Method for producing siloxane-(meth)acrylate macromonomers

Abstract

A method for preparing siloxane-(meth)acrylate macromonomers is provided. The method includes hydrosilylation, hydrolysis, and condensation. The by-products of the method may be recycled to produce additional siloxane-(meth)acrylate macromonomers. An exemplary siloxane-(meth)acrylate macromonomer prepared by the method is 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 160,953, filed on 15 March 2021, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 160,953 is incorporated herein by reference.

[0002] This invention relates to a method for producing siloxane-(meth)acrylate macromonomers.

[0003] Introduction Currently, siloxane-(meth)acrylate macromonomers can be synthesized via a direct platinum-catalyzed hydrosilylation reaction of a (meth)acryloxy-functional alkenyl compound with a silyl hydride, as exemplified in Formula 1 below, by the reaction of allyl methacrylate 1 with 1,1,1,3,5,5,5-heptamethyltrisiloxane 2. However, this direct reaction has the disadvantage of producing a considerable amount of byproducts, including oxysilyl esters and alkylene hydrosilylation products (exemplified in Formula 1 by oxysilyl ester 4 and propylene hydrosilylation adduct 5, respectively), resulting in a low yield of the desired product (exemplified by MD'M-ALMA3 in Formula 1) of only about 45% to 55%. The oxysilyl ester byproducts have a similar boiling point to the desired product, making distillation difficult, time-consuming, and expensive.

[0004] [ka] [Overview of the Initiative]

[0005] A method for preparing siloxane-(meth)acrylate macromonomers is disclosed. The method is as follows: (1) Formula (A)

[0006] [ka] A (meth) acrylate-functional alkenyl compound, wherein R , 4 , 1 , , , 5 , , 6 , , , , , 5 , 3 , , ,

[0008] , 2 , , , , is selected from the group consisting of H, alkyl, and aryl, and R 3 is selected from the group consisting of H, alkyl, and aryl, and R 4 is selected from the group consisting of H, alkyl, and aryl, and the subscript a is an integer having a value of 1 to 6, a (meth) acrylate-functional alkenyl compound, and (B) Formula

[0007]

Chemical formula

[0008]

Chemical formula

[0009] Step (1) in the above-described method may be carried out by any convenient means. Step (1) may include mixing and heating a starting material comprising (A) a (meth)acrylate-functionalized alkenyl compound, (B) a hydridosilane, and (C) a hydrosilylation catalyst (and, if present, (D) a (meth)acrylate polymerization inhibitor and / or (E) a solvent) at a temperature of 50°C to 70°C. Step (2) in the above-described method may be carried out by any convenient means. Step (2) may include mixing a starting material comprising (F) the (meth)acryloxyalkyl-functionalized silane prepared in step (1), (G) water, and (H) an organosilane at 23°C ± 2°C.

[0010] Step (3) in the method described above is performed after step (2). Step (3) may be performed once or more times during the method. For example, step (3) may include adding a desiccant after step (2), after step (4), or both. Alternatively, step (3) may include phase separation and decantation before step (4).

[0011] The method comprising steps (1), (2), and (3) described above may further comprise one or more optional additional steps. An optional step (4) is to neutralize the hydrolysis product by a technique comprising (I) adding a neutralizing agent, thereby forming a neutralized mixture. Step (4) may be performed after step (2) and / or after step (3). Step (4) may comprise the step of mixing the neutralizing agent with the hydrolysis product at 23°C ± 2°C. The method may optionally further comprise step (5) of condensing the neutralized mixture prepared in step (4) by a technique comprising (J) adding a condensation catalyst, thereby preparing a reaction mixture comprising an additional amount of (K) siloxane-(meth)acrylate macromonomer and an additional amount of by-products comprising (L) high-boiling oligomer and (M) low-boiling oligomer, thereby forming a condensation reaction product. Step (5) may be performed while mixing and heating the reaction mixture at a temperature of 50°C to 70°C. Optional step (6) includes stopping the reaction of the (J) condensation catalyst by adding a (N) condensation stopper to the condensation product, thereby forming a stopped product comprising the inorganic salts of the (J) condensation catalyst and the (N) condensation stopper. For example, ammonia gas may be bubbling through the condensation product and / or a base may be added to the condensation product while optionally heating and / or stirring to quench the condensation product.

[0012] The method may optionally further include an additional step (7) for recycling byproducts. The method generates byproducts comprising (L) a high-boiling oligomer and (M) a low-boiling oligomer in one or more steps described herein. Optional step (7) includes equilibrating (L) the high-boiling oligomer and (M) the low-boiling oligomer in the presence of (O) an additional condensation catalyst, thereby forming an additional amount of (K) siloxane-(meth)acrylate macromonomer. The low-boiling oligomer may be recycled from the byproducts. Alternatively, the low-boiling oligomer may be obtained from another source (for example, a new low-boiling oligomer may be purchased as described below).

[0013] The method further comprises step (8) of recovering the (K)siloxane-(meth)acrylate macromonomer. Step (8) may be performed after all the preceding method steps. Alternatively, step (8) may be performed multiple times between methods, i.e., after any of the above steps for producing the (K)siloxane-(meth)acrylate macromonomer. Step (8) may further recover by-products including (L) high-boiling oligomers and / or (M) low-boiling oligomers, and as a result the by-products may be recycled in the (above-above) method. Step (8) may be performed by any convenient means. Step (8) may include one or more filtrations, centrifugations, and / or decantations to remove solid by-products such as inorganic salts produced by the above-described neutralization and reaction termination steps. Step (8) may include stripping, distillation, or both, with heating and optionally reduced pressure. The starting materials used in the method, as well as the intermediates, products, and by-products, are described in more detail below.

[0014] (A) (meth)acrylate-functionalized alkenyl compounds The starting material (A) is,

[0015] [ka] A (meth)acrylate-functional alkenyl compound, wherein R in the formula 1 R is selected from the group consisting of H, alkyl, and aryl. 3 R is selected from the group consisting of H, alkyl, and aryl. 4 R is selected from the group consisting of H, alkyl, and aryl, and the subscript a is an integer with a value between 1 and 6. 1 , R 3 and R 4Suitable alkyl groups may have 1 to 12 carbon atoms or 1 to 6 carbon atoms. Examples of alkyl groups include 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 (and branched isomers having 5 to 12 carbon atoms), and further examples of alkyl groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, alkyl groups may be selected from the group consisting of methyl, ethyl, propyl, and butyl, or from the group consisting of methyl, ethyl, and propyl, or methyl or ethyl. Alternatively, alkyl groups may be methyl. Suitable aryl groups may be monocyclic or polycyclic and may have a pendant hydrocarbyl group. For example, aryl groups include phenyl, tolyl, xylyl, and naphthyl, and further, aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, the aryl group may be monocyclic, such as phenyl, tolyl, or benzyl, or the aryl group may be phenyl. Alternatively, R 1 , R 3 and R 4 Each of these may be selected from the group consisting of H and methyl. Alternatively, R 1 It could be H. Or, R. 3 It could be H. Or, R. 4 The compound may be methyl. Examples of suitable commercially available compounds for the starting material (A) include allyl (meth)acrylate. Suitable (meth)acrylate-functional alkenyl compounds are commercially available, for example, from Sigma Aldrich, Inc. (St. Louis, Missouri, USA). The starting material (A) may be one of the above-mentioned (meth)acrylate-functional alkenyl compounds or a combination of two or more (meth)acrylate-functional alkenyl compounds.

[0016] The starting material (A) and the (meth)acrylate-functionalized alkenyl compound are present in sufficient quantities to provide a molar ratio [(A):(B) ratio] of starting material (A):(B) to 0.5:1 to 1.5:1. Alternatively, the (A):(B) ratio may be at least 0.75, or at least 0.95, while at the same time the (A):(B) ratio may be up to 1.25:1, or 1.05:1. Alternatively, the (A):(B) ratio may be 0.75:1 to 1.25:1, or 0.95:1 to 1.05:1.

[0017] (B) Hydrangea The starting material (B) is,

[0018] [ka] It is a hydridosilane, and in the formula R 5 is a halogen or alkoxy, and each R 6 is independently selected from the group consisting of halogens, alkyls, aryls, and alkoxys, and alkyls and aryls are R 1 As described above, the halogen may be selected from bromo (Br), chloro (Cl), fluoro (F), and iodine (I), or selected from Br and Cl, or simply Cl. The alkoxy is of the formula OR 7 It may also be a base of, where R 7 R 1 The alkyl group mentioned above is the one in question. Alternatively, each R 6 R may be independently selected from the group consisting of halogens, alkyls, and aryls. Alternatively, each R 6The starting material (B) may be independently selected from the group consisting of halogens and alkyls. Examples of commercially available hydridosilanes include hydridohalosilanes such as dichloromethylsilane (MeHSiCl2), dimethylchlorosilane (Me2HSiCl), phenyldichlorosilane (PhHSiCl2), diphenylchlorosilane (Ph2SiHCl), ethyldichlorosilane (EtHSiCl2), diethylchlorosilane (Et2HSiCl), and combinations of two or more of these. Suitable hydridosilanes are commercially available, for example, from Sigma Aldrich, Inc., Dow Silicones Corporation (Midland, Michigan, USA), and Gelest, Inc. The starting material (B) may be one of the above-mentioned hydridosilanes or a combination of two or more hydridosilanes.

[0019] (C) Hydrosilylation reaction catalyst The starting material (C) is a hydrosilylation catalyst. The hydrosilylation catalyst facilitates the reaction between the alkenyl group in the starting material (A) (meth)acrylate-functionalized alkenyl compound and the silicon-bonded hydrogen atom in the starting material (B) hydridosilane. The catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation reaction catalyst may be (C1) a platinum group metal as described above, (C2) a compound of such a metal, such as rhodium diphosphine chelates such as chlorotris(triphenylphosphine)rhodium(I) (Wilkinson catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, (C3) a complex of the compound with a low molecular weight organopolysiloxane, or (C4) a platinum group metal compound microencapsulated in a matrix or core-shell structure. Examples of complexes between platinum and low molecular weight organopolysiloxanes include a complex of 1,3-diethyl-1,1,3,3-tetramethyldisiloxane and platinum (Karstedt catalyst), and a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby complex). Alternatively, the hydrosilylation catalyst may be a compound or complex (C5) as described above, microencapsulated in a resin matrix. Specific examples of platinum-containing catalysts suitable for use herein include chloroplatinic acid in either hexahydrate or anhydrous form, or platinum-containing catalysts obtained by a method involving the reaction of chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes described in Roy's U.S. Patent No. 6,605,734. These alkene-platinum-silyl complexes may be prepared, for example, by mixing 0.015 moles of (COD)PtCl2 with 0.045 moles of COD and 0.0612 moles of HMeSiCl2, where COD represents cyclooctadienyl.Other exemplary hydrosilylation catalysts include Speier's U.S. Patent No. 2,823,218, Ashby's No. 3,159,601, Lamoreaux's No. 3,220,972, Chalk et al.'s No. 3,296,291, Willing's No. 3,419,593, Modic's No. 3,516,946, and Karstedt's No. 3,814,7 This is described in Patent No. 30, Chandra's Patent No. 3,928,629, Lee et al.'s Patent No. 3,989,668, Lee et al.'s Patent No. 4,766,176, Lee et al.'s Patent No. 4,784,879, Togashi's Patent No. 5,017,654, Chung et al.'s Patent No. 5,036,117, and Brown's Patent No. 5,175,325, as well as in Togashi et al.'s European Patent Application Publication No. 0 347 895(A). Suitable hydrosilylation catalysts for the starting material (C) are commercially available, for example, SYL-OFF® 4000 catalyst and SYL-OFF® 2700, which are available from Dow Silicones Corporation (Midland, Michigan, USA).

[0020] The starting material (C) may be one hydrosilylation catalyst or a combination of two or more of the above hydrosilylation catalysts. The amount of (C) hydrosilylation catalyst in the composition depends on various factors, including the selection of starting materials (A), (B), and (C), but the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and alkenyl groups, or the amount of catalyst is sufficient to provide at least 0.01 ppm, or at least 0.05 ppm, or at least 0.1 ppm, or at least 0.5 ppm, or at least 1 ppm of platinum group metals, based on the total amount of starting materials (A), (B), and (C) used in step (1) of the method described herein. At the same time, the amount of catalyst is sufficient to provide up to 800 ppm, or up to 500 ppm, or up to 100 ppm of platinum group metals, on the same basis.

[0021] (D)(meth)acrylate polymerization inhibitor The starting material (D) is a (meth)acrylate polymerization inhibitor (inhibitor) which may be optionally added in step 1) of the method described above. If present, the starting material (D), the inhibitor may be used in an amount of >0 to <0.01% based on the weight of (K) silicone-(meth)acrylate macromonomer, or >0 to <2,000 ppm, or 1 ppm to 1,818 ppm, or 10 ppm to 500 ppm on the same basis. The starting material (D), the (meth)acrylate polymerization inhibitor, is selected from the group consisting of (D1) phenol compounds, (D2) quinone compounds, (D3) hydroquinone compounds, (D4) N-oxyl compounds, (D5) phenothiazine compounds, (D6) hindered amine compounds, and (D7) two or more combinations of (D1) to (D6). Suitable inhibitors for the starting material (D) are commercially available and include, for example, nitrobenzene, butylated hydroxytoluene, diphenylpicrylhydrazyl (DPPH), p-methoxyphenol, 2,4-di-t-butylcatechol, phenothiazine, N,N-diethylhydroxylamine, salts of N-nitrosophenylhydroxylamine, (2,2,6,6-tetramethylpiperidine-1-yl)oxidanil (TEMPO), and 4-hydroxy-(2,2,6,6-tetramethylpiperidine-1-yl)oxidanil (4-hydroxyTEMPO). Suitable inhibitors are commercially available, for example, from Sigma Aldrich, Inc. The starting material (D) may be one of the above-mentioned inhibitors or a combination of two or more inhibitors.

[0022] (E) Solvent The starting material (E) is a solvent, which may be used to facilitate the mixing of one or more starting materials. For example, (C) the hydrosilylation catalyst may be delivered in the solvent. Suitable solvents include polydialkylsiloxanes, aromatic hydrocarbons, aliphatic hydrocarbons, and combinations of two or more of these. Polyalkylsiloxanes with a suitable vapor pressure may be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyalkylsiloxanes such as DOWSIL® 200 Fluids and DOWSIL® OS Fluids, which are commercially available from Dow Silicones Corporation (Midland, Michigan, USA) and have a vapor pressure of 0.5 to 1.5 cSt. Aromatic hydrocarbons may have 6 to 20 carbon atoms, such as benzene, toluene, or xylene. Aliphatic hydrocarbons are exemplified by heptane, hexane, cyclohexane, or octane, or isoparaffinic solvents. Hydrocarbon solvents are commercially available from suppliers such as Sigma-Aldrich, Inc. (St. Louis, Missouri, USA). The starting material (E) may be one of the solvents described above or a combination of two or more solvents.

[0023] The amount of solvent varies depending on various factors, including the type of solvent selected, as well as the amount and type of other starting materials selected for the stripping coating composition. However, the amount of solvent may be 0% to 25% based on the total weight of all starting materials used in step (1).

[0024] (F)(meth)acryloxyalkyl functional silane The hydrosilylation reaction product prepared in step (1) of the above method comprises a (meth)acrylooxyalkyl functional silane.

[0025] [ka] In the formula, R 1 , R3 , R 4 , R 5 , R 6 And the subscript 'a' has the same meaning as above. Alternatively, in this expression, R 6 One example of this could be a halogen such as Cl. Or, R 6 Both examples may be alkyl or aryl. Alternatively, R 6 Both examples may be alkyl groups such as methyl. Or, R 6 One example of this may be a halogen, R 6 One example of this could be an alkyl group.

[0026] (G)Water The starting material (G) used in step (2) of the method is water. The water can be undiluted (i.e., without any carrier vehicle / solvent) and / or pure (i.e., free from or substantially free from minerals and / or other impurities), and is not generally limited. For example, the water may be treated or untreated. Examples of processes that may be used to purify the water include distillation, filtration, deionization, and two or more combinations thereof, thereby performing deionization, distillation, and / or filtration on the water. Alternatively, the water may be untreated (e.g., tap water, i.e., water from a city water system, or well water used without further purification). Or, the water may be purified before step (2). Or, the water may be used as a mixture (e.g., a solution or suspension) containing a solvent such as any of those listed above. Water may be used in amounts selected by those skilled in the art, depending on various factors, such as the specific organosilane (H) selected, and the halogen content of (F)(meth)acryloxyalkyl functional silane and (H)organosilane. However, the amount of water added in step (2) may be 2 to 1,000 moles per mole of (meth)acryloxyalkyl functional silane. Alternatively, the amount of water may be 5 to 900, or 10 to 800, or 15 to 700, or 20 to 600, or 25 to 500, or 30 to 400, or 35 to 300, or 40 to 200, or 50 to 200, or 100 to 150 moles, on the same basis.

[0027] (H) Organophyllum The starting material (H) is given by formula R 2 3SiR 5 It is an organosilane, in the formula R 5 As described above, each R 2 R 1The organosilane is independently selected from the group consisting of alkyls and aryls, as described above. Examples of organosilanes for use in the methods herein may be organosilanes selected from the group consisting of chlorotrimethylsilane (Me3SiCl), triphenylchlorosilane (Ph3SiCl), dimethylvinylchlorosilane (Me2ViSiCl), and combinations of two or more of these. Organosilanes are known in the art and are commercially available from various sources such as Dow Silicones Corporation (Midland, Michigan, USA) and Gelest, Inc. (Morrisville, Pennsylvania, USA). The starting material (H) may be one organosilane or a combination of two or more organosilanes as described above. The amount of (H) organosilane may be 0.5 moles to 100 moles per mole of (F) (meth)acryloxyalkyl functionalized silane. Alternatively, the amount of (H) organosilane may be 0.6 to 90 moles, or 0.7 to 80 moles, or 0.8 to 70 moles, or 0.9 to 80 moles, or 1 to 70 moles, or 1.1 to 60 moles, or 1.2 to 50 moles, or 1.3 to 40 moles, or 1.4 to 30 moles, or 1.5 to 20 moles, or 1.6 to 20 moles, or 1.7 to 15 moles, or 1.8 to 10 moles, or 1.9 to 5 moles, or 2 to 4 moles of (H) organosilane, according to the same criteria.

[0028] (I) Neutralizing agent The starting material (I) is a neutralizing agent that is added if any step (4) is included in the method described above. The neutralizing agent is an acid such as a by-product of hydrolysis and condensation (e.g., HCl, R 5 As stated above, formula HR 5The neutralizing agent can be any compound suitable for neutralizing the acid. The neutralizing agent may contain ammonia gas. Alternatively, the neutralizing agent may be a carbonate, a bicarbonate, or a combination thereof. For example, the neutralizing agent may contain sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof. Alternatively, the neutralizing agent may contain hydrotalcite. Suitable neutralizing agents are commercially available, for example, from Fisher Chemical (Waltham, Massachusetts, USA). The starting material (I) may be one of the neutralizing agents described above or a combination of two or more neutralizing agents. The amount of the neutralizing agent is between 1 and 100 equivalents based on the weight of organosilane, depending on various factors including the specific neutralizing agent selected and the amount of acid present. Alternatively, the amount of the neutralizing agent may be between 1.5 and 75, or 2 and 50, or 3 and 25, or 4 and 10 equivalents, on the same basis.

[0029] (J) Condensation catalyst The starting material (J) is a condensation catalyst. The condensation catalyst may be a strong acid such as sulfuric acid or sulfonic acid, for example, p-toluenesulfonic acid monohydrate, trifluoromethanesulfonic acid, heterogeneous sulfonic acid resin catalyst, or a combination thereof. Examples of such strong acids are known in the art, for example, as described in U.S. Patent No. 4,482,670 by Saam et al. Alternatively, the condensation catalyst may be a strong base such as potassium hydroxide, potassium methoxide, sodium hydroxide, sodium methoxide, potassium silanolate, or a combination of two or more of these. Examples of such strong bases are known in the art, for example, as described in U.S. Patent No. 8,470,925 by Liu et al. Suitable strong acids and strong bases for use as condensation catalysts (J) are commercially available, for example, from Sigma Aldrich, Inc. The starting material (J) may be one of the strong acids or a combination of two or more strong acids as described above. Alternatively, the starting material (J) may be one of the strong bases or a combination of two or more strong bases as described above. (J) The amount of condensation catalyst depends on catalyst selectivity and R 6Depending on various factors, including the selection of (J), the amount of (J) condensation catalyst may be 0.01% to 10% based on the weight of the starting material used in step (5) of the method described above. Alternatively, the amount of (J) condensation catalyst may be 0.1% to 5%, or 0.5% to 2%, or 1%, based on the same criteria.

[0030] (K) Siloxane-(meth)acrylate macromonomer The siloxane-(meth)acrylate macromonomer (K) formed by this method is,

[0031] [ka] It has, in the formula, R 1 , R 2 , R 3 , R 4 , and the subscript a are as described above, and each R 7 These are alkyl, aryl, and formula [(R 2 )3SiO 1 / 2 Selected independently from the base of ]. Or, at least one example R 7 is the formula [(R 2 3) SiO 1 / 2 It is the basis of ]. Or, R 7 Both examples are given by the expression [(R 2 3) SiO 1 / 2 It is the basis of ]. Or, R 7 One example is the expression [(R 2 )3SiO 1 / 2 It may also be a base of ], R 7 One example of this may be an alkyl group. The alkyl group may be methyl. An example of a siloxane-(meth)acrylate macromonomer prepared by this method is 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate.

[0032] When (K) siloxane-(meth)acrylate macromonomer is formed, by-products including (L) high-boiling oligomer and (M) low-boiling oligomer may also be formed. The term "high-boiling" means that (L) high-boiling oligomer has a higher boiling point than (K) siloxane-(meth)acrylate macromonomer, and the term "low-boiling" means that (M) low-boiling oligomer has a lower boiling point than (K) siloxane-(meth)acrylate macromonomer. When the reaction product containing (K), (L), and (M) is distilled, the (M) low-boiling oligomer may be formed in the light fraction, and the (L) high-boiling oligomer may be formed in the bottom fraction.

[0033] (L) High boiling point oligomer High-boiling-point oligomers may include the unit formula:

[0034] [ka] In the formula, R 1 , R 3 , R 4 And the subscript a is as described above, the subscript b is 0, 1 or 2, the subscript f is 0, 1 or 2, the quantity (b+f)=2, the subscript d may be 2-10 or 2-4, the subscript e may be 0-9 or 0 or 1, and the quantity (d+e) may be 2-10 or 2-4.

[0035] (M) Low boiling point oligomer Low boiling point oligomers are given by formula R 2 3Si-O-SiR 2 It may have 3, in the formula, R 2As described above, the starting material (M) may include hexamethyldisiloxane. Low-boiling oligomers may be produced (by-products) in one or more steps of the method described above. In addition to the low-boiling oligomers thus produced, other low-boiling oligomers such as hexamethyldisiloxane are commercially available, for example, from Dow Silicones Corporation and Gelest, Inc. New low-boiling oligomers may be purchased and may be added in one of steps (3) to (7) described above.

[0036] (N) Reaction stopper The starting material (N) is a reaction stopper added if any step (6) is included in the method described above. The reaction stopper can be any compound suitable for stopping the reaction of the (J) condensation catalyst described above. The reaction stopper may be the same as or different from the (I) neutralizer described above. The reaction stopper may include ammonia gas, and step (6) may include a step of bubbling ammonia gas through the condensation reaction product. Alternatively, the reaction stopper may be a base (reaction stoppage may be carried out by adding a base). The base may be pyridine, imidazole, and / or a hydroxide of a quaternary ammonium cation. Suitable reaction stoppers are commercially available, for example, from Fisher Chemical (Waltham, Massachusetts, USA). The starting material (N) may be one of the reaction stoppers described above or a combination of two or more reaction stoppers. The amount of reaction stopper depends on various factors, including the specific reaction stopper selected and the amount of (J) condensation catalyst present, but the amount of reaction stopper may be 0.01% to 10% based on the weight of the (J) condensation catalyst. Alternatively, the amount of (N) reaction stopper may be 0.1% to 5%, or 0.5% to 2%, or 1%, based on the same standard equal to 100 equivalents based on the weight of the (J) condensation catalyst. Alternatively, the amount of neutralizer may be 1.5 to 75%, or 2 to 50%, or 3 to 25%, or 4 to 10 equivalents, based on the same standard.

[0037] (O) Additional condensation catalyst The starting material (O) is an additional condensation catalyst as described above for the starting material (J). The starting material (O) can be added if step (7) is present in the method. The additional condensation catalyst may be the same as or different from the condensation catalyst selected for the starting material (J) used in step (4). The amount of the additional condensation catalyst used in step (7). The starting material (O) may be one strong acid or a combination of two or more strong acids as described above. Alternatively, the starting material (O) may be one strong base or a combination of two or more strong bases as described above. (O) The amount of the additional condensation catalyst depends on the catalyst selectivity and R 6 Depending on various factors including the selection of (O), the amount of additional condensation catalyst may be 0.01% to 10% based on the weight of the starting material used in step (5) of the method described above. Alternatively, the amount of additional condensation catalyst may be 0.1% to 5%, or 0.5% to 2%, or 1%, on the same basis. [Examples]

[0038] These examples are intended to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are summarized in Table 1.

[0039] [Table 1]

[0040] Example 1: Synthesis of MD'M-ALMA, Step 1 In this Example 1, methacryloxypropyldichloromethylsilane was prepared as follows.

[0041] [ka]

[0042] In a nitrogen-purged glove box, 31.5 g (250 mmol) of allyl methacrylate was placed in a 220 mL glass jar. 60–65 mg of 4-hydroxy-TEMPO (1000 ppm) and 25 μL (10 ppm) of Karrstedt catalyst (2% Pt in xylene) were added to the glass jar, and the mixture was heated to 60°C using a heat block. Once the jar reached equilibrium, 30.2 g (262.5 mmol) of dichloromethylsilane was added dropwise using a dropping funnel. During the addition, another 10 μL of Karrstedt catalyst (2% Pt in xylene) was added to complete the reaction. The heat block was removed, the reactants were allowed to exotherm, and the reaction was monitored by GC-MS. The reaction was completed within 3–5 hours.

[0043] GC-FID was performed under standard conditions (50°C for 2 minutes, increasing to 250°C at 20°C / min, and holding at 250°C for 10 minutes). No oxysilyl ester formation was observed. No elimination of propylene was observed. This reaction demonstrated a very clean conversion to a hydrosilylation product that does not contain any detectable branched isomers.

[0044] Once it was determined from the GC-FID that no starting material remained, stirring was stopped, and 60.2 g of the reaction product was obtained and used directly in the next step without further purification.

[0045] Example 2: Synthesis of MD'M-ALMA, Step 2: In this Example 2, methacryloxypropyldichloromethylsilane (430 mmol, 103 g) and chlorotrimethylsilane (TMS-Cl, 900 mmol, 100 g) were pre-mixed in a 500 mL round-bottom flask in a glove box. The flask was removed from the glove box, and its contents were slowly added to 1.25 L of water (75 mol) in a 2 L round-bottom flask via an additive funnel over 1 hour in open air. The reaction mixture was vigorously stirred at room temperature. After the addition was complete, the contents of the flask were stirred for a further 15 minutes. Aliquots were taken and analyzed by GC-FID.

[0046] Example 3: Synthesis of MD'M-ALMA, Step 3- The reaction mixture prepared in Example 2 was transferred to a separatory funnel, and the organic phase was separated from the aqueous layer. After repeating the separation, all the organic layers were collected, washed with NaHCO3 solution to neutralize the acid, dried with anhydrous Na2SO4, and then transferred to a 1 L round-bottom flask.

[0047] Next, 900 mg of p-toluenesulfonic acid monohydrate (1 wt%) was added to the flask, which was then placed on a preheated (60°C) metal block flask under a nitrogen atmosphere. The reaction mixture was held at 60°C for 30 minutes to equilibrium. After 30 minutes, the reaction mixture was cooled to room temperature, and another GC aliquot was taken and analyzed by GC-FID. The GC-FID analysis showed the product distribution as shown in Table 2 below.

[0048] [Table 2]

[0049] Example 4: Synthesis of MD'M-ALMA After equilibration in Example 3, the resulting reaction mixture was neutralized by bubbling ammonia gas through the reaction mixture to quench all residual p-toluenesulfonic acid. A white inorganic salt was formed, and after filtering the reaction mixture to remove all inorganic salts, it was transferred to a distillation flask, which was connected to a short-stroke distillation column used to remove low-boiling hexamethyldisiloxane and MD'M-ALMA.

[0050] Relatively high-quality MD'M-ALMA was recovered from short-step distillation: ·MD'M-ALMA purity=95.7% • MD'M-ALMA yield = 28% • Little to no product loss was observed in the light and bottom fractions.

[0051] [Table 3]

[0052] Example 5 After removing MD'M-ALMA and hexamethyldisiloxane from the reaction mixture prepared as described above, the distillation bottom (containing high-boiling oligomers) was combined with hexamethyldisiloxane (light form) and treated with p-toluenesulfonic acid monohydrate at 60-70°C before being returned to the mixture. The progress of the reaction was monitored by GC-FID, and the slow regeneration of MD'M-ALMA was observed within the reaction mixture by re-equilibrium chemistry. The results are shown in the table below.

[0053] [Table 4]

[0054] Definitions and Use of Terms All quantities, ratios, and percentages are based on weight unless otherwise specified. The “Summary of the Invention” and the “Abstract” are incorporated herein by reference. Unless otherwise specified in the context of the specification, the articles “a,” “an,” and “the” each refer to one or more. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in sections §2111.03 I, II, and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. The use of “for example,” “eg,” “such as,” and “including” to list examples is not limited to the examples listed. Therefore, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to,” and includes other similar or equivalent examples. Abbreviations used herein have the definitions in the following abbreviation table.

[0055] [Table 5]

[0056] The present invention is described in an exemplary manner, and it should be understood that the terms used are intended to be descriptive rather than restrictive. With respect to any group of Markush on which the description of individual features or embodiments herein relies, different, specific, and / or unforeseen results may be obtained from each element of that Markush group independently of all other elements of the Markush groups. Each element of a Markush group may be relied upon individually and / or in combination in particular embodiments within the scope of the following embodiments and claims, and will provide sufficient support.

[0057] Furthermore, any ranges and subranges on which the present invention is based, independently and comprehensively, fall within the scope of the following embodiments and claims, and are understood to describe and derive the entire range encompassing all and / or partial values ​​therein, even if those values ​​are not explicitly stated herein. Those skilled in the art will readily recognize that the listed ranges and subranges adequately describe and enable various embodiments of the present invention, and that such ranges and subranges can be further demarcated into more relevant half-, one-third, one-quarter, one-fifth, and any other subranges included within the range. As merely one example, the range "50-70" may be further described as the bottom third, i.e., 50-56, the middle third, i.e., 57-63, and the top third, i.e., 64-70. Alternatively, the range "50-70" may include the subrange "60-70," each individually and collectively within the following embodiments and claims, and may individually and / or collectively rely on specific embodiments within the following embodiments and claims, providing them with appropriate grounds. In addition, with respect to words defining or modifying ranges, such as "at least," "greater than," "less than," and "less than or equal to," such words should be understood to include subranges and / or upper or lower limits.

[0058] Embodiments of the present invention In the first embodiment, a method for preparing a siloxane-(meth)acrylate macromonomer is: (1) Formula (A)

[0059] [ka] A (meth)acrylate-functional alkenyl compound, wherein R 1 R is selected from the group consisting of H, alkyl, and aryl. 3 R is selected from the group consisting of H, alkyl, and aryl. 4 is selected from the group consisting of H, alkyl, and aryl, and the subscript a is an integer having a value from 1 to 6, and is a (meth)acrylate-functional alkenyl compound. Formula (B)

[0060] [ka] It is a hydridohalosilane, in which R 5 It is a halogen, and each R 6 The starting material comprises a hydridohalosilane independently selected from the group consisting of halogens and alkyls, (C) Hydrosilylation reaction catalyst and (D)(meth)acrylate polymerization inhibitor, Optionally, hydrosilylate in the presence of solvent E) thereby formula

[0061] [ka] A (meth)acryloxyalkyl functional halosilane, wherein R 1 , R 3 , R 4 , R 5 , R 6 , and the subscript a is defined above, forming a hydrosilylation reaction product containing a (meth)acryloxyalkyl functional halosilane, (2) (F) The (meth)acryloxyalkyl-functional halosilane prepared in step (1), (G) water, (H) an organohalosilane of the formula R 2 3SiR 5 wherein R 5 is as described above, and R 2 is alkyl, hydrolyzing a compound containing the organohalosilane to thereby form a hydrolysis product, (3) (K) a hydrolysis product containing a siloxane-(meth)acrylate macromonomer and (L) a high-boiling oligomer of the unit formula,

[0062] [Chemical formula] wherein R 1 , R 3 , R 4 , and the subscript a are as described above, the subscript b is 0, 1, or 2, the subscript f is 0, 1, or 2, the quantity (b + f) = 2, the subscript d is 2 - 4, the subscript e is 0 or 1, the quantity (d + e) is 2 - 4, a high-boiling oligomer, and M) an oligomer of the formula R 2 3Si - O - SiR 2 3, wherein R 2 is as described above, removing all or part of the water from the by-products containing the low-boiling oligomer, Optionally, neutralizing the hydrolysis product by a technique including (4) (I) adding a neutralizing agent to thereby form a neutralized mixture, Optionally, condensing the neutralized mixture by a technique including (5) (J) adding a condensation catalyst to thereby prepare a reaction mixture containing an additional amount of (K) a siloxane-(meth)acrylate macromonomer and an additional amount of by-products containing (L) a high-boiling oligomer and (M) a low-boiling oligomer, thereby forming a condensation reaction product, Optionally, the (J) condensation catalyst is deactivated by adding a (6)(N) reaction terminator to the condensation reaction product, thereby forming a deactivated product containing an inorganic salt of the (J) acid catalyst and the (N) reaction terminator. Optionally, (7) the (L) high-boiling oligomers and (M) low-boiling oligomers are equilibrated in the presence of an (O) additional condensation catalyst (formed in any of the preceding steps), thereby forming a further additional amount of the (K) siloxane-(meth)acrylate macromonomer. (8) recovering the (K) siloxane-(meth)acrylate macromonomer.

[0063] In a second embodiment, the method of the first embodiment further comprises recovering the (L) high-boiling oligomer.

[0064] In a third embodiment, the method of the first or second embodiment further comprises recovering the (M) low-boiling oligomer.

[0065] In a fourth embodiment, the method of any one of the preceding embodiments further comprises adding an additional new (M) low-boiling oligomer.

[0066] In a fifth embodiment, the method of the fourth embodiment further comprises equilibrating the (L) high-boiling oligomer and the (M) low-boiling oligomer in the presence of an (O) additional acid catalyst, thereby forming an additional amount of the siloxane-(meth)acrylate macromonomer.

[0067] In a sixth embodiment, in the method of any one of the preceding embodiments, the (A)(meth)acrylate-functional alkenyl compound has the formula

[0068]

Chemical formula

[0069] In the seventh embodiment, in any one of the methods of the prior embodiments, the (A)(meth)acrylate-functionalized alkenyl compound is selected from the group consisting of allyl acrylates and allyl methacrylates.

[0070] In the eighth embodiment, in any one of the methods of the prior embodiments, (B) in hydridohalosilane, each R 5 It is Cl.

[0071] In the ninth embodiment, in any one of the methods of the prior embodiments, (B) hydridohalosilane is selected from the group consisting of dichloromethylsilane (MeHSiCl2), dimethylchlorosilane (Me2HSiCl), phenyldichlorosilane (PhHSiCl2), diphenylchlorosilane (Ph2SiHCl), ethyldichlorosilane (EtHSiCl2), diethylchlorosilane (Et2HSiCl), and two or more combinations thereof.

[0072] In the tenth embodiment, in any one of the methods of the prior embodiments, (C) the hydrosilylation reaction catalyst is selected from the group consisting of (C1) platinum group metals, (C2) compounds of platinum group metals, (C3) complexes of compounds with alkenyl-functional organopolysiloxane oligomers, (C4) compounds microencapsulated in a matrix or core-shell structure, and (C5) complexes of compounds microencapsulated in a resin matrix.

[0073] In the eleventh embodiment, the platinum group metal is platinum in the method of the tenth embodiment.

[0074] In the twelfth embodiment, a (D)(meth)acrylate polymerization inhibitor is present in any one of the methods of the prior embodiments.

[0075] In the 13th embodiment, in the method of the 12th embodiment, (D) the (meth)acrylate polymerization inhibitor is selected from the group consisting of (D1) phenol compounds, (D2) quinone compounds, (D3) hydroquinone compounds, (D4) N-oxyl compounds, (D5) phenothiazine compounds, (D6) hindered amine compounds, and (D7) two or more combinations of (D1) to (D6).

[0076] In the 14th embodiment, in the method of the 12th or 13th embodiment, the (D)(meth)acrylate polymerization inhibitor is an N-oxyl compound selected from the group consisting of (2,2,6,6-tetramethylpiperidine-1-yl)oxyl (TEMPO), 4-hydroxy(2,2,6,6-tetramethylpiperidine-1-yl)oxyl, bis(2,2,6,6-tetramethylpiperidine-1-yl)oxyl sebacate (Bis-TEMPO), polymer-bound TEMPO, and two or more combinations thereof.

[0077] In the 15th embodiment, in any one of the methods of the 1st to 14th embodiments, (E) a solvent is present.

[0078] In the sixteenth embodiment, in the method of the fifteenth embodiment, (E) the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and two or more combinations thereof.

[0079] In the 17th embodiment, in any one of the methods of the prior embodiments, step (1) includes the step of mixing and heating the starting materials at a temperature of 50°C to 70°C.

[0080] In the 18th embodiment, in any one of the preceding embodiments, (H) organohalosilane is R 2 3SiR 5 It has, in the formula, R 2 As stated above, R 5 It is Cl.

[0081] In the 19th embodiment, in the method of the 18th embodiment, the (H) organohalosilane is selected from the group consisting of chlorotrimethylsilane (Me3SiCl), triphenylchlorosilane (Ph3SiCl), dimethylvinylchlorosilane (Me2ViSiCl), and two or more combinations thereof.

[0082] In the 20th embodiment, in any one of the methods of the prior embodiments, step (2) includes a step of mixing at 23°C ± 2°C.

[0083] In the 21st embodiment, in any one of the methods of the prior embodiments, step (3) includes a step of phase separation and decantation before step (4).

[0084] In the 22nd embodiment, in any one of the methods of the prior embodiments, step (3) includes the step of adding a desiccant after step (4).

[0085] In the 23rd embodiment, step (4) is present in any one of the methods of the prior embodiments, and step (4) includes mixing the neutralizing agent with the hydrolysis product at 23°C ± 2°C.

[0086] In the 24th embodiment, in the method of the 23rd embodiment, the neutralizing agent is selected from the group consisting of ammonia gas, carbonate, bicarbonate, hydrotalcite, or a combination of two or more thereof.

[0087] In the 25th embodiment, in any one of the methods of the prior embodiments, (J) the condensation catalyst is a strong acid or a strong base.

[0088] In the 26th embodiment, in any one of the methods of the prior embodiments, the (J) condensation catalyst is selected from the group consisting of sulfuric acid, sulfonic acid, potassium hydroxide, potassium methoxide, sodium hydroxide, sodium methoxide, potassium silanolate, and two or more combinations thereof.

[0089] In the 27th embodiment, in any one of the methods of the prior embodiments, (M) low-boiling oligomer comprises hexamethyldisiloxane.

[0090] In the 28th embodiment, step (5) is present in any one of the methods of the prior embodiments, and step (5) includes a step of mixing and heating at a temperature of 50°C to 70°C.

[0091] In the 29th embodiment, step (6) is present in the method of the 28th embodiment.

[0092] In the 30th embodiment, in the method of the 29th embodiment, the (N) reaction stopper comprises ammonia gas, and step (6) comprises bubbling ammonia gas through the condensation reaction product.

[0093] In the 31st embodiment, step (7) is present in any one of the methods of the prior embodiments.

[0094] In the 32nd embodiment, in the method of the 31st embodiment, in step (7), (O) the additional condensation catalyst is a strong acid or a strong base.

[0095] In the 33rd embodiment, in the method of the 32nd embodiment, (O) the additional condensation catalyst is selected from the group consisting of sulfuric acid, sulfonic acid, potassium hydroxide, potassium methoxide, sodium hydroxide, sodium methoxide, potassium silanolate, and two or more combinations thereof.

[0096] In the 34th embodiment, step (8) includes stripping, distillation, or both, in any one of the methods of the prior embodiments.

[0097] In the 35th embodiment, the siloxane-(meth)acrylate macromonomer is prepared by any one of the methods of the preceding embodiments.

[0098] In the 36th embodiment, the siloxane-(meth)acrylate macromonomer of the 35th embodiment is of the formula

[0099] [ka] It has, in the formula, R 1 , R 2 , R 3 , R 4 , and the subscript a are as described above, and each R 7 is alkyl and formula -OSiR 2 It is selected independently from the three bases. The present invention may provide the following embodiments. [1] A method for preparing a siloxane-(meth)acrylate macromonomer, wherein the method is: (1) Formula (A) [ka] A (meth)acrylate-functional alkenyl compound, wherein R 1 R is selected from the group consisting of H, alkyl, and aryl. 3 R is selected from the group consisting of H, alkyl, and aryl. 4 is selected from the group consisting of H, alkyl, and aryl, and the subscript a is an integer having a value from 1 to 6, and is a (meth)acrylate-functional alkenyl compound. Formula (B) [ka] A hydridosilane in the formula R 5 is a halogen or alkoxy, and each R 6 The starting material comprises a hydridosilane independently selected from the group consisting of halogens, alkyls, aryls, and alkoxys. (C) Hydrosilylation reaction catalyst and (D)(meth)acrylate polymerization inhibitor, (E) is optionally hydrosilylated in the presence of solvent, thereby formula [ka] A (meth)acryloxyalkyl functional silane, wherein R 1 、R3 、R 4 、R 5 、R 6 , and the subscript a is defined above, forming a hydrosilylation reaction product containing a (meth)acryloxyalkyl functional silane, (2) (F) The (meth)acryloxyalkyl functional silane prepared in step (1), (G) Water and, (H) Formula R 2 3 SiR 5 The organosilane is, in the formula, R 5 As stated above, R 2 The process involves hydrolyzing an alkyl, organosilane, and a compound containing it, thereby forming a hydrolysis product. (3) (K) The hydrolysis product comprising the siloxane-(meth)acrylate macromonomer and (L) a high boiling oligomer of unit formula,

change

[10] (I) The method according to [9] above, wherein the neutralizing agent is selected from the group consisting of ammonia gas, carbonate, bicarbonate, hydrotalcite, or two or more combinations thereof.

[11] (5)(J) The method according to [9], further comprising condensing the neutralized mixture by a technique including the addition of a condensation catalyst to prepare a reaction mixture comprising an additional amount of (K) the siloxane-(meth)acrylate macromonomer and an additional amount of the by-product comprising (L) the high-boiling oligomer and (M) the low-boiling oligomer, thereby forming a condensation reaction product.

[12] (J) The method according to

[11] above, wherein the condensation catalyst is selected from the group consisting of sulfuric acid, sulfonic acid, potassium hydroxide, potassium methoxide, sodium hydroxide, sodium methoxide, potassium silanolate, and two or more combinations thereof.

[13] (6) The method according to [9], further comprising adding (N) a reaction stopper to the condensation reaction product to (J) the condensation catalyst to stop the reaction, thereby forming a stopped reaction product comprising (J) the acid catalyst and (N) an inorganic salt of the reaction stopper.

[14] (N) The method according to

[13] above, wherein the reaction terminating agent is selected from the group consisting of ammonia gas, carbonate, bicarbonate, hydrotalcite, pyridine, imidazole, and / or quaternary ammonium cation hydroxides.

[15] (7) The method according to any one of the above [1] to

[14] , further comprising (O) equilibrating (L) the high-boiling oligomer and (M) the low-boiling oligomer in the presence of an additional condensation catalyst to thereby form a further additional amount of (K) siloxane-(meth)acrylate macromonomer.

Claims

1. A method for preparing a siloxane-(meth)acrylate macromonomer, wherein the method is: （１） (A) Formula 【Chemistry 1】 A (meth)acrylate-functional alkenyl compound, wherein R １ R is selected from the group consisting of H, alkyl, and aryl. ３ R is selected from the group consisting of H, alkyl, and aryl. ４ is a (meth)acrylate-functional alkenyl compound selected from the group consisting of H, alkyl, and aryl, where the subscript a is an integer having a value from 1 to 6, (B) Formula 【Chemistry 2】 A hydridosilane in which R ５ is a halogen or alkoxy, and each R ６ The starting material comprises a hydridosilane independently selected from the group consisting of halogens, alkyls, aryls, and alkoxys. (C) Hydrosilylation reaction catalyst and (D) (meth)acrylate polymerization inhibitor, (E) is optionally hydrosilylated in the presence of solvent, thereby formula 【Transformation 3】 (Meth)acryloxyalkyl-functional silane, where R in the formula １ R ３ R ４ R ５ R ６ and the subscript a are as defined above, to form a hydrosilylation reaction product comprising (meth)acryloxyalkyl-functional silane （２） (F) The (meth)acryloxyalkyl functional silane prepared in step (1), (G) Water and, (H) Formula R ２ ３ SiR ５ The organosilane is, in the formula, R ５ As stated above, R ２ The process involves hydrolyzing an alkyl, organosilane, and a compound containing it, thereby forming a hydrolysis product. (3) (K) The hydrolysis product comprising the siloxane-(meth)acrylate macromonomer and (L) a high boiling oligomer of a unit formula, 【Chemistry 4】 In the formula R １ , R ３ , R ４ , and the subscript a is as described above, the subscript b is 0, 1, or 2, the subscript f is 0, 1, or 2, the quantity (b + f) = 2, the subscript d is 2 to 10, the subscript e is 0 to 9, the quantity (d + e) ​​is 2 to 10, a high boiling point oligomer, and formula (M) R ２ ３ Si-O-SiR ２ ３ A low boiling oligomer of which R in the formula ２ As described above, this involves removing all or part of the water from the by-product containing low-boiling oligomers, Methods that include...

2. (A) The method according to claim 1, wherein the (meth)acrylate-functionalized alkenyl compound is selected from the group consisting of allyl acrylate and allyl methacrylate.

3. (B) The method according to claim 1, wherein the hydridosilane is a hydridohalosilane selected from the group consisting of dichloromethylsilane, dimethylchlorosilane, phenyldichlorosilane, diphenylchlorosilane, ethyldichlorosilane, diethylchlorosilane, and combinations of two or more of these.

4. The method according to claim 1, wherein the hydrosilylation reaction catalyst is selected from the group consisting of (C1) a platinum group metal, (C2) a compound of the platinum group metal, (C3) a complex of the compound with an alkenyl-functional organopolysiloxane oligomer, (C4) the compound microencapsulated in a matrix or core-shell structure, and (C5) a complex of the compound microencapsulated in a resin matrix.

5. (D) The method according to claim 1, wherein the (meth)acrylate polymerization inhibitor is present, and the (meth)acrylate polymerization inhibitor is selected from the group consisting of (D1) phenol compounds, (D2) quinone compounds, (D3) hydroquinone compounds, (D4) N-oxyl compounds, (D5) phenothiazine compounds, (D6) hindered amine compounds, and (D7) two or more combinations of (D1) to (D6).

6. The method according to claim 1, wherein the solvent is present and selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof.

7. The method according to claim 1, wherein step (1) is performed by mixing and heating the starting materials at a temperature of 50°C to 70°C.

8. (H) The method according to claim 1, wherein the organosilane is selected from the group consisting of chlorotrimethylsilane, triphenylchlorosilane, dimethylvinylchlorosilane, and two or more combinations thereof.

9. (4) The method according to claim 1, further comprising (I) neutralizing the hydrolysis product by a technique including adding a neutralizing agent to form a neutralized mixture.

10. (I) The method according to claim 9, wherein the neutralizing agent is selected from the group consisting of ammonia gas, carbonate, bicarbonate, hydrotalcite, or a combination of two or more thereof.

11. The method according to claim 9, further comprising (5) (J) condensing the neutralized mixture by a technique including adding a condensation catalyst, thereby preparing a reaction mixture comprising an additional amount of (K) the siloxane-(meth)acrylate macromonomer and an additional amount of the by-products comprising (L) the high-boiling oligomer and (M) the low-boiling oligomer, thereby forming a condensation reaction product.

12. (J) The method according to claim 11, wherein the condensation catalyst is selected from the group consisting of sulfuric acid, sulfonic acid, potassium hydroxide, potassium methoxide, sodium hydroxide, sodium methoxide, potassium silanolate, and two or more combinations thereof.

13. (6) The method according to claim 11, further comprising adding (N) a reaction stopper to the condensation reaction product to (J) the condensation catalyst to stop the reaction, thereby forming a reaction-stopped product containing the inorganic salts of (J) the condensation catalyst and (N) the reaction stopper.

14. (N) The method according to claim 13, wherein the reaction terminating agent is selected from the group consisting of ammonia gas, carbonate, bicarbonate, hydrotalcite, pyridine, imidazole, and / or quaternary ammonium cation hydroxides.

15. (7) The method according to any one of claims 1 to 14, further comprising (O) equilibrating (L) the high-boiling oligomer and (M) the low-boiling oligomer in the presence of an additional condensation catalyst, thereby forming a further additional amount of (K) siloxane-(meth)acrylate macromonomer.

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