Method for preparing ether-functionalized silicones

Abstract

A method for producing ether-functionalized silicones involves a hydrosilylation reaction between an acetate-capped alkenyloxy-functionalized ether and a polyorganohydrogensiloxane in the presence of a catalyst containing a bicyclic compound. The method may further include preparing the catalyst by combining a Karrstedt catalyst with a bicyclic compound to form a complex.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 416061, filed on 14 October 2022 under Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 416061 is incorporated herein by reference.

[0002] (Field of Invention) A method for preparing ether-functionalized silicones is described herein. More specifically, the method involves a hydrosilylation reaction of an acetate-capped alkenyloxy-functionalized ether with a polyorganohydrogensiloxane in the presence of a catalyst containing a bicyclic compound. [Background technology]

[0003] Introduction Silicone polyethers (SPEs) are widely used in multiple markets, including cosmetic care, home care, coatings, leather, defoamers, and as additives in polyurethanes. SPEs can be produced by Pt-catalyzed hydrosilylation between SiH siloxanes and olefin-terminated polyethers. The main Pt catalysts used to produce SPEs via hydrosilylation are platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (also known as the Karrstedt catalyst, as described in U.S. Patent No. 3,814,730) and chloroplatinic acid (also known as the Speier catalyst, as described in U.S. Patent No. 2,823,218).

[0004] However, Karstedt and Speier catalysts often result in inconsistent reactivity during the hydrosilylation reaction between SiH siloxanes and olefin-terminated polyethers due to impurities present in the starting materials. Variations in hydrosilylation rates and conversion rates can negatively impact users of SPEs produced by this method. [Overview of the project]

[0005] A method for preparing an ether-functional silicone, comprising combining (A) an acetate-capped alkenyloxy functional ether, (B) a polyorganohydrogensiloxane, and (C) a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst can be prepared by a method comprising combining i) a platinum(0)-siloxane complex and ii) a starting material comprising a bicyclic compound. [Modes for carrying out the invention]

[0006] In a method for preparing ether-functionalized silicones, the hydrosilylation catalyst may be prepared before combining the acetate-capped alkenyloxy-functionalized ether and / or polyorganohydrogensiloxane with the hydrosilylation catalyst, or the hydrosilylation catalyst may be prepared in situ. The preparation of the hydrosilylation catalyst is as follows: i) Platinum(0)-siloxane complex, wherein the complex is chemically bonded platinum and formula R m R' n R'' o SiO (4-m-n-o) / 2 Platinum(0)-siloxane complexes essentially consisting of unsaturated organosiloxanes (wherein each R is an independently selected monovalent hydrocarbon radical that does not contain aliphatic unsaturated hydrocarbon radicals, each R' is an independently selected monovalent aliphatic unsaturated hydrocarbon radical, each R'' is selected from R' radicals chemically bonded to platinum, the subscript m is 0-2, the subscript n is 0-2, the subscript o is 0.0002-3, and the amount (m+n+o) is 1-3), and ii)

[0007] [ka] and their combinations (in the formula, each R 3It can be carried out by a method including combining starting materials including a bicyclic compound selected independently from the group consisting of H, OH, acetate group, and ester group).

[0008] i) Platinum(0)-siloxane complex The platinum(0)-siloxane complex as starting material i) is known in the art and is described, for example, in U.S. Patent No. 3,814,730, which is incorporated herein by reference. This complex consists of chemically bonded platinum and the formula R m R’ n R’’ o SiO (4-m-n-o) / 2 (where each R is an independently selected monovalent hydrocarbon group without aliphatic unsaturation, each R’ is an independently selected monovalent aliphatic unsaturated hydrocarbon group, each R’’ is selected from R’ groups chemically bonded to platinum, the subscript m is 0 to 2, the subscript n is 0 to 2, the subscript o is 0.0002 to 3, and the amount (m + n + o) is 1 to 3) and may essentially consist of an unsaturated organosiloxane.

[0009] The platinum(0)-siloxane complex can be prepared by combining a platinum halide and an unsaturated organic silicon material which may be an organosiloxane of the formula R c R’ d SiO (4-c-d) / 2 (where R and R’ are as described above, the subscript c has a value equal to 0 or more and 2 or less, the subscript d has a value equal to 0.0002 or more and 3 or less, and the sum of c and d is equal to 1 or more and 3 or less). The platinum halide may be hexachloroplatinic acid or a metal salt such as NaHPtCl6n·H2O, KHPtCl6·nH2O, Na2PtCl6·nH2O, or K2PtCl6·nH2O. The complex can be made by contacting the unsaturated organic silicon material with the platinum halide to form a mixture having a certain concentration of inorganic halogen, treating the resulting mixture to remove the available inorganic halogen, and recovering the complex.

[0010] Alternatively, unsaturated organosilicon materials are given by the formula

[0011] [ka] The unsaturated organosiloxane may be (wherein R is alkyl, R' is alkenyl, the subscript h is an integer from 1 to 3, the subscript i is an integer from 1 to 3, and the amount (h+i) ≥ 2). Suitable alkyl groups for R include methyl, ethyl, propyl, and butyl, or methyl or ethyl, or methyl. Suitable alkenyl groups for R' include vinyl, allyl, and hexenyl, or vinyl and allyl, or vinyl. Alternatively, the unsaturated organosiloxane may be selected from the group consisting of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,3-trivinyltrimethyldisiloxane, 1,1,3,3-tetravinyl-1,3-dimethyldisiloxane, and hexavinyldisiloxane.

[0012] Alternatively, the complex may be a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, for example, containing the following formula.

[0013] [ka]

[0014] The starting material ii) is a bicyclic compound. A bicyclic compound is represented by formula ii-1).

[0015] [ka] Formula ii-2)

[0016] [ka] and combinations of both equation ii-1) and equation ii-2) (wherein each R3 (is selected independently from the group consisting of H, OH, acetate groups, and ester groups). The acetate group is defined as formula

[0017] [ka] (In the formula, D is a covalent bond or a divalent hydrocarbon group, R 4 It may have an alkyl group with 1 to 6 carbon atoms. The ester group is of the formula

[0018] [ka] (In the formula, D' is a covalent bond or a divalent hydrocarbon group (which may be the same as or different from D above), R 5 It may have an alkyl group with 1 to 6 carbon atoms. The divalent hydrocarbon group for D and D' is empirically defined as C r H 2x -(wherein the formula, the subscript r is between 2 and 10) may be present. For example, the divalent hydrocarbon group may be -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-CH2-, -CH2-CH2-CH(CH3)-, or -CH2-CH(CH3)-CH2-. Alternatively, D may be a covalent bond. Alternatively, D' may be a covalent bond. R 4 and R 5 Suitable alkyl groups can be independently selected from methyl, ethyl, propyl (including isopropyl and n-propyl), and butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl). Alternatively, R 4 It may be methyl or ethyl. Alternatively, it may be methyl. Alternatively, R 5 It may be butyl or t-butyl. Alternatively, the acetate group is

[0019] [ka] It may also be the ester group.

[0020] [ka] That's fine.

[0021] Alternatively, bicyclic compounds are represented by formula ii-3).

[0022] [ka] (In the formula, R 3 (as described above) may have R in this formula. 3 When is H, the bicyclic compound is (1R,4S)-bicyclo[2.2.1]hepta-2-ene (also called norbornene).

[0023] Alternatively, bicyclic compounds are represented by formula ii-4).

[0024] [ka] (In the formula, R 3 The above is true. The bicyclic compound may have one or more of the compounds shown in Table ii) below.

[0025] [Table 1]

[0026] The above i) platinum(0)-siloxane complex and ii) bicyclic compound can be mixed at room temperature, or 195The mixtures can be combined by any convenient means, such as mixing while heating for a sufficient time to show that the Pt NMR spectrum shows the disappearance of the peak belonging to the platinum(0)-siloxane complex (e.g., Karstedt catalyst) and the appearance of a new peak corresponding to the hydrosilylation reaction catalyst containing the Pt complex (with the bicyclic compound). The time may be 5 to 60 minutes, 10 to 60 minutes, or 30 minutes. Mixing may be carried out under ambient conditions, for example, under ambient pressure in the presence of air. The amounts of i) platinum(0)-siloxane complex and ii) bicyclic compound are not important as long as there are enough of both to form the Pt complex. For example, the amounts of ii) bicyclic compound and i) platinum(0)-siloxane complex can be used in a molar ratio of 1:1 of ii) bicyclic compound to platinum in i) platinum(0)-siloxane complex {ii):i) ratio}. Alternatively, a molar excess of the bicyclic compound may be used. For example, the amounts of ii) and i) may be sufficient to ensure that the molar ii):i) ratio of the bicyclic compound to platinum in the platinum(0)-siloxane complex is at least 1:1, or >1:1, or at least 5:1, while the molar ii):i) ratio may be up to 100:1, up to 50:1, or 20:1.

[0027] An exemplary reaction demonstrating the formation of the (C) hydrosilylation reaction catalyst described herein from Karstedt catalyst (Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) as starting material i) and norbornene as starting material ii) is shown in Scheme 1 below.

[0028] [ka]

[0029] The method for forming the hydrosilylation reaction catalyst may optionally further include iii) the use of a solvent. The use of a solvent can facilitate the combination of i) the platinum(0)-siloxane complex and ii) the bicyclic compound described above. The solvent may be any solvent capable of dissolving the platinum(0)-siloxane complex and ii) the bicyclic compound, such as organic solvents, such as aliphatic hydrocarbons, aromatic hydrocarbons, or hydrocarbons substituted with heteroatoms such as oxygen atoms, or combinations thereof. Suitable aromatic hydrocarbons include, for example, benzene, toluene, xylene, and combinations thereof. A suitable heteroatom-containing hydrocarbon solvent is THF. The amount of solvent is not important, and any amount sufficient to facilitate the contact between i) the platinum(0)-siloxane complex and ii) the bicyclic compound can be used. The solvent may be optionally removed before the use of the catalyst (for example, before combining (C) the hydrosilylation reaction catalyst used to prepare the ether-functionalized silicone with (A) an acetate-capped alkenyloxy functionalized ether and / or (B) a polyorganohydrogensiloxane). Alternatively, the solvent may function as a vehicle in the method for preparing the ether-functionalized silicone.

[0030] (A) Alkenyloxy functional ethers capped with acetate The starting material (A) in the method for preparing ether-functionalized silicones is an acetate-capped alkenyloxy functional ether. The acetate-capped alkenyloxy functional ether has the formula:

[0031] [ka] (In the formula, R 1 This is an alkenyl group with 2 to 6 carbon atoms, and each D 1 R is a divalent hydrocarbon group consisting of 2 to 10 independently selected carbon atoms. 7 R may have an alkyl group consisting of 1 to 6 carbon atoms, with the subscript c ≥ 1. 1Suitable alkenyl groups include vinyl, allyl, and hexenyl, or R 1 may be allyl or hexenyl, or R 1 It may also be an allele. 1 The divalent hydrocarbon group is in the empirical formula -C y H 2y -(In the formula, each subscript y can independently be 2-10, or 2-6, or 2-4, or 2-3). For example, each D 1 These can be independently selected from -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-CH2-, CH2-CH2-CH(CH3)-, or CH2-CH(CH3)-CH2-. Alternatively, each D 1 The group can be independently selected from the group consisting of -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, and -CH2-CH(CH3)-. 7 Suitable alkyl groups include methyl, ethyl, propyl (including isopropyl and n-propyl), and butyl (including n-butyl, isobutyl, sec-butyl, and t-butyl), as well as linear or branched alkyl groups with 5 or 6 carbon atoms. Alternatively, R 7 This may be methyl, ethyl, propyl, or butyl. Alternatively, R 7 It may be methyl or ethyl. Alternatively, R 7 This may be methyl. The subscript c represents the number of hydrocarbylene oxide (e.g., alkylene oxide) groups per molecule and has a value of at least 1 or at least 2. Alternatively, the subscript c may have a value of 1 to 200, or 2 to 50, or 2 to 30, or 3 to 16, or 4 to 12, or 5 to 10, or 6 to 8.

[0032] Alternatively, an acetate-capped alkenyloxy functional ether is given by formula:

[0033] [ka] (wherein the formula, the subscript a is between 0 and 4, each subscript b is independently between 2 and 10, and the subscript c is between 2 and 150). Alternatively, the subscript a may be 1, and the acetate-capped alkenyloxy functional ether may be an acetate-capped allyloxy functional ether. Alternatively, each subscript b may be between 2 and 6, or between 2 and 4, or between 2 and 3. Alternatively, the subscript c may be between 2 and 20, or between 3 and 16, or between 4 and 12, or between 5 and 10, or between 6 and 8.

[0034] Acetate-capped alkenyloxy functional ethers are known in the art and commercially available. For example, the allyloxy functional ether of formula H2C=CHCH2O(CH2CH2O)7COCH3 is commercially available from The Dow Chemical Company (Midland, Michigan, USA). Other examples of acetate-capped alkenyloxy functional ethers can be found, for example, in U.S. Patent No. 3,980,688, column 2, line 48 to column 3, line 29, and column 8, lines 32-63.

[0035] (B) Polyorganohydrogensiloxane The starting material (B) in the method for preparing ether-functionalized silicones is polyorganohydrogensiloxane. Polyorganohydrogensiloxane has the unit formula (R 2 2HSiO 1 / 2 ) d (R 2 3SiO 1 / 2 ) e (R 2 HSiO 2 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 2 SiO 3 / 2 ) h (HSiO 3 / 2 ) i (SiO 4 / 2 )j (ZO 1 / 2 ) k (In the formula, each R 2 is an independently selected monovalent hydrocarbon group, where the subscripts d, e, f, g, h, i, j, and k each represent the average number of each unit per molecule, and have values ​​such that d≧0, e≧0, f≧0, g≧0, h≧0, i≧0, j≧0, and k≧0, but may include (d+f+i)≧1 and (d+e+f+g+h+i+j+k)≧2. The subscripts may have values ​​such that 2≧(d+e+f+g+h+i+j)≧10,000. 2 Suitable monovalent hydrocarbon groups may not contain aliphatic unsaturated groups and include alkyl and aryl groups. Alkyl groups may have 1 to 6 carbon atoms. Alkyl groups are exemplified by, but are not limited to, methyl, ethyl, propyl (including isopropyl and n-propyl), and butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl). Alternatively, R 2 The alkyl group may be methyl or ethyl, or may be methyl. 2 The aryl group may be, for example, phenyl, tolyl, xylyl, or naphthyl, or it may be phenyl. Alternatively, each R 2 It can be an alkyl group. Or, each R 2 It may also be methyl.

[0036] Alternatively, the polyorganohydrogensiloxane may be substantially linear or linear. A substantially linear or linear polyorganohydrogensiloxane has the unit formula (R 2 2HSiO 1 / 2 ) d (R 2 3SiO 1 / 2 ) e (R 2 HSiO 2 / 2 ) f (R 2 2SiO 2 / 2 ) g (In the formula, R 2As described above, (d+e) may include (0≦d≦2, 0≦e≦2, quantity(d+e)=2, 0≦f≦10, and 0≦g≦50). Alternatively, d may be 0 and e may be 2. Alternatively, f may be 2~10, or 5~10, or 6~9, or 7~8. Alternatively, g may be 0~40, or 5~35, or 10~30, or 15~25.

[0037] Examples of polyorganohydrogensiloxanes suitable for use in this specification are given below. (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and (v) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (vi) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (vii) A combination of two or more of these.

[0038] Furthermore, linear polyorganohydrogensiloxanes are commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301 and HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301, HPM-502, and HMS-HM271. In addition, DOWSIL® 6-3570 is commercially available from The Dow Chemical Company (Midland, Michigan, USA).

[0039] In the method for preparing ether-functionalized silicones, (A) an acetate-capped alkenyloxy functionalized ether may be used in an amount of 5% to 80% by weight, based on the total weight of the starting materials (A), (B), and (C). Starting material (B), a polyorganohydrogensiloxane, may be used in an amount of 10% to 90% by weight, based on the total weight of the starting materials (A), (B), and (C). Starting material (C), a hydrosilylation reaction catalyst, may be used in an amount of 1 ppm to 0.1% by weight, based on the total weight of the starting materials (A), (B), and (C). The exact amount of each starting material depends on various factors, including the structure of the polyorganohydrogensiloxane and its SiH content, as well as the desired hydrosilylation reaction conditions such as temperature.

[0040] When starting materials comprising (A) an acetate-capped alkenyloxy functional ether, (B) a polyorganohydrogensiloxane, and (C) a hydrosilylation catalyst are combined under conditions that result in a hydrosilylation reaction between the alkenyl group of starting material (A) and the silicon-bonded hydrogen atom of starting material (B), an ether-functional silicone is formed via a hydrosilylation reaction. For example, (A) an acetate-capped alkenyloxy functional ether, (B) a polyorganohydrogensiloxane, and (C) one of the catalysts prepared as described above may be optionally placed in a reactor together with (D) a vehicle. The reactor may be equipped with temperature control means such as a jacket, and mixing means such as a stirrer and / or baffles. The temperature of the hydrosilylation reaction depends on various factors, including the amount of catalyst (C). The temperature in the reactor may be ≥40°C, or 80°C to 120°C. The hydrosilylation reaction can be carried out under inert conditions, for example, by purging the reactor headspace with an inert gas such as nitrogen or argon. The order of addition is not important, but (A) an alkenyloxy functional ether and (B) a polyorganohydrogensiloxane may be combined in the reactor, followed by the addition of (C) the catalyst. Alternatively, the starting material (A), an alkenyloxy functional ether, and optionally (D) a vehicle may be combined in the reactor. Some or all of the catalyst (C) may be combined with the starting material (A). The polyorganohydrogensiloxane may be added over time, intermittently or continuously, to control the exothermic reaction of the hydrosilylation reaction. The catalyst may also be added over time to help control the temperature and maintain the reaction rate.

[0041] The starting material (D), which is the vehicle used in this hydrosilylation reaction, is not important and may be the same as the solvent described above. Alternatively, a different vehicle may be used in addition to, or instead of, the solvent described above for use in the preparation of the catalyst. For example, vehicle (D) may be an aliphatic hydrocarbon such as hexane or heptane; a polar organic solvent such as isopropyl alcohol or acetone; a heterocyclic compound such as tetrahydrofuran; an aromatic hydrocarbon such as benzene, toluene, or xylene; or a halogenated hydrocarbon in which one or more hydrogen atoms of the above aliphatic or aromatic hydrocarbons are substituted with halogen atoms such as fluorine or chlorine. The amount of vehicle is not important and may be varied depending on the purpose. For example, vehicle (D) can be used to dissolve or disperse one of the starting materials, such as the hydrosilylation reaction catalyst (C). Alternatively, the hydrosilylation reaction may be carried out using all the starting materials dissolved in vehicle (D), and the amount may be, for example, 0 to 90% by weight of the vehicle based on the total weight of the starting materials (A), (B), (C), and (D).

[0042] The methods described herein may optionally further include one or more additional steps, such as the recovery of the ether-functionalized silicone prepared by the hydrosilylation reaction described above. Recovery may be carried out by any convenient means, such as stripping and / or distillation, optionally under reduced pressure with heating, in order to remove or minimize the amount of any (D) vehicle or solvent present, and / or to remove or minimize the amount of any unreacted (A) acetate-capped alkenyloxy functionalized ether and / or (B) polyorganohydrogensiloxane.

[0043] How to use The ether-functionalized silicones prepared as described above can be used in markets such as cosmetic care, home care, coatings, leather, defoamers, and as additives in polyurethanes. For example, the ether-functionalized silicones prepared as described above may be used in addition to, or in place of, ether-functionalized silicones for polyurethane applications, such as those disclosed in U.S. Patent No. 3,980,688 or European Patent No. 0275563(A1). [Examples]

[0044] The following 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 listed in Table 1.

[0045] [Table 2]

[0046] Preparation of catalyst Pt-I-1: Ligand-1 (117 mg, 1.24 mmol) and 3 mL of toluene were added to a 20 mL vial. The platinum catalyst, i.e., Karstedt catalyst (210 mg, 0.247 mmol Pt-metal), was slowly added to the vial, and the reaction mixture was stirred at room temperature for 30 minutes. 195 The Pt NMR spectrum showed the complete disappearance of the peak belonging to the Karrstedt catalyst (-6167 ppm) and the appearance of a new peak at -6296 ppm (Table 2). This solution containing the in-situ-generated catalyst complex was diluted with THF to a platinum metal concentration of 0.5 wt% and then used in the hydrosilylation reaction without further purification.

[0047] Preparation of catalyst Pt-I-2: An additional Pt catalyst was prepared using the same procedure as for Pt-I-1, except that 234 mg of ligand-1 was used. 195 The Pt NMR spectrum is identical to that of Pt-I-1, with a single peak at -6296 ppm.

[0048] [Table 3]

[0049] Reference Example 1 - Hydrosilylation reaction of organohydrogensiloxane and allyloxy functional ether In a typical procedure, a 100 mL two-necked round-bottom glass flask equipped with magnetic stirring was used as the reaction vessel. Heating was provided by a heated metal plate with a recess that fit into the bottom of the flask. The reaction was carried out in a glove box where the levels of oxygen or water were negligible. 22.926 g of organohydrogensiloxane 1 (MD) was added to the flask. 22 D2 H M (12 mmol) and 9.8 g of allyloxy functional ether 1 (allyl EO7-acetate, 24 mmol) were added. The mixture in the vial was heated to 80°C in a pi heating block in a glove box (N2) while stirring with a magnetic stirring rod. Then, the desired amount of Pt catalyst (as described above), diluted (with THF or toluene), was added to the reaction mixture, and the reaction process was monitored by in-situ Raman spectroscopy.

[0050] Raman spectroscopy monitoring A B&W Tek i-Raman Pro system with laser excitation at 785 nm was used. Spectra were collected in a backscatter configuration using a Kaiser half-inch diameter short-focus immersion optical system. Typical acquisition conditions included a 5-second exposure per scan, 6 scans per spectrum, and full laser power (approximately 300 mW). Spectra were collected continuously at approximately 32-second intervals.

[0051] As shown in Table 3, Pt-I-1 and Pt-I-2 showed higher activity compared to the Karstedt catalyst (Pt-Comparative-1) under the same Pt ​​loading and reaction conditions.

[0052] [Table 4]

[0053] Reference Example 2 - Hydrosilylation reaction with the addition of acetic anhydride In a glove box filled with N2, organohydrogensiloxane 1 (22.9 g), allyloxy functional ether 1 (9.8 g), and a magnetic stirring rod were added to a 100 mL round-bottom flask equipped with an in-situ Raman spectroscopy monitoring probe. Then, various amounts of acetic anhydride were added to the flask. The mixture in the flask was heated to 80°C on a Pi heating block with stirring. Next, a diluted platinum catalyst (0.5 wt% Pt in THF) was added to the reaction mixture, and the reaction process was monitored by in-situ Raman spectroscopy.

[0054] Acetic anhydride can poison the Karstedt catalyst (Pt-comparison-1), and the effect of acetic anhydride on the activity of the Karstedt catalyst increased with increasing acetic anhydride:Pt (molar ratio), as shown in Table 4. When the molar ratio of acetic anhydride to Pt was 3:1, acetic anhydride had only a small effect on the activity of the Karstedt catalyst, as shown in Table 4 (compared to acetic anhydride without t). 1 / 2 =2.5 minutes, t c Compared to 11 minutes, with acetic anhydride:Pt=3, t 1 / 2 (=2.2 min, tc=11.5). When the molar ratio of acetic anhydride to Pt was increased to 5:1, the reaction using the Karrstedt catalyst took 20 minutes to complete, which was significantly longer (almost twice as long) than the reaction time without acetic anhydride.

[0055] The inventors were surprised to find that acetic anhydride had a much smaller effect on the activity of the norbornene-Pt complex (Pt-I-1 or Pt-I-2) described above. The norbornene-Pt complex still showed good activity at a molar ratio of acetic anhydride to Pt of 5 (t 1 / 2 = 2.2 minutes and t c =11.15 minutes).

[0056] [Table 5]

[0057] Under the tested conditions, these examples showed that Pt-I-2 had better reactivity (shorter time to consume the allyl group) than the Karstedt catalyst at the same molar ratio of acetic anhydride:Pt.

[0058] Reference Example 3 - Hydrosilylation reaction using aged allyloxy-functional ether The batch of aged allyloxy-functional ether 1 showed low activity in the hydrosilylation reaction using the Karstedt catalyst, which was considered to be due to impurities generated during the aging process. The norbornene-Pt complex showed higher activity than the Karstedt catalyst in the hydrosilylation reaction with this aged allyloxy-functional ether 1 (Table 5). The hydrosilylation reaction using 2 ppm of the Karstedt catalyst never completed and only reached a conversion rate of 50%, while the reaction using 2 ppm of the Pt-norbornene complex completed in about 12 minutes.

[0059] [Table 6]

[0060] The consumption of the allyl group was plotted against the reaction time, and t 1 / 2 (time until the consumption of the allyl group reaches 50%) and t c (time until the consumption of the allyl group exceeds 99.9%) were recorded in Tables 3, 4, and 5. Data from comparative experiments (CE-1 to CE-6) using the Karstedt catalyst were used as a control. Data from working experiments (IE-1 to IE-7) using Pt-I-1 and Pt-I-2 prepared as described above consistently showed shorter reaction times and faster reaction rates than the Karstedt catalyst tested under the same conditions.

[0061] Reference Example 4 - Hydrosilylation reaction using additional Pt - the catalyst of the present invention In a glove box filled with N2, organohydrogensiloxane 2 (10.31 g), hydroxy-terminated polyether (21.86 g), and a magnetic stirring rod were added to a 100 mL round-bottom flask equipped with an in-situ Raman spectroscopy monitoring probe. The mixture in the flask was heated to 80°C on a Pi heating block while stirring. Diluted platinum catalyst (0.5 wt% Pt in THF) was then added to the reaction mixture, and the reaction process was monitored by in-situ Raman spectroscopy. The catalysts tested are shown in Table 6 below.

[0062] As shown in Table 6, Pt-I-2 to Pt-I-6 showed similar activity to Karstedt catalyst (Pt-Comparative-1) under the same Pt ​​loading and reaction conditions when hydroxyl-functionalized polyethers were included. Pt-I-7 showed lower activity compared to Karstedt catalyst (Pt-Comparative-1) and Pt-I-2 to 6.

[0063] [Table 7]

[0064] Comparative Examples CE-7 and CE-8 demonstrate that the decrease in reactivity observed with the Karrstedt catalyst when using acetate-capped allyloxy functional ethers in a hydrosilylation reaction process with organohydrogenpolysiloxanes did not occur when using hydroxyl-capped allyloxy functional ethers to prepare different ether-functionalized silicone products. The above examples and comparative examples demonstrate that when acetate-capped alkenyloxy functional ethers are used in a hydrosilylation reaction process with polyorganohydrogensiloxanes, the catalysts used in the processes described herein provide the unexpected benefit of shortening reaction time and increasing reaction rate. [Industrial applicability]

[0065] The above examples demonstrate that catalysts having norbornene (or norbornene derivatives) ligands provide shorter reaction times and faster reaction rates than Karstedt catalysts, given all other hydrosilylation reaction conditions being the same. Ether-functionalized silicones can be successfully prepared by the methods described herein. While not bound by theory, acetic anhydride (AA) is a major impurity present in acetate-capped alkenyloxy functional ethers, such as acetate-capped allyloxy functional ethers, and it is thought that this can poison Karstedt catalysts and adversely affect the hydrosilylation reactivity for forming ether-functionalized silicones. The above methods demonstrate that the catalysts described herein address this problem and can improve the hydrosilylation reactivity for forming ether-functionalized silicones.

[0066] Definitions and Usage of Terms All quantities, ratios, and percentages are given by weight unless otherwise indicated in the context of the specification. Unless otherwise specified in the context of the specification, the articles "a," "an," and "the" each refer to one or more. A disclosure of a Markush group includes the entire group, as well as any individual elements and subsets contained therein. For example, a disclosure of the Markush group vinyl, allyl, or hexenyl includes vinyl as its individual member; allyl and hexenyl as its subgroup; and any other individual members and subgroups contained therein. Abbreviations used herein are defined below in Table X.

[0067] [Table 8]

[0068] Embodiments of the present invention In the first embodiment, a method for preparing an ether-functionalized silicone is: I) Under the conditions for carrying out the hydrosilylation reaction, (A) Alkenyloxy functional ethers capped with acetate, (B) Polyorganohydrogensiloxane, Formula (C):

[0069] [ka] Hydrosilylation reaction catalyst containing Pt(0) complex This involves combining starting materials that include, in the formula,

[0070] [ka] This represents a single bond or a double bond. Each R is an independently selected monovalent hydrocarbon radical that does not contain aliphatic unsaturated compounds. Each D 3 These are independently selected from the group consisting of covalent bonds and divalent hydrocarbon groups of 1 to 4 carbon atoms,

[0071] [ka] If it is a double bond, then each R 6 It does not exist.

[0072] [ka] If it is a single bond, then each R 6 is R 3 And, Each R 3 It is independently selected from the group consisting of H, OH, acetate groups, and ester groups. The ester group is,

[0073] [ka] (In the formula, D’ is a covalent bond or a divalent hydrocarbon group, R 5 which has an alkyl group having 1 to 6 carbon atoms), The acetate group has the formula

[0074]

Chemical formula

[0075] In the second embodiment, in the method of the first embodiment, the Pt(0) complex has the formula

[0076]

Chemical formula

[0077]

Chemical formula

[0078]

Chemical formula

[0079] In the third embodiment, in the method of the first or second embodiment, the Pt(0) complex is given by formula:

[0080] [ka] Including, in the formula, R 3 H, OH, formula

[0081] [ka] The acetate group and formula

[0082] [ka] Selected from the group consisting of ester groups.

[0083] In the fourth embodiment, in any one of the methods of the first to third embodiments, the method is: It involves combining starting materials, and the starting materials are i) Platinum(0)-siloxane complex, wherein the complex is chemically bonded platinum and formula R m R' n R'' o SiO (4-m-n-o) / 2 Platinum(0)-siloxane complexes essentially consisting of unsaturated organosiloxanes (wherein each R is an independently selected monovalent hydrocarbon radical that does not contain aliphatic unsaturated hydrocarbon radicals, each R' is an independently selected monovalent aliphatic unsaturated hydrocarbon radical, each R'' is selected from R' radicals chemically bonded to platinum, the subscript m is 0-2, the subscript n is 0-2, the subscript o is 0.0002-3, and the amount (m+n+o) is 1-3). ii)

[0084] [ka] and their combinations (in the formula, each R 3 (which is a bicyclic compound selected from the group consisting of H, OH, acetate group, and ester group, and iii) Solvent, (optional) The method further includes an additional step of preparing a (C) hydrosilylation reaction catalyst by a method comprising combining starting materials, including the above.

[0085] In the fifth embodiment, in the method of the fourth embodiment, the Pt(0) complex is

[0086] [ka] Includes.

[0087] In the sixth embodiment, in the method of the fourth or fifth embodiment, the bicyclic compound is selected from the group consisting of (1R,4S)-bicyclo[2.2.1]hepta-2-ene, (1R,2S,4R)-bicyclo[2.2.1]hepta-5-ene-2-ol, (1R,4R)-bicyclo[2.2.1]hepta-5-ene-2-yl acetate, tert-butyl(1R,2S,4R)-bicyclo[2.2.1]hepta-5-ene-2-carboxylate, (1s,4s)-bicyclo[2.2.1]hepta-2,5-diene, and two or more combinations thereof.

[0088] In the seventh embodiment, in any one of the fourth to sixth embodiments, the starting material ii) is present in an amount sufficient to provide 20 moles or less of the bicyclic compound per mole of platinum in the hydrosilylation catalyst.

[0089] In the eighth embodiment, in the method of the seventh embodiment, the amount of starting material ii) is sufficient to provide a bicyclic compound:platinum metal molar ratio of 5:1 to 20:1.

[0090] In the ninth embodiment, in any one of the first to eighth embodiments, (A) an acetate-capped alkenyloxy functional ether is of the formula

[0091] [ka] (In the formula, R 1 This is an alkenyl group with 2 to 6 carbon atoms, and each D 1 It is a divalent hydrocarbon group consisting of 2 to 10 independently selected carbon atoms, with the subscript c ≥ 2.

[0092] In the tenth embodiment, in the method of the ninth embodiment, the acetate-capped alkenyloxy functional ether is of the formula

[0093] [ka] (In the formula, subscript a is between 0 and 4, subscript b is between 2 and 10, and subscript c is between 2 and 150).

[0094] In the 11th embodiment, in the method of the 10th embodiment, the acetate-capped alkenyloxy functional ether is of formula:

[0095] [ka] It is an allyloxy functional ether capped with acetate (wherein each subscript b is 2 or 3, and each subscript c is 6 to 8).

[0096] In the twelfth embodiment, in any one of the first to eleventh embodiments, the polyorganohydrogensiloxane is expressed by the unit formula (R 2 2HSiO 1 / 2 ) d (R 2 3SiO 1 / 2 )e (R 2 HSiO 2 / 2 ) f (R 2 2SiO 2 / 2 ) g (In the formula, each R 2 is an independently selected monovalent hydrocarbon group, and the subscripts d, e, f, and g represent the average amount per molecule of each unit in the formula, and include values ​​such that 0 ≤ d ≤ 2, 0 ≤ e ≤ 2, amount (d + e) ​​= 2, 0 ≤ f ≤ 10, and 0 ≤ g ≤ 50.

[0097] In the 13th embodiment, in the method of the 12th embodiment, each R 2 This is a methyl group.

Claims

1. A method for preparing ether-functionalized silicone, １） i) Chemically bonded platinum and formula R ｍ R' ｎ R'' ｏ SiO （４－ｍ－ｎ－ｏ）／２ Platinum(0)-siloxane complexes essentially consisting of unsaturated organosiloxanes (wherein each R is an independently selected monovalent hydrocarbon radical that does not contain aliphatic unsaturated hydrocarbon radicals, each R' is an independently selected monovalent aliphatic unsaturated hydrocarbon radical, each R'' is selected from R' radicals chemically bonded to platinum, the subscript m is 0 to 2, the subscript n is 0 to 2, the subscript o is 0.0002 to 3, and the amount (m + n + o) is 1 to 3). ii) 【Chemistry 1】 and their combinations (wherein each R ３ (which is a bicyclic compound selected from the group consisting of H, OH, acetate group, and ester group, and Optionally, iii) solvent, Combining starting materials that include, Optionally, 2) Dilute the product of step 1) with a vehicle. This results in the production of a hydrosilylation reaction catalyst containing a (C)Pt complex, ３） (A) Alkenyloxy functional ethers capped with acetate, (B) Polyorganohydrogensiloxane, (C) The hydrosilylation reaction catalyst, Combining starting materials that include, Methods that include...

2. The aforementioned unsaturated organosiloxane is, 【Chemistry 2】 The method according to claim 1, wherein R is alkyl, R' is alkenyl, the subscript h is an integer from 1 to 3, the subscript i is an integer from 1 to 3, and the amount (h + i) ≥ 2.

3. The method according to claim 1, wherein the starting material i) comprises a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

4. The starting material is the bicyclic compound described above. 【Transformation 3】 The formula has a set of formulas selected from the group consisting of combinations thereof, where each R ３ is -OH, formula 【Chemistry 4】 (In the formula, D' is a covalent bond or a divalent hydrocarbon group, R ５ (is an ester group of an alkyl group with 1 to 6 carbon atoms), and formula 【Transformation 5】 (wherein D is a covalent bond or a divalent hydrocarbon group, R ４ The method according to any one of claims 1 to 3, wherein is independently selected from the group consisting of acetate groups (which are alkyl groups with 1 to 6 carbon atoms).

5. The starting material ii) the bicyclic compound, 【Transformation 6】 The method according to claim 4, selected from the group consisting of the following.

6. The method according to claim 5, wherein the bicyclic compound that is the starting material ii) is norbornene.

7. The aforementioned acetate-capped alkenyloxy functional ether is, 【Transformation 7】 (wherein R １ is an alkenyl group having 2 to 6 carbon atoms, each D １ is an independently selected divalent hydrocarbon group having 2 to 10 carbon atoms, R ７ is an alkyl group having 1 to 6 carbon atoms, and the subscript c ≥ 1), the method according to any one of claims 1 to 6.

8. The aforementioned acetate-capped alkenyloxy functional ether is, 【Transformation 8】 The method according to claim 7, wherein the formula has (wherein the formula, the subscript a is 0 to 4, the subscript b is 2 to 10, and the subscript c is 2 to 150).

9. The aforementioned polyorganohydrogensiloxane has the unit formula (R ２ ２ HSiO １／２ ) ｄ (R ２ ３ SiO １／２ ) ｅ (R ２ HSiO ２／２ ) ｆ (R ２ ２ SiO ２／２ ) ｇ (R ２ SiO ３／２ ) ｈ (HSiO ３／２ ) ｉ (SiO ４／２ ) ｊ (ZO １／２ ) ｋ (In the formula, each R ２ The method according to any one of claims 1 to 8, wherein is an independently selected monovalent hydrocarbon group, and the subscripts d, e, f, g, h, I, j, and k each represent the average number of each unit per molecule, having values ​​such that d≧0, e≧0, f≧0, g≧0, h≧0, i≧0, j≧0, and k≧0, provided that the amount (d+f+i)≧1 and the amount (d+e+f+g+h+i+j+k)≧2.

10. The aforementioned polyorganohydrogensiloxane has the unit formula (R ２ ２ HSiO １／２ ) ｄ (R ２ ３ SiO １／２ ) ｅ (R ２ HSiO ２／２ ) ｆ (R ２ ２ SiO ２／２ ) ｇ (In the formula, R ２ The method according to claim 9, wherein the above is true, and the conditions are 0 ≤ d ≤ 2, 0 ≤ e ≤ 2, quantity (d + e) ​​= 2, 0 ≤ f ≤ 10, and 0 ≤ g ≤ 50, and quantity (d + f) ≥ 1.

11. The method according to any one of claims 1 to 10, wherein the starting material ii) is present in an amount sufficient to provide 20 moles or less of the bicyclic compound per mole of platinum in the hydrosilylation reaction catalyst, or the amount of the starting material ii) is sufficient to provide a bicyclic compound:platinum metal molar ratio of 5:1 to 20:

1.

12. The method according to any one of claims 1 to 11, wherein the solvent is present in step 1), and the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof.

13. The method according to any one of claims 1 to 13, wherein step 1) is carried out by mixing at a temperature of 20°C to 30°C, and step 2) is carried out by mixing and heating at a temperature of 40°C to 120°C, or both.

14. The method according to any one of claims 1 to 14, further comprising forming the platinum(0)-siloxane complex, which is the starting material i), by a method comprising mixing the platinum halide and the unsaturated siloxane to form a mixture before step 1), and then treating the mixture to remove available inorganic halogens.

15. An ether-functionalized silicone copolymer prepared by the method described in any one of claims 1 to 14.

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