3SiO 1 / 2 ) mm (R 4 2R VE SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h , each R 4 is as described above for formula (B1-1), and each R VE is as described above for formula (VE1-1), each Z is as described above for unit formula (B2-1), and the subscripts mm, nn, and oo are as described above for unit formula (B2-17).

[0235] Alternatively, (VE2) the vinyl ester functional polyorganosiloxane may include (VE2-18) a vinyl ester functional silsesquioxane resin, i.e., a resin containing trifunctional units. The vinyl ester functional silsesquioxane resin is represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R VE SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R VE SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R VE SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R VEis as defined above for formula (VE1-1), each Z is as defined above for unit formula (B2-1), and the subscripts a, b, c, d, e, f and h are as defined above for formula (B2-18).

[0236] Alternatively, the vinyl ester functional silsesquioxane resin may be represented by the unit formula (VE2-19): (R 4 SiO 3 / 2e (R VE SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein each R 4 is as described above for formula (B1-1), and each R VE is as described above for formula (VE1-1), each Z is as described above for unit formula (B2-1), and subscripts e, f, and h are as described above for formula (B2-19). Alternatively, the vinyl ester functional silsesquioxane resin may contain, in addition to the T units described above, units of the formula (R 4 2SiO 2 / 2 ) c (R 4 R VE SiO 2 / 2 ) d where subscripts c and d are as defined above. Alternatively, the vinyl ester functional silsesquioxane resin may further comprise a difunctional (D') unit of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R VE SiO 1 / 2 ) b , i.e., M'''D'''T''' resin, where subscripts a and b are as defined above. EXAMPLES

[0237] These examples are provided 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 the examples are listed in Table 1 below.

[0238]

Table 1-1

[0239]

Table 1-2

[0240]

Table 1-3

[0241] In this synthesis example 1, the procedure for making 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (aldehyde siloxane 1) was carried out as follows: In a nitrogen filled glove box, Rh(acac)(CO)2 (6.7 mg, 0.026 mmol), Ligand 1 (30.2 mg, 0.0360 mmol), and toluene (5.0 g, 0.054 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, vinylmethylbis(trimethylsiloxy)silane (20.2 g, 81.2 mmol) and toluene (57.7 g, 627 mmol) were charged to a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen through a dip tube and carefully released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing it to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi with syngas and then released three times before pressurizing to 80 psig through the dip tube. The reaction temperature was set to 90°C. The stirring speed was set to 500 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set to 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The N / I ratio was measured as the N / I ratio of the final product. 1 Determined by 1 H NMR analysis.

[0242] In this synthesis example 2, the procedure for making 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal (aldehyde siloxane 2) was carried out as follows. In a nitrogen-filled glove box, Rh(acac)(CO)2 (18.1 mg, 0.0699 mmol), ligand 1 _(88.0 mg, 0.105 mmol), and toluene (5.0 g, 0.054 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 1,3-divinyltetramethyldisiloxane (44.8 g, 240 mmol) and toluene (40.0 g, 488 mmol) were charged to a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen through a dip tube and carefully released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized with syngas to 100 psi, then released three times and then pressurized to 80 psig through a dip tube. The reaction temperature was set at 90° C. The agitation speed was set at 500 RPM. Once the desired temperature was reached, the intermediate cylinder containing syngas was connected to the reactor. The pressure was set at 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The N / I ratio was recorded as the N / I ratio of the final product. 1 Determined by 1 H NMR analysis.

[0243] In this synthesis example 3, the procedure for making tetrapropanal-tetramethylcyclotetrasiloxane (aldehyde siloxane 3) was carried out as follows: In a nitrogen-filled glovebox, Rh(acac)(CO)2 (5.9 mg, 0.019 mmol), Ligand 1 (28.6 mg, 0.0341 mmol), and toluene (5.0 g, 0.054 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (45.0 g, 130 mmol) and toluene (40.0 g, 488 mmol) were charged to a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen through a dip tube and carefully released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing it to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi with syngas and then released three times before pressurizing to 80 psig through the dip tube. The reaction temperature was set to 90°C. The stirring speed was set to 500 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set to 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The N / I ratio was measured as the N / I ratio of the final product. 1 Determined by 1 H NMR analysis.

[0244] In this Synthesis Example 4, the synthesis of a Q-type branched hexenyl polyorganosiloxane polymer was carried out as follows.

[0245] A. Synthesis of hexenyl neopentamer

[0246] [ka]

[0247] In a typical procedure, a 500 mL multi-neck reactor was fitted with a Dean-Stark trap with a thermocouple, overhead stirrer, nitrogen sweep, and condenser. The reactor was charged with 1,3-di-5-hexenyl-1,1,3,3-tetramethyldisiloxane (78.84 g, 0.26 moles, 0.55 equiv.) and acetic acid (129.7 g, 2.16 moles, 4.5 equiv.) and purged with overhead nitrogen. Triflic acid (0.3089 g, 2.1 mmol, 0.1 wt%) was added dropwise to the reactor using a syringe. The mixture in the reactor was then stirred and heated to 45 °C under N2. Tetraethoxysilane (TEOS, 100 g, 0.48 moles, 1 equiv.) was added dropwise to the reaction mixture via an addition funnel, and the reaction mixture temperature was maintained at 45-50 °C during the TEOS addition. After the TEOS addition, the reaction was allowed to proceed at 80° C. until completion. The reaction was monitored by GC-MS. After completion of the reaction, the reaction mixture was cooled to room temperature and subsequently washed twice with DI water, three times with saturated NaHCO3 solution, and twice again with DI water. The crude product was dried over anhydrous Na2SO4 and then stripped at 180° C. to remove residual volatiles. A pale yellow oil was obtained (yield=88%).

[0248] BQ-Branched Hexenyl Polyorganosiloxane Q-(D 36 M hex Synthesis of 4

[0249] [ka]

[0250] In a nitrogen-filled glove box, Rh(acac)(CO)2 (75.5 mg, 0.292 mmol), Ligand 1 (489.1 mg, 0.58 mmol), and toluene (10.0 g, 0.108 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, Q-branched hexenylsiloxane (150 g, 13.59 mmol) was charged to a 300 mL 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 released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi with syngas and then released three times before being pressurized to 80 psig through the dip tube. The reaction temperature was set at 70°C. The stirring speed was set at 600 RPM. Once the desired temperature was reached, the reactor was connected to the intermediate cylinder containing the syngas. The pressure was set at 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The N / I ratio was calculated as the N / I ratio of the final product. 1 Determined by 1 H NMR analysis.

[0251] In this synthesis example 5, the allyl-siloxanes listed in Table 1 were prepared as follows. In a typical procedure, a 500 mL multi-neck reactor was fitted with a thermocouple, overhead stirrer, nitrogen sweep, and a Dean-Stark trap with condenser. The reactor was charged with 1,3-diallyltetramethyldisiloxane (13.81 g, 64.38 mmol, 1 eq.) and octamethylcyclotetrasiloxane (D4, 487 g, 1.64 mol, 25.5 eq.) and purged with overhead nitrogen. The mixture in the reactor was stirred and heated to 140° C. under a nitrogen atmosphere, and then dilute potassium silanolate (10 wt % in D4, 1.2809 g) was added to the reactor. The reaction was allowed to proceed at 140° C. for 4 hours and monitored by off-line NMR. Once the reaction was complete, octylsilylphosphonate (2.5 wt% in D4, 2.967 g) was added to the reactor to neutralize the reaction. Heat was then turned off and the reactor was allowed to cool to ambient temperature. The final allyl-siloxane was obtained by removing the volatile cyclics under vacuum.

[0252] In this synthesis example 6, the aldehyde-MQ resin described in Table 1 was prepared as follows. In a nitrogen-filled glove box, Rh(acac)(CO)2 (3.8 mg, 0.0147 mmol), Ligand 1 (27.28 mg, 0.0325 mmol), and toluene (5.0 g, 57.9 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, the vinyl-MQ resin was dissolved in 100 mL of water. (DOWSIL™ 6-3444 Int) (37.5 g) and toluene (112.5 g, 1.22 moles) were loaded into a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen through a dip tube and carefully released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi with syngas and then released three times before pressurizing to 80 psig through the dip tube. The reaction temperature was set to 70° C. The agitation speed was set to 500 RPM. Once the desired temperature was reached, an intermediate cylinder containing syngas was connected to the reactor. The pressure was set to 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as synthesis gas was fed to the reactor through a pressure reducing regulator. The N / I ratio was calculated based on the N / I ratio of the final product. 1 Determined by 1 H NMR analysis.

[0253] In this Synthesis Example 7, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)dipropanal (M Pr-ald D7M Pr-ald ) was prepared as follows. In a nitrogen filled glove box, Rh(acac)(CO)2 (9.3 mg, 0.0359 mmol), Ligand 1 (58.1 mg, 0.069 mmol), and heptane (10.0 g, 99.8 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)divinyl (M) from DSC was analyzed. Vi D7M Vi) (700 g, 1.027 moles) was charged into a 2 L autoclave reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen through a dip tube and carefully released three times through a valve connected to the head space. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi with syngas and then released three times before pressurizing to 80 psig through a dip tube. The reaction temperature was set at 70° C. Once the desired temperature was reached, with the stirring speed set at 800 RPM, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set at 100 psi. The progress of the reaction was monitored by a data logger that measured the pressure in the intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The resulting product was 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)dipropanal (M Pr-ald D7M Pr-ald ), which contained aldehyde-siloxane 4.

[0254] In this Synthesis Example 8, M Vi 2D 180 is hydroformylated to give M Pr-Ald D 180 M Pr-Ald In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.0050 g), Ligand 1 (0.0326 g), and toluene (5.0 g) were added to a 60 mL vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogeneous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, the M from the DSC was measured. Vi 2D 180(200 g) was loaded into a Parr reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen through a dip tube and carefully released through a valve connected to the headspace. The pressurization / venting cycle with nitrogen was 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 loading port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then vented three times before being pressurized to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 70° C. The heater and stirring were turned on. Once the desired temperature was reached, the reactor was connected to a 300 mL intermediate cylinder containing the syngas for the reaction. The pressure drop from the 300 mL intermediate cylinder was used to monitor the progress of the reaction and recorded by a data logger. 1 Complete conversion of the vinyl group was observed after 3.5 h reaction time as monitored by 1 H NMR.

[0255] In this Synthesis Example 9, MD 8.2 D Pr-Ald 3.7 M was synthesized as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.0191 g), Ligand 1 (0.1324 g), and toluene (76.74 g) were added to a 125 mL bottle equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogeneous solution was formed. 3.65 g of the solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, the MD from the DSC was 8.2 D vi 3.7M (180 g) was loaded into a Parr reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen through a dip tube and carefully released through a valve connected to the headspace. The pressurization / venting cycle with nitrogen was 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 loading port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then vented three times before being pressurized to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 70° C. The heater and stirring were turned on. Once the desired temperature was reached, the reactor was connected to a 300 mL intermediate cylinder containing the syngas for the reaction. The pressure drop from the 300 mL intermediate cylinder was used to monitor the progress of the reaction and recorded by a data logger. 1 Complete conversion of the vinyl group was observed after 24 h reaction time as monitored by 1 H NMR.

[0256] In this Synthesis Example 10, vinyl siloxane 7, M vi 2D 329 The hydroformylation of was carried out as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.380 g), Ligand 1 (2.45 g), and toluene (90 g) were added to a 125 mL vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous solution was formed. 8.6 g of the solution was then transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M vi 2D 329(1394 g) was charged into a 2 liter autoclave reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen through a dip tube and carefully released through a valve connected to the head space. 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 loading port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then vented three times before being pressurized to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 90° C. The heater and agitation were turned on. Once the desired temperature was reached, the reactor was connected to a cylinder containing the syngas for the reaction. A mass flow totalizer was used to monitor the progress of the reaction. 1 Complete conversion of the vinyl groups was observed after overnight stirring, as determined by H NMR, and M Pr-Ald 2D 329 was formed.

[0257] In this Example 11, vinyl siloxane 8, M Vi 2D 25 The hydroformylation of was carried out as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.0252 g), Ligand 1 (1.63 g), and toluene (50 g) were added to a 125 mL vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M Vi 2D 25(1000 g) was charged into a 2 liter autoclave reactor. The reactor was sealed and pressurized to 100 psig (689 kPa) with nitrogen through a dip tube and carefully released through a valve connected to the head space. 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 loading port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then vented three times before being pressurized to 20 psig (138 kPa) below the desired pressure through a dip tube. The reaction temperature was set to 80° C. The heater and agitation were turned on. Once the desired temperature was reached, the reactor was connected to a cylinder containing the syngas for the reaction. A mass flow totalizer was used to monitor the progress of the reaction. 1 Complete conversion of the vinyl group was observed after 2 h reaction time as monitored by H NMR, and M Pr-Ald 2D 25 was formed.

[0258] In this Synthesis Example 12, vinyl siloxane 16, M Vi 2D 77 The hydroformylation of was carried out as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (0.0050 g), Ligand 1 (0.0227 g), and toluene (30.09 g) were added to a 60 mL vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M Vi 2D 77(140.12 g) and toluene (46.92 g) were charged to a 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 loading port. The reactor was pressurized to 100 psig (689 kPa) with syngas and then vented three times before being pressurized to 20 psig (138 kPa) below the desired pressure via a dip tube. The reaction temperature was set to 90° C. The heater and stirring were turned on. Once the desired temperature was reached, the reactor was connected to a 300 mL intermediate cylinder containing the syngas for the reaction. The progress of the reaction was monitored using the pressure drop from a 300 mL intermediate cylinder and recorded by a data logger. 1 Complete conversion of the vinyl group was observed after 10 h reaction time as monitored by H NMR, and M Pr-Ald 2D 77 was formed.

[0259] In this Synthesis Example 13, the hydroformylation of the branched oligomer was carried out as follows.

[0260] [ka]

[0261] In a nitrogen-filled glovebox, Rh(acac)(CO)2 (15.1 mg, 0.0583 mmol), Ligand 1 (76.4 mg, 0.0911 mmol), and toluene (7.49 g, 0.0814 mmol) were added to a 30 mL glass vial equipped with a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, 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 (145.0 g, 189.2 mmol) was charged to a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (689 kPa) with nitrogen through a dip tube and carefully released three times through a valve connected to the headspace. The reactor was then pressure tested by pressurizing it to 300 psi (2068 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi (689 kPa) with syngas and then released three times before pressurizing to 80 psi (552 kPa) through a dip tube. The reaction temperature was set to 100°C. The stirring speed was set to 500 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set to 100 psi (689 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. More than 98% conversion was observed after 200 min. The N / I ratio was 1 Determined by 1 H NMR analysis.

[0262] In this Synthesis Example 14, the hydroformylation of the branched oligomer was carried out as follows.

[0263] [ka]

[0264] In a nitrogen filled glove box, 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 glove box. In a fume hood, Si10Hex (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 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 110°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 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.

[0265] In this synthesis example 15, the procedure for making 3-(ethoxydimethylsilyl)propanal (aldehyde alkoxysilane 1) was carried out as follows. In a nitrogen-filled glovebox, Rh(acac)(CO)2 (14.3 mg, 0.055 mmol), ligand 1 (100.9 mg, 0.12 mmol), and toluene (70 g) were added to a 60 mL vial equipped with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous solution was formed. 3.5 g of the solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, vinylalkoxysilane 1, Me2Si(OEt)Vi, (40 g, 307 mmol) was charged to a 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. The pressurization / venting cycle with nitrogen was 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 loading port. The reactor was pressurized to 100 psig (690 kPa) with syngas, then vented three times before pressurizing to 109 psig (752 kPa) through the dip tube. The reaction temperature was set to 70°C. The heater and stirring were turned on. Once the desired temperature was reached, the reactor was connected to a 300 mL intermediate cylinder containing the syngas for the reaction. The pressure drop from the 300 mL intermediate cylinder was used to monitor the progress of the reaction and recorded by a data logger. 1 Complete conversion of the vinyl group was observed after 23 h reaction time, as monitored by 1 H NMR, with the formation of 3-(ethoxydimethylsilyl)propanal.

[0266] In this synthesis example 16, the hydroformylation of vinyltrimethylsilane was carried out as follows: In a nitrogen-filled glovebox, Rh(acac)(CO)2 (0.0007 g), Ligand 1 (0.0043 g), and toluene (0.90 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 solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, vinyltrimethylsilane (53.0 g) 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 As monitored by 1 H-NMR, 99.5% conversion of the vinyl groups was observed after 20 h reaction time, resulting in the formation of propylaldehyde-functional trimethylsilane.

[0267] In this Reference Example A, the oxidation of an aldehyde-functional organosilicon compound was carried out as follows. In a typical procedure, 150 g of the aldehyde-siloxane was placed in a 250 mL glass reactor. The aldehyde-siloxane was stirred with a mechanical or magnetic stirrer and air was continuously injected below the liquid surface with a stainless steel needle at a rate of 50-200 cc / min. The progress of the reaction was monitored by 1 The reaction was continued until a high conversion was achieved, as determined using H-NMR analysis. The mixture of aldehyde starting material and reaction product was 1 H, 13 C-NMR, and 29The conversion and yield were mainly analyzed by Si-NMR, GC / MS, and GPC. 1 The results were based on H-NMR data.

[0268] In this Example 1, MD Pr-Ald M (MD prepared as described in Synthesis Example 1) vi The oxidation of M (the hydroformylation product of M) gave the following results:

[0269] [ka]

[0270] [Table 2]

[0271] In this Example 2, MD 8.2 D Pr-Ald 3.7 M (vinyl siloxane 5, prepared according to Synthesis Example 9, MD 8.2 D vi 3.7 Oxidation of M) (the hydroformylation product of M) was carried out as follows.

[0272] [ka]

[0273] Aldehyde-siloxane 5 (100.4 g) was charged to a 250 mL reaction flask equipped with a PTFE coated stir bar. Air was bubbled through the liquid surface with a needle at 50 cc / min at ambient temperature 20-25°C. The reaction was run for 244 hours, yielding 101 g of a clear, slightly yellow product. Product analysis by NMR was performed using CDCl3 solvent. 96.8% aldehyde conversion was achieved. The product contained 83 mol% linear carboxy-propyl groups and 6.8 mol% branched carboxy-propyl groups (89.8% total acid).

[0274] In this Example 3, aldehyde-siloxane 2, M Pr-Ald M Pr-Ald (Vinylsiloxane 2, prepared as described in Synthesis Example 2, M vi M vi The oxidation of the hydroformylation product of (a) was carried out as follows.

[0275] [ka]

[0276] Crude aldehyde-siloxane 2 (309 g) and 3-pentanone solvent (76 g) were added to a 500 mL reaction flask equipped with an overhead paddle stirrer and a needle for subsurface air addition. The oxidation reaction was run with stirring at 400 rpm and an air addition rate of 100 cc / min. The reaction was allowed to continue for 187 hours. 340.9 g of a clear, slightly yellow product solution was collected. 1 H-NMR analysis showed 96% aldehyde conversion, 91.3 mol % carboxylic acid and 5 mol % formyl ester.

[0277] In this Example 4, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was used. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The oxidation of the hydroformylation product of (a) was carried out as follows.

[0278] [ka]

[0279] Crude aldehyde-siloxane 4 (195.3 g) was charged to a 250 mL European flask equipped with a PTFE-coated magnetic stir bar. Air was sparged subsurface with a needle at 100 cc / min and the mixture was stirred at maximum speed with a magnetic stirrer. The reaction was stirred at 16, 40, and 64 hours. 1The reaction was analyzed by H-NMR. After 64 hours the reaction was stopped. A clear slightly yellow product liquid (194.6 g) was collected. The reaction reached 96.6% aldehyde conversion, 89.7% acid, and 4.0% formyl ester.

[0280] In this Example 5, aldehyde-siloxane 3, D, prepared according to Synthesis Example 3, was used. Pr-Ald 4 (Vinylsiloxane 3, D vi Oxidation of the hydroformylation product of 4) was carried out as follows.

[0281] [ka]

[0282] The oxidation reaction was carried out in a 250 mL European flask with magnetic stirring. 50.25 g of aldehyde-siloxane 3 was charged. The reaction was run at ambient temperature 20-25 °C starting with bubbling air subsurface through a needle at 80 cc / min. After 2 hours, 3-pentanone solvent (50 mL) was added and the air rate was increased to 100 cc / min. After 46 hours, additional 3-pentanone (50 mL) was added. After 69 hours, additional 3-pentanone (25 mL) was added. After 77 hours, additional 3-pentanone (50 mL) was added and the air rate was reduced to 10 cc / min due to sample viscosity. After 165 hours, the reaction was stopped. The reaction was sparged with nitrogen overnight to remove 2.74 g of solvent and 52.17 g of a slightly yellow viscous oil was collected.

[0283] In this Example 6, aldehyde-siloxane 6, M, prepared according to Synthesis Example 8, was used. Pr-Ald D 180 M Pr-Ald (Vinylsiloxane 6, M Vi 2D 180 The oxidation of the hydroformylation product of (a) was carried out as follows.

[0284] [ka]

[0285] Coarse M Pr-Ald D 180 M Pr-Ald The solution (189.27 g) was charged to a 250 mL tapered-sided glass flask with mechanical overhead stirring. The reaction was run with approximately 100 cc / min of air starting at ambient temperature of 21.9° C. The reaction was stopped after 67 hours with 98.6% aldehyde conversion. The oxidation reaction product contained 91.8% acid, 2% formyl ester, and 1.4% unreacted aldehyde.

[0286] In this Example 7, M prepared according to Example 4 acid -D7-M acid was equilibrated with D4 in the presence of DOWEX™ DR-2030 as follows: D4 was dried over molecular sieves. acid -D7-M acid was dried over molecular sieves and filtered through a 0.45 μm PTFE syringe filter. DOWEX™ DR-2030 (0.40 g) and D4 (65.2 g) were added to a 250 mL reaction flask equipped with an overhead stirrer, thermoprobe, water-cooled condenser, nitrogen headspace purge, and heating mantle and heated to 60° C. acid -D7-M acid (13.37 g) was added via syringe. The resulting clear mixture was then stirred overnight at 60° C. for 21 hours to give a clear, mobile fluid which was analyzed by Si-NMR, showing a DP of 74.7. The reaction was continued for an additional 3 hours and, while still warm, the reaction mixture was filtered through a medium capacity disposable filter funnel to remove the catalyst, giving 75.32 g of a clear, slightly viscous liquid. The fluid was stripped on a rotary evaporator at 16 torr and 95° C. for 30 minutes to give 70.51 g of product fluid. Si-NMR analysis of the product fluid showed a DP of 76 and 16% D4.

[0287] In this Example 8, D4 was dried over molecular sieves. DOWEX™ DR-2030 (0.5 g) and D4 (108 g) were added to a 250 mL reaction flask equipped with an overhead stirrer, thermoprobe, and heating mantle bar and heated to 80° C. Using a syringe pump, bis-trimethylsiloxy-terminated poly(dimethyl / methyl, carboxypropyl) siloxane copolymer (MD4) prepared in Example 2 was added to a 250 mL reaction flask equipped with an overhead stirrer, thermoprobe, and heating mantle bar and heated to 80° C. 8.2 D acid 3.7 M, 9 g) was added dropwise over a period of 3 hours. The mixture was then stirred at 80° C. overnight for 14 hours to give a thick liquid. The reaction mixture contained some gelled material. While still warm, the reaction mixture was filtered through a coarse sintered glass funnel to remove the gelled material and catalyst, giving 101 g of a clear thick liquid. Si-NMR showed a DP of 259.

[0288] In this Example 9, oxidation of (M2T)3T propionaldehyde (prepared as described in Example 13) was carried out as follows.

[0289] [ka]

[0290] Crude (M2T) 3T propionaldehyde (90 g, n:i ratio 77:1) was charged to a 240 mL septum cap bottle equipped with a PTFE coated stir bar. A needle was used to sparge air subsurface at 50 cc / min and the mixture was stirred for 64 hours. A clear, slightly yellow liquid (90.0 g) was collected. 1 H-NMR analysis showed the acid, formyl ester, and unreacted aldehyde in proportions of 97.8, 1.82, and 0.39 mol %, respectively.

[0291] In this Example 10, MD (prepared as shown in Synthesis Example 1) with 3-pentanone and / or N-hydroxyphthalimide Pr-Ald The oxidation of M was investigated as follows. Pr-AldFour oxidation experiments were set up for the oxidation of M. In experiment A, 3.0 g of undiluted MD Pr-Ald In experiment B, 4.5 g of undiluted MD containing 0.04 g (approximately 1 wt%) of N-hydroxyphthalimide was used. Pr-Ald In experiment C, 3.0 g of MD Pr-Ald In experiment D, 2.8 g of MD and 3.0 g of 3-pentanone were used. Pr-Ald M, 2.8 g of 3-pentanone, and 0.015 g of N-hydroxyphthalimide (MD Pr-Ald 0.5% by weight relative to M was used. Each oxidation was carried out for 24 hours using 10 cc / min air and 500 rpm agitation. The results are shown in Table 3 below.

[0292] [Table 3]

[0293] In this Example 11, oxidation of the aldehyde-functional MQ resin (hydroformylation product prepared according to Synthesis Example 6) was carried out as follows: A 40 mL septum-capped vial equipped with a PTFE-coated magnetic stir bar was charged with 25 g of the aldehyde-MQ resin from Synthesis Example 6. Air was bubbled beneath the surface of the solution at a rate of 20 cc / min at a temperature of 22° C. while stirring at 1000 RPM using a magnetic stir plate. The reaction was continued for 184 hours and the liquid product was collected. Quantitative precipitation of the product was performed. 13 C-NMR analysis revealed 95% conversion, with 83% acid and 12% formyl ester.

[0294] In this Example 12, the oxidation of 3-(ethoxydimethylsilyl)propanal (the hydroformylation product prepared according to Synthesis Example 15) was carried out as follows: A 40 mL vial was charged with a magnetic stirrer and 3-(ethoxydimethylsilyl)propanal [Me2Si(OEt)CH2CH2CHO] (7.16 g, 44.7 mmol). Air was bubbled subsurface at 40 cc / min. A stir plate was used and set at 1000 RPM. The reaction was run at 2, 21, 42, and 116 hours. 1The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 116 hours. 4.31 g of a pale yellow liquid was collected. 1 Analysis by H-NMR spectroscopy revealed a 96.2% aldehyde conversion, 95.2% acid, and 1.0% formyl ester. 13 This was further supported by C-NMR spectroscopy data.

[0295] In this Example 13, the oxidation of 3-(ethoxydimethylsilyl)propanal (the hydroformylation product prepared according to Synthesis Example 15) was carried out as follows: A 40 mL vial was charged with a magnetic stirrer and 3-(ethoxydimethylsilyl)propanal [Me2Si(OEt)CH2CH2CHO] (6.96 g, 43.4 mmol). Air was bubbled subsurface at 5 cc / min. A stir plate was used and set at 1000 RPM. The reaction was run at 16, 24, 51, 62, and 144 hours. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 144 hours. 5.56 g of a pale yellow liquid was collected. 1 Analysis by H-NMR spectroscopy revealed 93.5% aldehyde conversion, 92.6% acid, and 0.9% formyl ester.

[0296] [ka]

[0297] In this Example 14, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was used. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The RT oxidation of the hydroformylation product of (III) was carried out as follows: A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald(10.1 g, 13.2 mmol). Subsurface air was blown at 40 cc / min. The reaction was carried out at room temperature with a stir plate set at 1000 RPM. The reaction was stirred at 30 minutes, 1 hour, 2 hours, 4 hours, 7 hours, and 23 hours. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 23 hours. 9.35 g of a colorless liquid was obtained. 1 Analysis by H-NMR spectroscopy revealed 96.5% aldehyde conversion, 87.0% acid, and 6.1% formyl ester.

[0298] In this Example 15, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was used. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The 60° C. oxidation of the hydroformylation product of (1, 2, 3, 4-hexanediaminetetraacetate) was carried out as follows: A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald (9.99 g, 13.1 mmol). Subsurface air was blown at 40 cc / min. The reaction was run at 60° C. with a stir plate set at 1000 RPM. The reaction was run at 30 minutes, 1 hour, 2 hours, 4 hours, 7 hours, and 23 hours. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 23 hours. 9.12 g of a colorless liquid was obtained. 1 Analysis by H-NMR spectroscopy revealed 98.3% aldehyde conversion, 84.7% acid, and 10.2% formyl ester.

[0299] In this Example 16, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was used. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The 100° C. oxidation of the hydroformylation product of (1) was carried out as follows: A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald(10.1 g, 13.2 mmol) was added. Subsurface air was blown at 40 cc / min. The reaction was run at 100° C. with a stir plate set at 1000 RPM. The reaction was run at 30 minutes, 1 hour, 2 hours, 4 hours, 7 hours, and 23 hours. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 23 hours. 8.55 g of a colorless liquid was obtained. 1 Analysis by H-NMR spectroscopy revealed a 98.4% aldehyde conversion, 80.0% acid, and 16.0% formyl ester. Examples 14-16 demonstrated that the oxidation reaction can be carried out at different temperatures.

[0300] In this Example 17, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was used. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The 0° C. oxidation of the hydroformylation product of M was carried out as follows. A 250 mL jacketed glass reactor was charged with M Pr-Ald D7M Pr-Ald (91.1 g, 119 mmol). Subsurface air was sparged at 100 cc / min. The reaction was carried out at 0° C. and an overhead stirrer was used for stirring, set at 500 RPM. The reaction was run at 20, 23, 44, 67, and 140 hours. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 140 hours. 78.6 g of a colorless liquid was obtained. 1 Analysis by H-NMR spectroscopy revealed 92.3% aldehyde conversion, 88.7% acid, and 2.5% formyl ester.

[0301] [ka]

[0302] In this Example 18, oxidation of the aldehyde-functional silane (hydroformylation product prepared according to Synthesis Example 16) was carried out as follows: A 40 mL septum-capped vial equipped with a PTFE-coated magnetic stir bar was charged with 5.7 g of the propyl-aldehyde-functional trimethylsilane from Synthesis Example 16. Air was bubbled beneath the surface of the solution at a rate of 5 cc / min at a temperature of 22° C. while stirring at 1400 RPM using a magnetic stir plate. The reaction was continued for 22 hours and 5.8 g of liquid product was collected. 1 H-NMR analysis revealed a conversion of 97.6%, with 91.2% acid and 6.4% formyl ester.

[0303] In this Example 19, aldehyde-siloxane 7, M, prepared according to Synthesis Example 10, was used. Pr-Ald D 329 M Pr-Ald (Vinylsiloxane 7, M Vi 2D 329 The oxidation of the hydroformylation product of (a) was carried out as follows.

[0304] [ka]

[0305] Coarse M Pr-Ald D 329 M Pr-Ald The solution (1315 g) was charged to a 2 L, 3-neck glass flask equipped with mechanical overhead stirring and a temperature controlled heating mantle. The reaction was run with air added at approximately 200 cc / min using two subsurface needles. The reaction temperature was controlled at 30° C. and the reaction was stirred at 400 RPM. The reaction was run for 115 hours. 1 H-NMR analysis revealed a conversion of 96.4%, with 91.6% acid and 4.8% formyl ester.

[0306] In this Example 20, M prepared according to Example 4 acid -D7-M acidwas equilibrated with D4 in the presence of trifluoromethanesulfonic acid to produce carboxy-end-functionalized PDMS as follows: M acid -D7-M acid (3.3 g) and D4 (7.95 g) were added to form a homogenous solution. The mixture was heated to 90° C. A solution of 1 wt % triflic acid in dichloromethane (100 uL) was added to the vial syringe. The mixture was stirred at 90° C. for 16 h with a headspace nitrogen purge (50 cc / min). The product was analyzed by NMR and GPC. Si-NMR showed a DP of 42.

[0307] In this Example 21, MD prepared according to Example 1 Pr-acid M was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to produce pendant carboxy-functionalized PDMS as follows: MD was placed in a 40 mL septum-capped vial equipped with a PTFE-coated stir bar. Pr-acid M (0.95 g) and D4 (9.5 g) were added to form a homogenous solution. The mixture was heated to 90° C. and the vial was purged with nitrogen. A solution of 1 wt % triflic acid in dichloromethane (100 uL) was added to the vial syringe. The mixture was stirred at 90° C. with a headspace nitrogen purge for 17 hours. At 25 hours reaction time, the nitrogen purge was removed and replaced with a static nitrogen headspace pad. At 113 hours, the reaction was stopped. The product was analyzed by NMR and GPC. Si-NMR showed a DP of 57.

[0308] In this Example 22, MD prepared according to Example 2 8.2 D Pr-Acid 3.7 M was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to produce pendant carboxy-functionalized PDMS as follows: MD was placed in a 40 mL septum-capped vial equipped with a PTFE-coated stir bar. 8.2 D Pr-Acid 3.7M (0.8 g) and D4 (12 g) were added to form a cloudy mixture. The mixture was heated to 90° C. and became cloudy. A solution of 1 wt % triflic acid in dichloromethane (120 uL) was added to the vial syringe. After 3 minutes, the mixture became clear. The mixture was stirred at 90° C. for 15 hours with a headspace nitrogen pad. The product was analyzed by NMR and GPC. Si-NMR showed a DP of 290.

[0309] In this Example 23, MD prepared according to Example 2 8.2 D Pr-Acid 3.7 M and M prepared according to Example 4 acid -D7-M acid was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to produce PDMS functionalized with pendant and terminal carboxy groups as follows: MD 8.2 D Pr-Acid 3.7 M(1.1g), M acid -D7-M acid (0.73 g), and D4 (16 g) were added to form a mixture. The mixture was heated to 90° C. and a solution of 1 wt % triflic acid in dichloromethane (150 uL) was added to the vial syringe. The mixture was stirred at 90° C. with a headspace nitrogen purge for 19 hours. 0.53 g of material was collected from the headspace purge. The product was analyzed by NMR and GPC. Si-NMR showed a DP of 160.

[0310] In this Example 24, aldehyde-siloxane 9, M, prepared according to Synthesis Example 12, was used. Pr-Ald D 77 M Pr-Ald (Vinylsiloxane 16, M Vi 2D 77 The oxidation of the hydroformylation product of (a) was carried out as follows.

[0311] [ka]

[0312] Coarse M Pr-Ald D 77 M Pr-Ald The solution (185 g) was charged into a 250 mL European tapered wall flask with mechanical overhead stirring. The reaction was carried out at ambient temperature of 20-25°C with 50-100 cc / min of air. The oxidation was carried out for 68 hours. 1 H-NMR analysis revealed a conversion of 96.9%, with 87.5% acid and 9.3% formyl ester. The end of the reaction mixture contained 1.5% by weight toluene. 139.17 g of a yellow liquid was collected.

[0313] In this Example 25, the oxidation of (M2T)3T heptanoic acid (prepared as described in Example 14) was carried out as follows: Crude (M2T)3T heptanoic acid (100 g), containing approximately 5% by weight 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 reaction mixture was analyzed by 1H-NMR until completion. After 24 hours, the reaction was stopped and the (M2T)3T-heptanoic acid product was collected as a clear orange liquid.

[0314] In this Example 26, aldehyde-siloxane 8, M, prepared according to Synthesis Example 11, was used. Pr-Ald D 25 M Pr-Ald (Vinylsiloxane 8, M Vi 2D 25 The oxidation of the hydroformylation product of (a) was carried out as follows.

[0315] [ka]

[0316] Crude M containing approximately 3% by weight toluene Pr-Ald D 25 M Pr-AldThe solution (572 g) was charged into a 500 mL European tapered wall flask with mechanical overhead stirring. The reaction was carried out at ambient temperature with 200 cc / min air starting at 22° C. The oxidation was carried out for 72 hours. 1 H-NMR analysis revealed 98.4% conversion, with 91.2% acid and 7.2% formyl ester. 550.7 g of a clear, slightly colored liquid was collected.

[0317] In this Example 27, aldehyde-siloxane 4, M, prepared according to Synthesis Example 7, was synthesized in the presence of 285 nm UV light. Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The RT oxidation of the hydroformylation product of M was carried out as follows. Pr-Ald D7M Pr-Ald (5.00 g, 6.5 mmol). Subsurface air was blown at 20 cc / min. The reaction was carried out at room temperature and was not stirred. The samples were irradiated for the specified times using a 285 nm UV LED. The reaction was irradiated at 15 min, 1 h, 3 h, 5 h, 8 h, and 13 h. 1 The reaction was monitored by H-NMR spectroscopy. The reaction was stopped after 13 hours. 3.84 g of a colorless liquid was obtained. 1 Analysis by H-NMR spectroscopy revealed a 97.1% conversion of the aldehyde, 90.3% of the acid, and 4.5% of the formyl ester. Pr-Ald D7M Pr-Ald The reaction was repeated in the absence of UV light using (5.00 g, 6.5 mmol) and the same air blowing rate (20 cc / min). After 13 hours under these conditions, 1 H-NMR spectroscopy revealed 64.2% aldehyde conversion, 60.6% acid, and 3.0% formyl ester. 1 H-NMR spectroscopy revealed 97.1% aldehyde conversion, 90.3% acid, and 4.5% formyl ester.

[0318] The above reaction was repeated, except without UV irradiation. After 13 hours under these conditions, 1 H-NMR spectroscopy revealed 64.2% aldehyde conversion, 60.6% acid, and 3.0% formyl ester, indicating that the reaction still took place but at a slower rate.

[0319] [ka]

[0320] In this Example 28, aldehyde-siloxane 4, prepared according to Synthesis Example 7, was synthesized in the presence of peracid (3-chloroperbenzoic acid, oxidant 1). Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The RT oxidation of the hydroformylation product of (III) was carried out as follows: A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald (2.22 g, 2.9 mmol). In a separate 40 mL vial, 3-chloroperbenzoic acid (1.22 g, 7.13 mmol) and deuterated benzene (2.58 g) were added to form a white slurry. The slurry was diluted with M Pr-Ald D7M Pr-Ald The reaction was added over 2 minutes to a vial containing 1 It was analyzed by H-NMR spectroscopy. 1 Analysis by H-NMR spectroscopy revealed 87.9% aldehyde conversion, 58.8% acid, and 29.1% formyl ester.

[0321] [ka]

[0322] In this Example 29, aldehyde-siloxane 4, prepared according to Synthesis Example 7, was synthesized in the presence of an organic peroxide (di-tert-butyl peroxide, oxidant 2). Pr-Ald D7M Pr-Ald(Vinylsiloxane 4 M vi D7M vi The 100° C. oxidation of the hydroformylation product of (1) was carried out as follows. A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald (0.95 g, 1.2 mmol) and tert-butyl peroxide (0.50 mL, 0.40 g, 2.72 mmol). The reaction was stirred under a N2 atmosphere and heated at 100° C. Aliquots were removed after 15 min, 1.5 h, and 3 h. 1 The molar ratio between the desired acid and the starting material was determined by H-NMR spectroscopy. Pr-Ald D7M Pr-Ald A control experiment was performed using (0.95 g, 1.2 mmol) with no added oxidant and heated at 100 °C under N2. Aliquots of this reaction were taken after 15 min, 1.5 h, and 3 h. 1 The molar ratio between the desired acid and the starting material was determined by H-NMR spectroscopy. The results from these experiments are presented in Table 4. After 3 hours, the reaction was stopped. 0.72 g of a colorless liquid was obtained.

[0323] [Table 4]

[0324] [ka]

[0325] In this Example 30, aldehyde-siloxane 4, prepared according to Synthesis Example 7, was synthesized in the presence of an organic hydroperoxide (tert-butyl hydroperoxide, oxidant 3). Pr-Ald D7M Pr-Ald (Vinylsiloxane 4 M vi D7M vi The 100° C. oxidation of the hydroformylation product of (1) was carried out as follows. A 40 mL vial was equipped with a magnetic stirrer and Pr-Ald D7M Pr-Ald(0.95 g, 1.2 mmol) and tert-butyl hydroperoxide (0.50 mL, 5.5 mmol / mL, 2.75 mmol). The reaction was stirred under a N2 atmosphere and heated at 100° C. Aliquots were removed after 15 min, 1.5 h, and 3 h. 1 The molar ratio between the desired acid and the starting material was determined by H-NMR spectroscopy. Pr-Ald D7M Pr-Ald A control experiment was performed using (0.95 g, 1.2 mmol) with no added oxidant and heated at 100 °C under N2. Aliquots of this reaction were taken after 15 min, 1.5 h, and 3 h. 1 The molar ratio between the desired acid and the starting material was determined by H-NMR spectroscopy. The results from these experiments are presented in Table 5. After 3 hours, the reaction was stopped. 0.73 g of a colorless liquid was obtained.

[0326] [Table 5]

[0327] [ka]

[0328] In this Example 31, a three-necked 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 equipped 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 25 above, and vinyl acetate (186.0 g, 2.163 mol) were added to the reactor. Nitrogen was bubbled through a needle below the surface of the mixture for 5 minutes with vigorous stirring. 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). To the flask was added 200 mL of hexane. The mixture was filtered through a disposable filter containing 7 g of silica. The filtrate was concentrated under rotary evaporation to give a yellow viscous liquid (165.0 g, 96% purity). MEHQ (60.3 mg) was added to the material. The resulting material was stored in an amber bottle until further use.

[0329] In this synthesis example 17, 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, Si10ViHex (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 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. This material was named Si10PrAld.

[0330] In this Synthesis Example 18, crude Si10PrAld (51.92 g) prepared as above in Synthesis Example 17, 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 and plant air was sparged subsurface through a needle at 100 cc / min. The reaction mixture was analyzed by 1H-NMR until completion. After 24 hours, the reaction was stopped and the resulting Si10PrAcid product (50.5 g) was collected as a clear, slightly yellow liquid.

[0331] In this Example 32, a three-necked 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 equipped 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 Synthesis Example 18, 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 for 5 minutes with vigorous stirring. Palladium acetate (0.3406 g, 0.001520 mol) and phenanthroline (0.4273 g, 0.002371 mol) were added through a 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 transferred to a round-bottom flask and evaporated on a rotary evaporator at 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 containing 7 g of silica. The filtrate was concentrated on a rotary evaporator to give a yellow viscous liquid.

[0332] In this Example 33, a linear vinyl ester functional polydimethylsiloxane was prepared using the carboxy functional polydimethylsiloxane MCR-B12 from Gelest 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 equipped with a J-Kem controller was used to control the heating. A magnetic stir bar, MCR-B12 from Gelest Inc. (200.0 g, 0.1333 moles), and vinyl acetate (114.7 g, 1.333 moles) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle for 5 minutes with vigorous stirring. Palladium acetate (0.149 g, 0.000667 moles) and phenanthroline (0.18 g, 0.0010 moles) were added through a 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 transferred to a round-bottom flask and evaporated on a rotary evaporator at 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 containing 7 g of silica. The filtrate was concentrated on a rotary evaporator to give a yellow-orange liquid.

[0333] [ka]

[0334] Synthesis of MCR-V21-aldehyde In this synthesis example 19, 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 with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogenous 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.

[0335] Synthesis of MCR-V21-acid In this Example 34, the oxidation of MCR-V21-aldehyde, prepared as described in Synthesis Example 19, was carried out as follows: 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 reaction mixture was analyzed by 1H-NMR until completion. After 24 hours, the reaction was stopped and the MCR-V21 acid product was collected as a clear orange liquid.

[0336] Synthesis of MCR-V21-vinyl ester In this Example 35, a linear vinyl ester functional polydimethylsiloxane was prepared starting from a carboxy functional polydimethylsiloxane prepared by hydroformylation of Gelest's MCR-V21. 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 equipped 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 Synthesis Example 19, and vinyl acetate (26.1 g, 0.302 moles) were added to the reactor. Nitrogen was bubbled under the surface of the mixture through a needle for 5 minutes with vigorous stirring. 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 via 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 transferred to a round bottom flask and evaporated on a rotary evaporator at 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 containing 7 g of silica. The filtrate was concentrated on a rotary evaporator to give 72.1 g of a brown liquid.

[0337] Synthesis of Si4-aldehyde In this synthesis example 20, 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 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 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, 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 / 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. 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.

[0338] Synthesis of Si4-acid In this Example 36, the oxidation of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal (Si4-aldehyde) (prepared as described in Synthesis Example 20) was carried out as follows: Si4-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 reaction mixture was analyzed by 1H-NMR until completion. After 24 hours, the reaction was stopped and the 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanoic acid (Si4-aldehyde) product was recovered as a clear orange liquid.

[0339] Synthesis of Si4-vinyl ester In this Example 37, 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 equipped 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 for 5 minutes with vigorous stirring. Palladium acetate (0.214 g, 0.000955 mol) and phenanthroline (0.214 g, 0.0012 mol) and MEHQ (0.036 g, 0.00029 mol) were added via 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 transferred to a round bottom flask and evaporated on a rotary evaporator at 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 containing 7 g of silica. The filtrate was concentrated on a rotary evaporator to give 27.6 g of a clear oil. [Industrial Applicability]

[0340] The above examples show that by using the process of the present invention, various aldehyde-functional organosilicon compounds can form carboxy-functional organosilicon compounds through oxidation reaction, and then form vinyl ester-functional organosilicon compounds through vinyl exchange reaction.The process described herein can form vinyl ester-functional organosilicon compounds with one or more carboxy groups per molecule.In addition, the process can have one or more of the following advantages: low cost, simple process, minimal by-product formation, relatively low pressure, low temperature below 60°C (less likely to decompose sensitive molecules, less capital cost, safer), minimal by-products, and good reaction control.In addition, the process does not require purification or separation of starting materials such as (E) aldehyde-functional organosilicon compounds before use.

[0341] Definitions and Use of Terms All amounts, ratios, and percentages herein 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.

[0342] [Table 6]

[0343] The following test methods were used herein: FTIR: The concentration of silanol groups present in polyorganosiloxane resins (e.g., polyorganosilicate resins and / or silsesquioxane resins) was determined using FTIR spectroscopy according to ASTM standard E-168-16. GPC: The molecular weight distribution of polyorganosiloxanes was determined by GPC using an Agilent Technologies 1260 Infinity chromatograph and toluene as the solvent. The instrument was equipped with three columns, a PL gel 5 μm, 7.5×50 mm guard column and two Plgel 5 μm, Mixed-C 7.5×300 mm columns. Calibration was performed using polystyrene standards. Samples were made by dissolving polyorganosiloxanes in toluene (approximately 1 mg / mL), and then the solution was immediately analyzed by GPC (flow rate of 1 mL / min, column temperature of 35° C., run time of 25 minutes). 29 Si-NMR: The alkenyl content of the starting material (B) can be measured by the technique described in "The Analytical Chemistry of Silicones" ed. A. Lee Smith, Vol. 112 in Chemical Analysis, John Wiley & Sons, Inc. (1991). Viscosity: Viscosity can be measured, for example, for polymers (e.g., certain (B2) alkenyl-functional polyorganosiloxanes, aldehyde-functional polyorganosiloxanes, carboxy-functional polyorganosiloxanes, and vinyl ester-functional polyorganosiloxanes) having a viscosity of 120 mPa·s to 250,000 mPa·s with a Brookfield DV-III cone & plate viscometer equipped with a #CP-52 spindle at 25°C and 0.1 to 50 RPM. Those skilled in the art will recognize that as the viscosity increases, the rotation speed decreases and that the appropriate spindle and rotation speed can be selected.

[0344] EMBODIMENTS OF THE PRESENT DISCLOSURE In a first embodiment, the process for preparing a vinyl ester functional organosilicon compound comprises: 1) Under conditions in which the hydroformylation reaction is carried out, (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional organosilicon compound; and (C) A rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand has the formula:

[0345] [ka] 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’ are each independently an alkyl group having 3 to 20 carbon atoms, and a group of the formula -SiR 17 3 (in the formula, each R 17 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 or alkyl groups; Optionally, mixing the starting materials with a solvent (D). thereby forming a hydroformylation reaction product comprising an aldehyde-functional organosilicon compound; and Optionally, 2) recovering the amino-functional organosilicon compound; and 3) Under conditions in which an oxidation reaction occurs, (E) an aldehyde-functional organosilicon compound; and (F) an oxygen source; Optionally, (G) an oxidation reaction catalyst; optionally, (H) a second solvent; (I) forming an oxidation reaction product comprising a carboxy-functional organosilicon compound; and optionally, 4) (I) recovering the carboxy-functional organosilicon compound; and 5) under conditions conducive to a vinyl exchange reaction; (I) a carboxy-functional organosilicon compound; (J) vinyl acetate compounds, (K) vinyl exchange reaction catalyst, optionally, (L) a third solvent; and Optionally, mixing starting materials including ((X) an inhibitor; thereby preparing a transvinylation reaction product comprising a vinyl ester functional organosilicon compound; and optionally, 6) recovering the vinyl ester functional organosilicon compound.

[0346] In a second embodiment, in the process of the first embodiment, the starting material (B) is a compound represented by the formula (B1): R A x SiR 4 (4-x) wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R 4 are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, acyloxy groups of 2 to 18 carbon atoms, and hydrocarbyloxy functional groups of 1 to 18 carbon atoms, and the subscript x is 1 to 4.

[0347] In a third embodiment, in the process of the first embodiment or the second embodiment, the alkenyl-functional organosilicon compound is represented by the unit formula: 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 4 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; subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has a value such that 0≦h / (e+f+g)≦1.5, with the proviso that if e=f=g=0, then h≧0, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0348] In a fourth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is cyclic and (R 4 RA SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (wherein c is >0 to 6, and d is 3 to 12), and combinations thereof.

[0349] In a fifth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is linear and has the unit formula (B3): (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0350] In a sixth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) mm (R 4 2R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percentage of each unit in the polyorganosilicate resin, and the subscripts mm, nn, and oo have average values ​​such that mm≧0, nn≧0, oo>0, and 0.5≦(mm+nn) / oo≦4.

[0351] In a seventh embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0 <h / (e+f)<1.5である。

[0352] In an eighth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane has the general formula: R A SiR 12 3, wherein R A is as above, and each R 12 But R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R 15 is R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and each R16 is R 13 and -[OSiR 13 2] ii OSiR 13 3, where the subscript ii has a value such that 0≦ii≦100.

[0353] In a ninth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula (B2-13): (R 4 3SiO 1 / 2 ) q (R 4 2R A SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t wherein the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the branched polyorganosiloxane a viscosity of greater than 170 mPa s as measured by a rotational viscometer (described below along with the test methods).

[0354] In a tenth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula (B2-15): (R 4 3SiO 1 / 2 ) aa (R A R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R A R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) ddwherein subscript aa≧0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee≧0.

[0355] In the eleventh embodiment, in any one of the third to tenth embodiments, each R A is independently selected from the group consisting of vinyl, allyl, and hexenyl.

[0356] In a twelfth embodiment, in the process of the eleventh embodiment, each R A is vinyl.

[0357] In the thirteenth embodiment, in any one of the processes of the third to eleventh embodiments, each R 4 is independently selected from the group consisting of methyl and phenyl.

[0358] In a fourteenth embodiment, the process of the first embodiment further comprises II) equilibrating the carboxy-functional organosilicon compound with a cyclic polydiorganosiloxane in the presence of an equilibration catalyst.

[0359] In a fifteenth embodiment, in the process of any one of the first to fourteenth embodiments, R in the bisphosphite ligand 6 and R 6’ are each selected from the group consisting of a methoxy group and a t-butyl group; R 7 and R 7’ are each a t-butyl group, and R 8 , R 8’ , R 9 , R 9’ , R 10 , R 10’ , R 11 , and R 11’ are each hydrogen.

[0360] In a sixteenth embodiment, in the process of any one of the first to fifteenth embodiments, starting material (C) is present in an amount sufficient to provide from 0.1 ppm to 300 ppm Rh, based on the combined weight of starting materials (A), (B), and (C).

[0361] In a seventeenth embodiment, in the process of any one of the first to sixteenth embodiments, the starting material (C) has a molar ratio of bisphosphite ligand / Rh of 1 / 1 to 10 / 1.

[0362] In an eighteenth embodiment, in the process of any one of the first to seventeenth embodiments, the conditions in step 3) are selected from the group consisting of: i) a temperature of 20°C to 50°C, ii) a pressure of 3 psia to 100 psia, iii) the oxygen source having 21% to 100% oxygen, and iv) a combination of two or more of conditions i), ii), and iii).

[0363] In a nineteenth embodiment, in the process of any one of the first to eighteenth embodiments, (C) the rhodium / bisphosphite ligand complex catalyst is formed by mixing a rhodium precursor with a bisphosphite ligand to form a rhodium / bisphosphite ligand complex, and mixing the rhodium / bisphosphite ligand complex with the starting material (A) with heating prior to step 1).

[0364] In a twentieth embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first or second embodiment has the formula (E1-1): R Ald x SiR 4 (4-x) where each R Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R 4are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, acyloxy groups of 2 to 18 carbon atoms, and hydrocarbyloxy functional groups of 1 to 18 carbon atoms, and the subscript x is 1 to 4.

[0365] In a twenty-first embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first or second embodiment has the unit formula (E2-1): (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein each R Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a hydrocarbyloxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 4 and each R 4are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (E2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has a value such that 0≦h / (e+f+g)≦1.5, with the proviso that if e=f=g=0, then h≧0, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0366] In a twenty-second embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is cyclic and (R 4 R Ald SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (wherein c is >0 to 6, and d is 3 to 12), and combinations thereof.

[0367] In a twenty-third embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is linear and has the unit formula (E3): (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0368] In a twenty-fourth embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) mm (R 4 2R Ald SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percentage of each unit in the polyorganosilicate resin, and the subscripts mm, nn, and oo have average values ​​such that mm≧0, nn≧0, oo>0, and 0.5≦(mm+nn) / oo≦4.

[0369] In a twenty-fifth embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h where f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0 <h / (e+f)<1.5である。

[0370] In a twenty-sixth embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is branched and has the unit formula: RAld SiR 12 3, wherein each R 12 is R 13 and -OSi(R 14 ) 3, each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 3 are selected, and 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, with the subscript ii having a value such that 0≦ii≦100, with the proviso that R 12 At least two of -OSi(R 14 )3.

[0371] In a twenty-seventh embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) q (R 4 2R Ald SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) twherein the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the Q-branched polyorganosiloxane a viscosity of greater than 170 mPa s as measured by a rotational viscometer (described below along with the test methods).

[0372] In a twenty-eighth embodiment, in the process of the twenty-first embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) aa (R Ald R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R Ald R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd wherein subscript aa≧0, subscript bb>0, subscript cc is 15-995, subscript dd>0, and subscript ee≧0.

[0373] In the twenty-ninth embodiment, in any one of the processes of the twenty-first to twenty-eight embodiments, each R Ald is independently selected from the group consisting of propylaldehyde, butyraldehyde, and heptylaldehyde.

[0374] In the 30th embodiment, in any one of the processes of the 21st to 29th embodiments, each R 4 is independently selected from the group consisting of methyl and phenyl.

[0375] In a thirty-first embodiment, the process of any one of the first to thirtieth embodiments, wherein step 2) is present and further comprises recovering the aldehyde-functional organosilicon compound prior to step 3).

[0376] In a thirty-second embodiment, an oxidation reaction catalyst is added in step 3) of the process of any one of the first to thirty-first embodiments.

[0377] In a thirty-third embodiment, in the process of the thirty-second embodiment, the oxidation reaction catalyst comprises a transition metal complex.

[0378] In a thirty-fourth embodiment, in the process of the thirty-third embodiment, the transition metal complex comprises a transition metal selected from the group consisting of Co, Cu, Ni, Mn, and Rh.

[0379] In a thirty-fifth embodiment, in the process of the thirty-second embodiment, the oxidation reaction catalyst is an organic catalyst containing an N-hydroxy functional group.

[0380] In a thirty-sixth embodiment, in the process of the thirty-fifth embodiment, the organic catalyst is selected from the group consisting of N-hydroxyphthalimide and 2,2,6,6-tetramethylpiperidin-1-yl)oxyl.

[0381] In a thirty-seventh embodiment, the process of any one of the first through thirty-sixth embodiments includes the presence of step 4), and further includes recovering the carboxy-functional organosilicon compound from the oxidation reaction product after step 3).

[0382] In a thirty-eighth embodiment, in the process of the second embodiment, the carboxy functional organosilicon compound is represented by the formula: R Car x SiR 4 (4-x) wherein each R Car are independently selected expressions

[0383] [ka] wherein G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms, and each R 4 is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, acyloxy groups of 2 to 18 carbon atoms, and hydrocarbyloxy functional groups of 1 to 18 carbon atoms, and the subscript x is 1 to 4.

[0384] In a thirty-ninth embodiment, in the process of the third embodiment, the carboxy-functional organosilicon compound is represented by the unit formula: 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Car SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein each R Car are independently selected expressions

[0385] [ka] where G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, and each R 4is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a hydrocarbyloxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 4 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; subscripts a, b, c, d, e, f, and g represent the number of each unit in the unit formula and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has a value such that 0≦h / (e+f+g)≦1.5 with the proviso that if e=f=g=0, then h≧0, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0386] In a fortieth embodiment, in the process of the thirty-ninth embodiment, the carboxy-functional polyorganosiloxane is cyclic and (R 4 R Car SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d wherein subscript c is >0-6 and subscript d is 3-12.

[0387] In a forty-first embodiment, in the process of the thirty-ninth embodiment, the carboxy-functional polyorganosiloxane is linear and has the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4R Car SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0388] In a forty-second embodiment, in the process of the thirty-ninth embodiment, the carboxy-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) mm (R 4 2R Car SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percentage of each unit in the polyorganosilicate resin, and the subscripts mm, nn, and oo have average values ​​such that mm≧0, nn≧0, oo>0, and 0.5≦(mm+nn) / oo≦4.

[0389] In a forty-third embodiment, in the process of the thirty-ninth embodiment, the carboxy-functional polyorganosiloxane is represented by the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Car SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Car SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Car SiO 3 / 2 ) f (ZO 1 / 2 ) hwherein f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0 <h / (e+f)<1.5である。

[0390] In a forty-fourth embodiment, in the process of the thirty-ninth embodiment, the carboxy-functional polyorganosiloxane is branched.

[0391] In the 45th embodiment, in any one of the processes of the 38th embodiment to the 43rd embodiment, each R Car are independently -(C2H4)C(=O)OH, -(C3H6)C(=O)OH, and -(C6H 12 )C(=O)OH.

[0392] In the 46th embodiment, in any one of the processes of the 38th embodiment to the 45th embodiment, each R 4 is independently selected from the group consisting of methyl and phenyl.

[0393] In a 47th embodiment, in the process of any one of the previous embodiments, the oxidation reaction is carried out at a temperature between 0°C and 100°C.

[0394] In a 48th embodiment, in the process of any one of the above embodiments, the starting material is exposed to ultraviolet light during the oxidation reaction in step 3).

[0395] In a forty-ninth embodiment, in the process of any one of the above embodiments, the (J) vinyl acetate functional compound has the formula (I):

[0396] [ka] In the formula, R 3 is an alkyl group having 1 to 6 carbon atoms.

[0397] In a 50th embodiment, in the process of the 48th embodiment, the (J) vinyl acetate functional compound comprises vinyl acetate.

[0398] In a fifty-first embodiment, in the process of any one of the above embodiments, (K) the vinyl exchange reaction catalyst comprises a palladium-phenanthroline complex.

[0399] In a fifty-second embodiment, in the process of any one of the above embodiments, (L) a solvent suitable for use in the vinyl exchange reaction is present, and the solvent comprises an aliphatic hydrocarbon.

[0400] In a fifty-third embodiment, in the process of any one of the above embodiments, (X) an inhibitor is present.

[0401] In a fifty-fourth embodiment, in the process of the fifty-third embodiment, the inhibitor comprises 4-methoxyphenol.

[0402] In a fifty-fifth embodiment, in the process of any one of the previous embodiments, the vinyl exchange reaction is carried out at a temperature between 0°C and 150°C.

[0403] In a fifty-sixth embodiment, in the process of any one of the above embodiments, the vinylation reaction is carried out for up to 250 hours.

Claims

1. 1. A process for preparing a vinyl ester functional organosilicon compound, said process comprising: Under conditions in which the vinyl exchange reaction takes place, (I) a carboxy-functional organosilicon compound; (J) Formula 【Chemistry 1】 wherein R ３ is an alkyl group having 1 to 6 carbon atoms; and (K) a vinyl exchange reaction catalyst; mixing the starting materials, optionally including (L) a solvent; thereby preparing a reaction mixture comprising said vinyl ester functional organosilicon compound; and optionally recovering said vinyl ester functional organosilicon compound.

2. (I) the carboxy-functional organosilicon compound is Under the conditions in which the oxidation reaction takes place, (E) an aldehyde-functional organosilicon compound; and (F) an oxygen source; (I) thereby forming an oxidation reaction product comprising said carboxy-functional organosilicon compound; 10. The process of claim 1, wherein said carboxy-functional organosilicon compound is prepared by a process comprising:

3. 3. The process of claim 2, wherein the oxygen source is selected from the group consisting of air, oxygen gas, and a peroxide compound.

4. 4. The process of claim 2 or 3, wherein the oxygen source is used at a partial pressure of from 3 psia (20 kPa) to 100 psia (690 kPa).

5. 5. The process of any one of claims 2 to 4, wherein the starting materials mixed under conditions to effect the oxidation reaction further comprise an additional material selected from the group consisting of: (G) an oxidation reaction catalyst; (H) a second solvent; and both the oxidation reaction catalyst and the second solvent.

6. 6. The process of claim 5, wherein the oxidation reaction catalyst is present and comprises a transition metal complex comprising a metal selected from the group consisting of Co, Cu, Mn, Ni, Rh, and combinations of two or more thereof.

7. 6. The process of claim 5, wherein the oxidation reaction catalyst is present and comprises an organic catalyst that includes an N-hydroxy functional group.

8. The process according to any one of claims 2 to 7, wherein the oxidation reaction is carried out at a temperature of from 0 to 100°C.

9. The process according to any one of claims 2 to 8, wherein the oxidation reaction is carried out in the presence of UV irradiation.

10. (E) the aldehyde-functional organosilicon compound is Under conditions to catalyze a hydroformylation reaction, (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional organosilicon compound; and (C) A rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand has the formula: 【Chemistry 2】 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 (In the formula, each R １７ 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 or and alkyl groups; and a rhodium / bisphosphite ligand complex catalyst, thereby forming a hydroformylation reaction product comprising said aldehyde-functional organosilicon compound; mixing the starting materials, optionally including (D) a solvent; (E) thereby forming a hydroformylation reaction product comprising said aldehyde-functional organosilicon compound; and and optionally, (E) recovering said aldehyde-functional organosilicon compound.

11. In the bisphosphite ligand, R ６ and R ６’ are each selected from the group consisting of a methoxy group and a t-butyl group; R ７ and R ７’ are each a t-butyl group, R ８ , R ８’ , R ９ , R ９’ , R １０ , R １０’ , R １１ , and R １１’ The process of claim 10 , wherein each is hydrogen.

12. 12. The process of claim 10 or 11, wherein (C) the rhodium / bisphosphite ligand complex catalyst is present in an amount sufficient to provide from 0.1 ppm to 300 ppm Rh, based on the combined weight of starting materials (A), (B), and (C).

13. 13. The process of any one of claims 10 to 12, wherein (C) the rhodium / bisphosphite ligand complex catalyst has a molar ratio of bisphosphite ligand / Rh of from 1 / 1 to 10 / 1.

14. The conditions for catalyzing the hydroformylation reaction in step 1) are i) a temperature between 30°C and 150°C; ii) a pressure between 101 kPa and 6,895 kPa; iii) CO / H in syngas from 3 / 1 to 1 / 3 ２ and iv) a combination of two or more of conditions i), ii), and iii).

15. 15. The process of any one of claims 10 to 14, wherein (C) the rhodium / bisphosphite ligand complex catalyst is formed by mixing a rhodium precursor with the bisphosphite ligand to form a rhodium / bisphosphite ligand complex, and mixing the rhodium / bisphosphite ligand complex with starting material (A) with heating prior to step 1).

16. The vinyl ester functional organosilicon compound has the formula: 【Chemistry 3】 wherein G is a divalent hydrocarbon group free of aliphatic unsaturation having from 2 to 8 carbon atoms.

17. A vinyl ester functional organosilicon compound prepared by the process of any one of claims 1 to 16.

18. The vinyl ester functional organosilicon compound has the formula: ＶＥ ｘ SiR ４ （４－ｘ） wherein each R ＶＥ is the formula 【Chemistry 4】 G is a linear or branched divalent hydrocarbon group of 2 to 8 carbon atoms free of aliphatic unsaturation, 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, and subscript x is 1 to 4.

19. The vinyl ester functional organosilicon compound has the unit formula: ４ ３ SiO １／２ ) ａ (R ４ ２ R ＶＥ SiO １／２ ) ｂ (R ４ ２ SiO ２／２ ) ｃ (R ４ R ＶＥ SiO ２／２ ) ｄ (R ４ SiO ３／２ ) ｅ (R ＶＥ SiO ３／２ ) ｆ (SiO ４／２ ) ｇ (Z.O. １／２ ) ｈ wherein R ＶＥ is the formula 【Chemistry 5】 where G is a linear or branched divalent hydrocarbon group of 2 to 8 carbon atoms free of aliphatic unsaturation, and each R ４ is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms, and each Z is selected from the group consisting of a hydrogen atom and R ４ and wherein the subscripts a, b, c, d, e, f, and g represent the number of each unit in the unit formula and have values ​​such that subscript a > 0, subscript b > 0, subscript c > 0, subscript d > 0, subscript e > 0, subscript f > 0, subscript g > 0; and subscript h has a value such that 0 < h / (e+f+g) < 1.5, with the proviso that if e = f = g = 0, then h > 0, 10,000 > (a + b + c + d + e + f + g) > 2, and the quantity (b + d + f) > 1.

20. The vinyl ester functional polyorganosiloxane is i) (R ４ R ＶＥ SiO ２／２ ) ｄ (wherein the subscript d is 3 to 12); ４ ２ SiO ２／２ ) ｃ (R ４ R ＶＥ SiO ２／２ ) ｄ wherein c is >0 to 6 and d is 3 to 12, and combinations thereof; ii) Unit formula: (R ４ ３ SiO １／２ ) ａ (R ４ ２ R ＶＥ SiO １／２ ) ｂ (R ４ ２ SiO ２／２ ) ｃ (R ４ R ＶＥ SiO ２／２ ) ｄ wherein the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2; iii) Unit formula: (R ４ ３ SiO １／２ ) ｍｍ (R ４ ２ R ＶＥ SiO １／２ ) ｎｎ (SiO ４／２ ) ｏｏ (Z.O. １／２ ) ｈ wherein the subscripts mm, nn, and oo represent the mole percentage of each unit in said polyorganosilicate resin, and the subscripts mm, nn, and oo have average values ​​such that mm≧0, nn≧0, oo>0, and 0.5≦(mm+nn) / oo≦4; iv) Unit formula: (R ４ ３ SiO １／２ ) ａ (R ４ ２ R ＶＥ SiO １／２ ) ｂ (R ４ ２ SiO ２／２ ) ｃ (R ４ R ＶＥ SiO ２／２ ) ｄ (R ４ SiO ３／２ ) ｅ (R ＶＥ SiO ３／２ ) ｆ (Z.O. １／２ ) ｈ wherein f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0<h / (e+f)<1.5; v) Unit formula: R ＶＥ SiR １２ ３ wherein each R １２ But, R １３ and -OSi(R １４ ) ３ Each R １３ is a monovalent hydrocarbon group, and each R １４ But, R １３ , -OSi(R １５ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ Each R １５ But, R １３ , -OSi(R １６ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ Each R １６ But, R １３ and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ where subscript ii has a value such that 0≦ii≦100, with the proviso that R １２ At least two of -OSi(R １４ ) ３ a branched vinyl ester functional polyorganosiloxane, vi) Unit formula: (R ４ ３ SiO １／２ ) ｑ (R ４ ２ R ＶＥ SiO １／２ ) ｒ (R ４ ２ SiO ２／２ ) ｓ (SiO ４／２ ) ｔ wherein the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to said Q-branched polyorganosiloxane a viscosity of greater than 170 mPa·s as measured by a rotational viscometer (described below along with the test methods); vii) A unit formula: (R ４ ３ SiO １／２ ) ａａ (R ＶＥ R ４ ２ SiO １／２ ) ｂｂ (R ４ ２ SiO ２／２ ) ｃｃ (R ＶＥ R ４ SiO ２／２ ) ｅｅ (R ４ SiO ３／２ ) ｄｄ wherein subscript aa > 0, subscript bb > 0, subscript cc is 15-995, subscript dd > 0, and subscript ee > 0.

21. The vinyl ester functional organosilicon compound has the formula: 【Chemistry 6】 wherein R ４ is as described above, and each R ２’’ is R ４ and formula 【Chemistry 7】 wherein G is a divalent hydrocarbon radical free of aliphatic unsaturation having from 2 to 8 carbon atoms, with the proviso that: One R per molecule ２’’ is said vinyl ester functional group and subscript z is 0-48.

22. The vinyl ester functional organosilicon compound has the formula: 【Chemistry 8】 wherein G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, and each R １２ are independently -OSi(R １４ ) ３ and R １３ Each R １３ is a monovalent hydrocarbon group, and each R １４ But, R １３ , -OSi(R １５ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ Each R １５ But, R １３ , -OSi(R １６ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSI R １３ ３ Each R １６ But, R １３ , -OSi(R １７ ) ３ , and -[OSiR ２ ] ｉｉ OSI R １３ ３ Each R １７ But, R １３ and -[OSiR １３ ２ ] ｉｉ OSI R 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 the groups are -OSi(R １４ ) ３ and said vinyl ester functional organosilicon compound has from 4 to 16 silicon atoms per molecule.

23. The vinyl ester functional organosilicon compound has the structure: 【Chemistry 9】 wherein R １５ 22. The vinyl ester functional organosilicon compound of claim 21 , wherein:

24. The vinyl ester functional organosilicon compound has the structure: 【Chemistry 10】 wherein R １３ and R １５ 22. The vinyl ester functional organosilicon compound of claim 21 , wherein:

25. The vinyl ester functional organosilicon compound has the structure: 【Chemistry 11】 wherein R １３ and R １５ 22. The vinyl ester functional organosilicon compound of claim 21 , wherein:

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