WO2020070964A1 - 高分子重合開始剤及び高分子重合開始剤の製造方法 - Google Patents

高分子重合開始剤及び高分子重合開始剤の製造方法

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WO2020070964A1
WO2020070964A1 PCT/JP2019/030395 JP2019030395W WO2020070964A1 WO 2020070964 A1 WO2020070964 A1 WO 2020070964A1 JP 2019030395 W JP2019030395 W JP 2019030395W WO 2020070964 A1 WO2020070964 A1 WO 2020070964A1
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substituted
polymerization initiator
sio
group
general formula
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French (fr)
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龍ノ介 秦
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Shin-Etsu Chemical Co Ltd
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Shin-Etsu Chemical Co Ltd
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Priority to US17/276,095 priority Critical patent/US11629234B2/en
Priority to EP19869632.0A priority patent/EP3862367A4/en
Priority to KR1020217008702A priority patent/KR102731687B1/ko
Priority to CN201980063287.3A priority patent/CN112771082A/zh
Publication of WO2020070964A1 publication Critical patent/WO2020070964A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
    • C08F283/004—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment modified by incorporation of silicium atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • the present invention relates to a novel polymer polymerization initiator and a method for producing the polymer polymerization initiator.
  • a (meth) acrylic graft silicone having a silicone chain in a main chain and a (meth) acrylic (the term “(meth) acryl” used in the following description refers to methacryl and acryl) has a side chain. Since it has both a hydrophobic part and a polar part, it works as a surfactant and is used as a powder treatment agent and a cosmetic material.
  • Patent Documents 1 and 2 disclose methods for producing this (meth) acrylic graft silicone.
  • Examples of the polymerization initiator in the method for producing a (meth) acrylic graft silicone of Patent Document 1 include radical polymerization initiators such as an azo initiator, a peroxide initiator, a persulfate initiator, and a photopolymerization initiator.
  • radical polymerization initiators such as an azo initiator, a peroxide initiator, a persulfate initiator, and a photopolymerization initiator.
  • a radical polymerization initiator specifically, a thermal polymerization initiator or a photopolymerization initiator is mentioned.
  • (meth) acrylic grafted silicones have a radical generated by a usual radical polymerization initiator as disclosed in Patent Document 1 and Patent Document 2, and a chain transfer reaction causes a radical transfer on a sulfur atom of a mercapto-modified silicone. Then, the (meth) acrylic monomer is synthesized by polymerization.
  • a usual radical initiator which is a radical generating source also serves as a polymerization initiation point, and the (meth) acrylic monomer is polymerized. For this reason, there is a problem that the final product is a mixture of the (meth) acrylic graft silicone and the (meth) acrylic polymer.
  • a polymer polymerization initiator is a polymer having a functional group that can be a polymerization initiation point, and by polymerizing a monomer using the polymer polymerization initiator, a graft copolymer, a block copolymer, or the like is obtained. Characteristic polymers can be polymerized. Further, theoretically, since the polymerization starting point exists only on the polymer chain, it is possible to suppress the product from being a mixture of the above (meth) acrylic graft silicone and the (meth) acrylic polymer. .
  • Patent Document 3 discloses a silicone having a ketene silyl acetal structure as an intermediate for synthesizing a sulfonyl-modified silicone. However, it has not been used as a polymer polymerization initiator.
  • the present invention has been made in view of the above circumstances, and has as its object to provide a polymer polymerization initiator for obtaining a (meth) acrylic graft silicone by group transfer polymerization, and a method for producing the polymer polymerization initiator. I do.
  • a polymer polymerization initiator represented by the following general formula (I) is provided.
  • M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g (I)
  • M 1 R 1 3 SiO 1/2
  • M 2 R 1 2 R 2 SiO 1/2
  • D 1 R 1 2 SiO 2/2
  • D 2 R 1 R 2 SiO 2/2
  • T 1 R 1 SiO 3/2
  • Q SiO 4/2
  • R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms.
  • R 2 is a group having a ketene silyl acetal structure represented by the following general formula (II).
  • A is a single bond or a divalent organic group
  • R 3 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having a carbon number of 1 ⁇ 4
  • R 4 Is each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • a, b, c, d, e, f, and g are 0 or a positive integer, provided that b + d + f ⁇ 1
  • the number average molecular weight of the polymerization initiator represented by the general formula (I) is 1, 000-1,000,000 g / mol.
  • the bonding order of the siloxane units represented by M 1 , M 2 , D 1 , D 2 , T 1 , T 2 , and Q is arbitrary. ]
  • a (meth) acrylic graft silicone can be synthesized by group transfer polymerization without the presence of a (meth) acrylic polymer derived from a usual radical initiator.
  • the method for producing a polymer polymerization initiator described above wherein the compound represented by the following general formula (III) is hydrosilylated to a hydrogen siloxane represented by the following general formula (IV).
  • a method for producing a polymerized polymerization initiator which comprises a step of adding by a reaction.
  • A is a single bond or a divalent organic group
  • R 3 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having a carbon number of 1 ⁇ 4
  • R 4 Is each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 5 is each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, at least one of which is a hydrogen atom H, i, j, and k are 0 or a positive integer, provided that h + i + j ⁇ 1, and the number average molecular weight of
  • the polymer polymerization initiator of the present invention can be produced by such an addition reaction.
  • a (meth) acrylic graft silicone can be synthesized by group transfer polymerization without the presence of a (meth) acrylic polymer derived from a usual radical initiator.
  • FIG. 1 is an overall view of a 1 H NMR chart after a reaction between a hydrogen siloxane and a compound represented by formula (1) in Example 1.
  • a silicone having a ketene silyl acetal structure represented by the following general formula (I) can be used as a polymer polymerization initiator capable of synthesizing a (meth) acrylic graft silicone by group transfer polymerization They have found that they can be suitably used, and have completed the present invention.
  • M 1 R 1 3 SiO 1/2
  • M 2 R 1 2 R 2 SiO 1/2
  • D 1 R 1 2 SiO 2/2
  • D 2 R 1 R 2 SiO 2/2
  • T 1 R 1 SiO 3/2
  • Q SiO 4/2
  • R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms. .
  • R 2 is a group having a ketene silyl acetal structure represented by the following general formula (II).
  • A is a single bond or a divalent organic group
  • R 3 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having a carbon number of 1 ⁇ 4
  • R 4 Is each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • a, b, c, d, e, f, and g are 0 or a positive integer, provided that b + d + f ⁇ 1
  • the number average molecular weight of the polymerization initiator represented by the general formula (I) is 1, 000-1,000,000 g / mol.
  • the bonding order of the siloxane units represented by M 1 , M 2 , D 1 , D 2 , T 1 , T 2 , and Q is arbitrary. ]
  • the polymer polymerization initiator of the present invention is represented by the above general formula (I), wherein R 2 has a ketene silyl acetal structure. Since the ketene silyl acetal structure functions as an initiator for group transfer polymerization, it can be used as a polymer polymerization initiator for group transfer polymerization.
  • R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms; It is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms, and more preferably a methyl group or a phenyl group.
  • R 2 is a group having a ketene silyl acetal structure represented by the general formula (II).
  • the bonding order of the repeating units represented by M 1 , M 2 , D 1 , D 2 , T 1 , T 2 , and Q is arbitrary, and the sequence constituted by each repeating unit is , May be irregular or regular.
  • a, b, c, d, e, f, and g are 0 or positive integers
  • the number average molecular weight of the polymerization initiator represented by the general formula (I) is 1,000 to 1,000,000 g / mol.
  • the number average molecular weight is more preferably from 1,000 to 100,000 g / mol, and still more preferably the number average molecular weight is from 2,000 to 20,000 g / mol.
  • the number average molecular weight is a value in terms of polystyrene in GPC (gel permeation chromatography) analysis (hereinafter, the number average molecular weight means the same converted value).
  • the number average molecular weight means the same converted value.
  • A is a single bond or a divalent organic group, preferably an alkylene group having 1 to 10 carbon atoms, or —O—, —S— and NR— (R is A substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms (provided that it is an oxygen atom, a sulfur atom, etc.), which may contain one or more selected from 1 to 20 monovalent hydrocarbon groups. And nitrogen atoms are not adjacent to each other), and more preferably an alkylene group having 0 to 6 carbon atoms.
  • R 3 is each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 alkyl groups, and more preferably a methyl group.
  • R 4 is each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group.
  • the polymer polymerization initiator of the present invention can be obtained by adding a compound represented by the following general formula (III) to a hydrogensiloxane represented by the following general formula (IV) by a hydrosilylation reaction.
  • This production method comprises the step of converting a compound represented by the following general formula (III):
  • the method includes a step of adding the hydrogen siloxane represented by the following general formula (IV) by a hydrosilylation reaction to obtain the polymer polymerization initiator.
  • the bonding order of the siloxane units represented by M 3 , D 3 , T 3 , and Q is arbitrary.
  • A is as described above, and is a single bond or a divalent organic group, preferably an alkylene group having 0 to 10 carbon atoms or —O—, —S— and NR— ( R is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms (provided that oxygen is a monovalent hydrocarbon group having 1 to 20 carbon atoms). Atom, sulfur atom and nitrogen atom are not adjacent to each other), and more preferably an alkylene group having 0 to 6 carbon atoms.
  • R 3 is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 and more preferably a methyl group.
  • R 4 is independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group.
  • Examples of the compound represented by the general formula (III) include compounds having the following structures, but are not limited thereto.
  • R 5 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, and is preferably Is an alkyl group having 1 to 6 carbon atoms. However, at least one is a hydrogen atom.
  • h, i, j, and k are 0 or a positive integer
  • the number average molecular weight of the hydrogen siloxane represented by the above general formula (IV) is 500 to 900,000 g / mol, more preferably 1,000 to 900,000 g / mol.
  • the addition reaction is preferably performed in the presence of a catalyst, and a known addition reaction catalyst can be used.
  • a metal catalyst containing platinum, palladium, rhodium, ruthenium, gold, nickel and the like can be mentioned.
  • a catalyst containing platinum, palladium, or rhodium is preferable.
  • the catalyst has a platinum, more specifically, PtCl 4, H 2 PtCl 6 ⁇ 6H 2 O, Pt- ether complexes, Pt-olefin complexes, PdCl 2 (PPh 3) 2 , PdCl 2 (PhCN) 2 , RhCl 2 (PPh 3 ) 3 (where Ph is a phenyl group) can be used.
  • the catalyst may be a single kind or a mixture of two or more kinds.
  • the catalyst can be used after being diluted with a solvent such as an alcohol, an aromatic, a hydrocarbon, a ketone, or a basic solvent, if necessary.
  • a solvent such as an alcohol, an aromatic, a hydrocarbon, a ketone, or a basic solvent, if necessary.
  • a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and a neutralized sodium bicarbonate of chloroplatinic acid (Karstedt catalyst) is most preferred as the addition reaction catalyst.
  • the amount of the catalyst may be a catalyst amount.
  • the amount of catalyst is an amount sufficient to allow the above addition reaction to proceed. 0.02 parts by mass or less, preferably 0.0001 to 0.02 parts by mass, particularly preferably 0.0003 to 0.005 parts by mass, based on 100 parts by mass of the hydrogen siloxane, in terms of the main metal of the metal catalyst. It is.
  • the catalyst may be added from the beginning of the reaction or may be added several times during the reaction.
  • the production method of the present invention allows the reaction to proceed sufficiently even with a small amount of catalyst. However, if the amount of the catalyst is too small, the reaction rate becomes slow. On the other hand, if the amount of the catalyst is too large, the reaction rate is not particularly improved, which is uneconomical.
  • the amount of the compound represented by the general formula (III) is not particularly limited. Usually, the amount of the alkenyl group contained in the compound represented by the general formula (III) per one hydrosilyl group contained in the hydrogen siloxane The total number is from 0.1 to 10, preferably from 0.5 to 2.
  • Organic solvents include, for example, aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; chlorinated solvents such as chloroform, dichloromethane, and carbon tetrachloride; and tetrahydrofuran.
  • ether solvents such as diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, dimethylformamide (DMF), acetonitrile and the like can be used.
  • aromatic hydrocarbons such as toluene are most preferred.
  • the addition reaction temperature is 20 to 250 ° C, preferably 40 to 180 ° C, particularly preferably 80 to 120 ° C.
  • the reaction time is within 20 hours, preferably within 12 hours, particularly preferably within 8 hours.
  • the polymer polymerization initiator of the present invention can produce (meth) acryl-grafted silicone by group transfer polymerization.
  • the (meth) acrylic grafted silicone produced by the polymer polymerization initiator of the present invention has a small amount of by-product polymer unlike the case where it is synthesized by radical polymerization. Useful for agents, oil repellents, release agents, paint additives.
  • the number average molecular weight referred to in the present invention refers to a number average molecular weight measured by GPC and using polystyrene as a standard substance under the following conditions.
  • M Me , MH , D Me , D Ph , DH , T Me , and Q siloxane units, and each siloxane unit has the following structure.
  • M Me Me 3 SiO 1/2
  • MH Me 2 HSiO 1/2
  • D Me Me 2 SiO 2/2
  • D Ph Ph 2 SiO 2/2
  • DH MeHSiO 2/2
  • T Me MeSiO 3/2
  • Q SiO 4/2
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • Example 1 In a three-necked flask equipped with a thermometer and a condenser, 100 parts by mass of hydrogensiloxane (number-average molecular weight 7,780 g / mol) having an average composition of M Me 2 D Me 103 DH 30 and the following formula (1) ) was dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • FIG. 1 is an overall view of the 1 H NMR chart after the reaction between the hydrogen siloxane and the compound represented by the formula (1) in Example 1.
  • the obtained product was analyzed by 1 H NMR, and the peak derived from the hydrosilyl group disappeared, and 0.2 ppm, 0.5 ppm, 1.4-1.6 ppm, and 3.7 ppm of 1 H chemical shift were analyzed. It was confirmed that there was a peak near the ketene silyl acetal structure in the vicinity.
  • Example 2 In a three-necked flask equipped with a thermometer and a condenser tube, 100 parts by mass of hydrogen siloxane (number average molecular weight 6,490 g / mol) represented by M Me 2 D Me 123 DH 10 and the above formula (1) 28.4 parts by mass of the compound represented by the formula (1) was added and dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • hydrogen siloxane number average molecular weight 6,490 g / mol
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number average molecular weight: 13,110 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketene silyl acetal structure was present.
  • Example 3 In a three-necked flask equipped with a thermometer and a condenser tube, 100 parts by mass of hydrogen siloxane (number average molecular weight 7,740 g / mol) having an average composition of M Me 2 D Me 113 DH 20 and the above formula (1) 55.6 parts by mass of the compound represented by the formula (1) was added and dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • hydrogen siloxane number average molecular weight 7,740 g / mol
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number average molecular weight: 14,960 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketene silyl acetal structure was present.
  • Example 4 In a three-necked flask equipped with a thermometer and a condenser, 100 parts by mass of hydrogen siloxane (number average molecular weight 1,080 g / mol) represented by M Me 2 D Me 10 DH 5 and the above formula (1) ) was dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number-average molecular weight: 2,850 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketesilyl acetal structure was present.
  • Example 5 In a three-necked flask equipped with a thermometer and a condenser tube, 100 parts by mass of hydrogen siloxane (number average molecular weight 2,950 g / mol) represented by MH 2 D Me 40 and 100 parts by mass of the above formula (1) 16.9 parts by mass of the compound to be obtained were added and dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • hydrogen siloxane number average molecular weight 2,950 g / mol
  • MH 2 D Me 40 100 parts by mass of the above formula (1) 16.9 parts by mass of the compound to be obtained were added and dissolved in 100 parts by mass of toluene.
  • the temperature of the solution was raised to
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number-average molecular weight: 3,920 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketene silyl acetal structure was present.
  • Example 6 In a three-necked flask equipped with a thermometer and a condenser, 100 parts by mass of hydrogen siloxane (number average molecular weight 4,220 g / mol) represented by M Me 2 D Ph 9 DH 43 and the above formula (1) ) was added and dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number average molecular weight: 14,500 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketene silyl acetal structure was present.
  • Example 7 In a three-necked flask equipped with a thermometer and a condenser tube, 100 parts by mass of hydrogen siloxane (number average molecular weight 9,850 g / mol) having an average composition represented by M Me 6 D Me 113 DH 20 T Me 4 and the above 28.4 parts by mass of the compound represented by the formula (1) was added and dissolved in 100 parts by mass of toluene. The temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise.
  • hydrogen siloxane number average molecular weight 9,850 g / mol
  • the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours. Thereafter, the solvent was removed at 120 ° C. and 10 mmHg to obtain the desired product (number-average molecular weight: 15,230 g / mol).
  • the obtained product was analyzed by 1 H NMR, and it was confirmed that the peak derived from the hydrosilyl group had disappeared and the peak derived from the ketene silyl acetal structure was present.
  • Example 8 Necked flask equipped with a with a thermometer and a cooling tube, average composition M Me 100 M H 20 siloxane represented by Q 60 (number average molecular weight 7,720g / mol) and 100 parts by mass of the above formula (1) was added and dissolved in 100 parts by mass of toluene.
  • the temperature of the solution was raised to 100 ° C. by an oil bath, and 0.0333 parts by mass of a toluene solution of a neutralized chloroplatinic acid / sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt%) was added dropwise. After the dropwise addition, the temperature of the solution was maintained at 100 ° C., and the mixture was stirred for 6 hours.

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JPH03244612A (ja) * 1990-02-23 1991-10-31 Mitsubishi Rayon Co Ltd 酸素透過性成形物
US5326890A (en) 1992-10-16 1994-07-05 Rensselaer Polytechnic Institute Sulfonated silicones and methods for their production
JP2008274116A (ja) 2007-04-27 2008-11-13 Three M Innovative Properties Co グラフト化シリコーンポリマー及びそれよりなる製品
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JPH03244612A (ja) * 1990-02-23 1991-10-31 Mitsubishi Rayon Co Ltd 酸素透過性成形物
US5326890A (en) 1992-10-16 1994-07-05 Rensselaer Polytechnic Institute Sulfonated silicones and methods for their production
JP2008274116A (ja) 2007-04-27 2008-11-13 Three M Innovative Properties Co グラフト化シリコーンポリマー及びそれよりなる製品
JP2014177447A (ja) 2013-02-13 2014-09-25 Kao Corp オルガノポリシロキサングラフトポリマー
JP2015131938A (ja) * 2013-12-13 2015-07-23 信越化学工業株式会社 低起泡性室温硬化型オルガノポリシロキサン組成物の製造方法及び自動車オイルシール
JP2018059073A (ja) * 2016-10-04 2018-04-12 信越化学工業株式会社 （メタ）アクリル酸トリイソプロピルシリルと（メタ）アクリル酸誘導体の共重合体およびその製造方法

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