Hydroxyalkyl group-containing polysiloxane and method for producing the same

Abstract

This hydroxyalkyl group-containing polysiloxane represented by formula (1) has a high thermal resistance and produces few dehydrogenation reactants generated from OH groups and SiH groups of a raw material compound. (1): (R1 3SiO1 / 2)k (R1 2SiO2 / 2)p (R1SiO3 / 2)q(SiO4 / 2)r [R1 is a group, etc., selected from formulas (2)-(5) (2): -CH2-CH2-Y-OH, etc. (3): -O-Y-CH=CH2 (4): -O-Y'-CH=CH-CH3 (5): -O-Y-CH2-CH2-* (Y and Y' represent a divalent hydrocarbon group; * indicates a bonding point with an Si atom in another siloxane.)　When the numbers of formulas (2)-(5) are noted as n2-n5, n2>0, n3≥0, n4≥0, n5≥0, n2+n3+n4+n5≥1, and 0.97<n2 / (n2+n3+n4+n5)≤1.0 are satisfied, and also k>0, p≥0, q≥0, r≥0, and k+p+q≥2 are satisfied.]

Description

[Technical Field]

[0001] The present invention relates to a hydroxyalkyl group-containing polysiloxane and a method for producing the same. [Background technology]

[0002] Hydroxyalkyl group-containing polysiloxanes are used in a variety of applications, including paint additives, cosmetics, and resin modifiers. As a resin modifier, for example, using hydroxyalkyl group-containing polysiloxanes during the synthesis of polyurethane resins can impart the heat resistance, cold resistance, water resistance, chemical resistance, electrical properties, and gas permeability characteristic of siloxanes. As an example of a hydroxyalkyl group-containing polysiloxane, Patent Document 1 proposes one obtained by a hydrosilylation reaction between allyl glycol and a hydrogen siloxane.

[0003] However, in the hydrosilylation reaction between allyl glycol and hydrogen siloxane described in Patent Document 1, the compatibility between allyl glycol and hydrogen siloxane is poor. Therefore, in addition to the main hydrosilylation reaction, impurities may be generated during the reaction process due to a side reaction in which the hydroxyl group of allyl glycol and the hydrosilyl group of hydrogen siloxane are dehydrogenated. Furthermore, the resulting hydroxyl group-containing polysiloxane may have ether groups and therefore have low heat resistance. Therefore, there is a strong demand for hydroxyalkyl group-containing polysiloxanes that have fewer dehydrogenation reaction products between the hydroxyl group and hydrosilyl group of the raw material compound and high heat resistance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-224060 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydroxyalkyl group-containing polysiloxane having a small dehydrogenation reaction product between a hydroxy group and a hydrosilyl group of a raw material compound and having high heat resistance.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the following hydroxyalkyl group-containing polysiloxane has a small dehydrogenation reaction product between a hydroxy group and a hydrosilyl group of a raw material compound and has high heat resistance, and thus have arrived at the present invention.

[0007] That is, the present invention is 1. A hydroxyalkyl group-containing polysiloxane represented by the following formula (1), (R 1 3SiO 1 / 2 ) k (R 1 2SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1) [In the above formula, R 1 is, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms and a group selected from the following formulas (2) to (5), -CH2-CH2-Y-OH or -CH2-CH2-Y-O-* (2) -O-Y-CH=CH2(3) -O-Y’-CH=CH-CH3(4) -O-Y-CH2-CH2-* (5) (In the above formula, Y is a divalent hydrocarbon group having 3 to 20 carbon atoms, Y’ is a divalent hydrocarbon group having 2 to 19 carbon atoms, and the asterisk * indicates a bonding point directly bonded to a silicon atom in another hydroxyalkyl group-containing polysiloxane molecule.) When the number of the groups represented by the above formula (2) is n2, the number of the groups represented by the above formula (3) is n3, the number of the groups represented by the above formula (4) is n4, and the number of the groups represented by the above formula (5) is n5, n2 > 0, n3 ≥ 0, n4 ≥ 0, n5 ≥ 0, n2 + n3 + n4 + n5 ≥ 1, and it is a number satisfying 0.97 < n2 / (n2 + n3 + n4 + n5) ≤ 1.0. Also, k > 0, p ≥ 0, q ≥ 0 and r ≥ 0 are numbers, provided that k + p + q ≥ 2. The bonding order of each siloxane unit shown in the parentheses above is arbitrary. 2. The hydroxyalkyl group-containing polysiloxane according to 1, wherein r = 0 in the above formula (1). 3. The following formula (6) (R 1 3SiO 1 / 2 ) k (R 2 2SiO 2 / 2 ) p (R 2 SiO 3 / 2 ) q (6) (In the above formula, R 2 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. R 1 , k, p and q are the same as above.) The hydroxyalkyl group-containing polysiloxane according to 2, which is represented by 4. The following formula (7) (R 3 3SiO 1 / 2 ) k (R 3 2SiO 2 / 2 ) p (R 3 SiO 3 / 2 ) q (SiO 4 / 2 ) r (7) (In the above formula, R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that one or more of R 3 are hydrogen atoms. k, p 、 q and r are the same as above.) The organohydrogenpolysiloxane represented by the following formula (9) CH2=CH-Y-OH (9) (In equation (9) above, Y is the same as above.) A method for producing a hydroxyalkyl group-containing polysiloxane according to any one of 1 to 3, comprising a hydrosilylation reaction with an alkenyl alcohol represented by the above in the presence of a catalyst. To provide. [Effects of the Invention]

[0008] The hydroxyalkyl group-containing polysiloxane of the present invention has fewer dehydrogenation reaction products between the hydroxyl group and hydrosilyl group of the raw material compound compared to conventional products, and has high heat resistance. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below. [Hydroxyalkyl group-containing polysiloxane] The hydroxyalkyl group-containing polysiloxane of the present invention is represented by the following formula (1). (R 1 3SiO 1 / 2 ) k (R 1 2SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1)

[0010] In the above equation (1), R 1 These are, independently of each other, monovalent hydrocarbon groups having 1 to 20 carbon atoms and groups selected from the following formulas (2) to (5). -CH2-CH2-Y-OH or -CH2-CH2-YO-* (2) -OY-CH=CH2(3) -O-Y'-CH=CH-CH3(4) -OY-CH2-CH2-* (5)

[0011] R 1 The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Examples include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10; cycloalkyl groups having 3 to 20 carbon atoms, preferably 4 to 10; alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10; aryl groups having 6 to 20 carbon atoms, preferably 6 to 10; and aralkyl groups having 7 to 20 carbon atoms, preferably 8 to 10. R 1 Specific examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. R 1 The monovalent hydrocarbon group is more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, and even more preferably a methyl, ethyl, propyl, butyl, or phenyl group.

[0012] In equations (2), (3), and (5) above, Y is a divalent hydrocarbon group having 3 to 20 carbon atoms. The divalent hydrocarbon group Y having 3 to 20 carbon atoms can be linear, branched, or cyclic. Examples include alkylene groups with 3 to 20 carbon atoms, preferably 3 to 19; cycloalkylene groups with 3 to 20 carbon atoms, preferably 4 to 10; alkenylene groups with 3 to 20 carbon atoms, preferably 4 to 10; arylene groups with 6 to 20 carbon atoms, preferably 6 to 10; and aralkylene groups with 7 to 20 carbon atoms, preferably 8 to 10. However, it is preferable that the group does not contain an ether bond. Specific examples of divalent hydrocarbon groups of Y include alkylene groups such as trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and eicosadecylene; cycloalkylene groups such as cyclopentylene and cyclohexylene; alkenylene groups such as propenylene; arylene groups such as phenylene, methylphenylene, and naphthylene; and aralkylene groups such as benzylene and phenethylene.

[0013] The divalent hydrocarbon group of Y is preferably an alkylene group having 3 to 18 carbon atoms, more preferably trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, or decamethylene groups, even more preferably trimethylene, propylene, tetramethylene, hexamethylene, octamethylene, or nonamethylene groups, even more preferably trimethylene, hexamethylene, or nonamethylene groups, and particularly preferably hexamethylene or nonamethylene groups. If the number of carbon atoms is less than 3 or greater than 20, the dehydrogenation reaction products between the hydroxyl group and the hydrosilyl group of the starting compound increase.

[0014] In formula (4) above, Y' is a divalent hydrocarbon group having 2 to 19 carbon atoms. The divalent hydrocarbon group Y' having 2 to 19 carbon atoms can be linear, branched, or cyclic. Examples include alkylene groups with 2 to 19 carbon atoms, preferably 2 to 18; cycloalkylene groups with 3 to 19 carbon atoms, preferably 4 to 10; alkenylene groups with 2 to 19 carbon atoms, preferably 2 to 10; arylene groups with 6 to 19 carbon atoms, preferably 6 to 10; and aralkylene groups with 7 to 19 carbon atoms, preferably 8 to 10. However, it is preferable that it does not contain an ether bond. Specific examples of the divalent hydrocarbon group Y' include those similar to the groups with 3 to 19 carbon atoms exemplified for Y, and further, the ethylene group as an alkylene group and the vinylene group as an alkenylene group.

[0015] As the divalent hydrocarbon group of Y', it is preferably an alkylene group having 2 to 17 carbon atoms, more preferably an ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene group, still more preferably an ethylene, trimethylene, propylene, pentamethylene, hexamethylene, octamethylene group, even more preferably a trimethylene, pentamethylene, octamethylene group, and particularly preferably a pentamethylene, octamethylene group.

[0016] R 1 Among these, it is preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a group represented by the formula (2) to (5), more preferably methyl, ethyl, propyl, butyl, phenyl, or a group represented by the formula (2) to (5), still more preferably methyl, butyl, phenyl, or a group represented by the formula (2) to (5), and particularly preferably a methyl group, a phenyl group, or a group represented by the formula (2) to (5).

[0017] In the hydroxyalkyl group-containing polysiloxane represented by the above formula (1), when the number of the groups represented by the above formula (2) is n2, the number of the groups represented by the above formula (3) is n3, the number of the groups represented by the above formula (4) is n4, and the number of the groups represented by the above formula (5) is n5, it is a number satisfying n2 > 0, n3 ≥ 0, n4 ≥ 0, n5 ≥ 0, and n2 + n3 + n4 + n5 ≥ 1. Furthermore, it is a number satisfying 0.97 < n2 / (n2 + n3 + n4 + n5) ≤ 1.0. When n2 / (n2 + n3 + n4 + n5) ≤ 0.97, the number of hydroxyalkyl groups is small. Particularly in applications where hydroxyalkyl groups are reacted and used, the number of reaction sites decreases, making it difficult to obtain sufficient performance. Therefore, the lower limit is preferably 0.98 ≤ n2 / (n2 + n3 + n4 + n5), more preferably 0.99 ≤ n2 / (n2 + n3 + n4 + n5). The value of n2 / (n2 + n3 + n4 + n5) is 29 determined by Si-NMR analysis.

[0018] Furthermore, in equation (1) above, k, p, q, and r are numbers that are independent of each other, where k>0, p≧0, q≧0, and r≧0, provided that k+p+q≧2. k is preferably a number between 2 and 5, more preferably a number between 2 and 4, and even more preferably 2 or 3. p is preferably a number between 2 and 100, more preferably a number between 3 and 50, and even more preferably a number between 3 and 20. q is preferably a number between 0 and 3, more preferably a number between 0 and 2, and even more preferably 0 or 1. r is preferably a number between 0 and 3, more preferably a number between 0 and 2, even more preferably 0 or 1, and particularly preferably r=0. The bonding order of each siloxane unit shown in the parentheses above is not particularly restricted; they may be bonded randomly or form a block structure.

[0019] The weight-average molecular weight of the hydroxyalkyl group-containing polysiloxane of the present invention is preferably 300 to 20,000, more preferably 300 to 15,000, even more preferably 400 to 8,000, even more preferably 500 to 4,000, and particularly preferably 600 to 1,500. The above weight-average molecular weight is the value calculated on a polystyrene basis by gel permeation chromatography (GPC) measured under the following conditions. [Measurement conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (THF solution with a concentration of 0.3% by mass)

[0020] The hydroxyalkyl group-containing polysiloxane represented by formula (1) above may have any molecular structure, such as linear, branched, cyclic, or three-dimensional network. Particularly preferred are linear or branched siloxanes. Such linear or branched siloxanes are preferably those represented by the following formula (6). (R 1 3SiO 1 / 2 ) k (R 2 2SiO 2 / 2 ) p (R 2 SiO 3 / 2 ) q (6)

[0021] In the above formula (6), R 2 These are monovalent hydrocarbon groups with 1 to 20 carbon atoms, independently of each other. R 2 A specific example of a monovalent hydrocarbon group is R 1 Examples of the same groups as those exemplified above include R 2 The group is preferably an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms, more preferably a methyl, ethyl, propyl, butyl, or phenyl group, even more preferably a methyl, butyl, or phenyl group, and particularly preferably a methyl or phenyl group. In the above formula (6), R 1 k, p, and q are the same as above.

[0022] [Manufacturing method] The hydroxyalkyl group-containing polysiloxane of the present invention, represented by formula (1) above, can be obtained, for example, by hydrosilylation reaction of an organohydrogenpolysiloxane with an alkenyl alcohol. In the present invention, by using an alkenyl alcohol with a specific alkyl chain length as a raw material relative to the organohydrogenpolysiloxane, the hydrosilylation reaction proceeds selectively, and a hydroxyalkyl group-containing polysiloxane with few dehydrogenation reaction products between the hydroxyl group of the alkenyl alcohol and the hydrosilyl group of the organohydrogenpolysiloxane can be obtained.

[0023] (a) Organohydrogenpolysiloxane As the organohydrogenpolysiloxane, for example, those represented by the following formula (7) are preferable. (R 3 3SiO 1 / 2 ) k (R 3 2SiO 2 / 2 ) p (R 3 SiO 3 / 2 ) q (SiO 4 / 2 ) r (7)

[0024] In the above formula (7), R 3 is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. However, among R 3 , one or more are hydrogen atoms, and preferably two or more are hydrogen atoms.

[0025] R 3 Specific examples of the monovalent hydrocarbon group of R 1 are the same as those exemplified by R 3 . R is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, propyl, butyl, phenyl group, still more preferably a hydrogen atom, methyl, butyl, phenyl group, and particularly preferably a hydrogen atom, methyl group, phenyl group.

[0026] As the organohydrogenpolysiloxane, those represented by the following formula (8) are more preferable. (R 3 3SiO 1 / 2 ) k (R 2 2SiO 2 / 2 ) p (R[[ID=(68]] 2 SiO 3 / 2 ) q (8) (In the above formula (8), R 2 , R 3 , k, p and q are the same as above.)

[0027] Specific examples of the organohydrogenpolysiloxane represented by the above formula (7) include, for example, dimethylpolysiloxane blocked with dimethylhydrogen siloxy groups at both ends of the molecular chain, methylhydrogenpolysiloxane blocked with dimethylhydrogen siloxy groups at both ends of the molecular chain, methylhydrogen siloxane-dimethylsiloxane copolymer blocked with dimethylhydrogen siloxy groups at both ends of the molecular chain, methylhydrogen siloxane-diphenylsiloxane copolymer blocked with dimethylhydrogen siloxy groups at both ends of the molecular chain, methylhydrogen siloxane-dimethylsiloxane-diphenylsiloxane copolymer blocked with dimethylhydrogen siloxy groups at both ends of the molecular chain, (CH3)3SiO 1 / 2 units, (CH3)2HSiO 1 / 2 units, (CH3)2SiO units and CH3SiO 3 / 2 units copolymer, (CH3)2HSiO 1 / 2 units, (CH3)2SiO units and CH3SiO 3 / 2 units copolymer, (CH3)2HSiO 1 / 2 units, (C6H5)2SiO units, (CH3)2SiO units and CH3SiO 3 / 2 units copolymer, (CH3)(C6H5)HSiO 1 / 2 units, (CH3)2SiO units and CH3SiO 3 / 2 units copolymer, (CH3)2HSiO 1 / 2 units, (CH3)2SiO units and C6H5SiO 3 / 2 units copolymer, etc. These may be used alone or in combination of two or more.)

[0028] (b) Alkenyl alcohol On the other hand, as the alkenyl alcohol, for example, those represented by the following formula (9) are preferable.) CH2=CH-Y-OH (9) (In the above formula (9), Y is the same as above.)

[0029] Specific examples of alkenyl alcohols represented by formula (9) above include 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, 11-dodecen-1-ol, 13-tetradecen-1-ol, 15-hexadecene-1-ol, 17-octadecen-1-ol, 19-eicosen-1-ol, 21-docosen-1-ol, 2-methyl-3-buten-1-ol, 3-methyl-4-penten-1-ol, 3-methyl-5-hexen-1-ol, etc. These may be used individually or in combination of two or more. Among these, 4-penten-1-ol, 7-octen-1-ol, and 10-undecene-1-ol are preferred.

[0030] The amount of alkenyl alcohol used in the reaction is preferably such that the total number of alkenyl groups is in excess of the number of hydrosilyl groups in the organohydrogenpolysiloxane. For example, the ratio is such that there are 1 to 5 alkenyl groups, preferably 1 to 2, and particularly preferably 1 to 1.5, for every 1 hydrosilyl group. If there is less than 1 alkenyl group, there may not be enough alkenyl groups, leading to dehydrogenation and an increase in the amount of dehydrogenated reaction products. On the other hand, if there are more than 5 alkenyl groups, a large amount of alkenyl alcohol may remain in the reaction system, making it uneconomical.

[0031] Hydrosilylation addition reactions are preferably carried out under catalysis, but the catalyst is not particularly limited, and conventionally known addition reaction catalysts can be used. Specific examples of catalysts include, for example, elemental platinum group metals such as platinum (including platinum black), palladium, rhodium, and ruthenium, as well as metal catalysts containing these platinum group metals, gold, nickel, etc. Among these, catalysts containing platinum, palladium, or rhodium are preferred. Specific examples of catalysts containing platinum, palladium, or rhodium include, for example, PtCl4, H2PtCl6·6H2O, Pt-ether complexes, Pt-olefin complexes, PdCl2(PPh3)2, PdCl2(PhCN)2, RhCl2(PPh3)3 (wherein Ph is a phenyl group), platinum chloride, chloroplatinic acid or chloroplatinate, and complexes of vinyl group-containing siloxanes. These catalysts may be used individually or as a mixture of two or more. These catalysts may be used after being diluted with solvents such as alcohols, aromatics, hydrocarbons, ketones, or basic solvents, as needed. Among these, a catalyst containing platinum is more preferable, even more preferable is a complex of platinum chloride, platinum chloride, or platinum chloride salt with a vinyl group-containing siloxane, even more preferable is a complex of platinum chloride with a vinyl group-containing siloxane, and particularly preferable is a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane with a sodium bicarbonate neutralized product of platinum chloride (Karstedt catalyst), which is the most suitable as an addition reaction catalyst.

[0032] The amount of catalyst is not particularly limited and should be a catalytic amount. A catalytic amount is an amount sufficient to carry out the above addition reaction. For example, per 100 parts by mass of organohydrogenpolysiloxane, the amount of the metal catalyst, calculated on a main metal basis, is preferably 0.02 parts by mass or less, more preferably 0.00001 to 0.02 parts by mass, even more preferably 0.0001 to 0.01 parts by mass, and particularly preferably 0.0003 to 0.005 parts by mass. The catalyst may be added entirely at the beginning of the reaction, or in several portions during the reaction. Even a small amount of catalyst can allow the reaction to proceed sufficiently. However, if the amount of catalyst is too small, the reaction rate may become too slow; therefore, an amount above the lower limit is preferable. Conversely, if the amount of catalyst is too large, the reaction rate will not improve significantly, and it may become uneconomical.

[0033] If the resulting hydroxyl group-containing siloxane contains a large amount of residual metal catalyst, it can cause discoloration. Therefore, it is preferable to have a small amount of residual metal catalyst. In the production method of the present invention, the amount of metal catalyst contained in the resulting hydroxyl group-containing siloxane can be preferably 0.02 parts by mass or less, more preferably 0.01 parts by mass or less, and even more preferably 0.005 parts by mass or less, based on the amount of main metal atoms per 100 parts by mass of the siloxane. Furthermore, after the addition reaction is complete, any remaining metal catalyst may be adsorbed and removed using activated carbon or the like.

[0034] A solvent may be used in the hydrosilylation addition reaction as needed. Any solvent that does not inhibit the reaction can be used, including toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, dimethylformamide (DMF), acetonitrile, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. The solvent may or may not be removed by distillation after the addition reaction is complete.

[0035] The addition reaction temperature is preferably 20 to 250°C, more preferably 40 to 180°C, and even more preferably 80 to 120°C. The reaction time is preferably 1 hour or more, more preferably 20 hours or less, even more preferably 12 hours or less, and particularly preferably 8 hours or less.

[0036] The hydroxyalkyl group-containing polysiloxane of the present invention is useful, for example, in the synthesis of polyester resins and urethane resins, as well as in paint additives, cosmetics, and the like. [Examples]

[0037] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Note that in the following examples, 29Si-NMR analysis was performed using an ECX-500II (manufactured by JEOL Ltd.) with deuterated chloroform as the measurement solvent. In the example below, Me represents a methyl group.

[0038] [Example 1] 500 parts by mass of organohydrogenpolysiloxane represented by the formula H-(Me2SiO)9-SiMe2H were mixed with 298.28 parts by mass of 7-octen-1-ol and 0.5 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass), and the mixture was heated and stirred at 100°C for 6 hours. Then, impurities were removed at 140°C and 2 mmHg, and 3.95 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.995. Furthermore, when 2 g of the product was weighed into a 50 mL beaker and heated in air at 120°C for 1 week, the change in weight-average molecular weight was found to be 257%, and the residual rate calculated from the amount of product remaining in the beaker was 92%.

[0039] [Example 2] 180 parts by mass of organohydrogenpolysiloxane represented by the formula H-(Me2SiO)9-SiMe2H were mixed with 65.41 parts by mass of 4-penten-1-ol and 0.18 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass). The mixture was heated and stirred at 100°C for 4 hours. After that, impurities were removed at 120°C and 1 mmHg, and 0.9 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.985. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 641%, and the remaining percentage was 90%.

[0040] [Example 3] 150 parts by mass of organohydrogenpolysiloxane represented by the formula H-(Me2SiO)9-SiMe2H were mixed with 107.93 parts by mass of 10-undecen-1-ol and 0.15 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass). The mixture was heated and stirred at 120°C for 4 hours. After that, impurities were removed at 150°C and 1 mmHg, and 0.75 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.995. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 175%, and the remaining percentage was 98%.

[0041] [Example 4] Formula (Me3SiO 1 / 2 ) 0.45 (HMe2SiO 1 / 2 ) 2.55 (Me2SiO 2 / 2 ) 61.48 (MeSiO 3 / 2 ) 2.0740 parts by mass of organohydrogenpolysiloxane represented by [formula] were mixed with 5.02 parts by mass of 7-octen-1-ol and 0.04 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass). The mixture was heated and stirred at 120°C for 4 hours. After that, impurities were removed at 150°C and 1 mmHg, and 0.2 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.992. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 334%, and the remaining percentage was 99%.

[0042] [Comparative Example 1] 190 parts by mass of organohydrogenpolysiloxane represented by the formula H-(Me2SiO)9-SiMe2H were mixed with 57.8 parts by mass of 3-buten-1-ol and 0.19 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass). The mixture was heated and stirred at 80°C for 6 hours. After that, impurities were removed at 120°C and 2 mmHg, and 0.95 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.780. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 401%, and the remaining percentage was 83%.

[0043] [Comparative Example 2] 150 parts by mass of organohydrogenpolysiloxane represented by the formula H-(Me2SiO)9-SiMe2H were mixed with 64.65 parts by mass of allyl glycol and 0.15 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass), and the mixture was heated and stirred at 120°C for 4 hours. After that, impurities were removed at 120°C and 1 mmHg, and 0.75 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.970. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 588%, and the remaining percentage was 78%.

[0044] [Comparative Example 3] Formula (Me3SiO 1 / 2 ) 0.45 (HMe2SiO 1 / 2 ) 2.55 (Me2SiO 2 / 2 ) 61.48 (MeSiO 3 / 2 ) 2.07 40 parts by mass of organohydrogenpolysiloxane represented by [formula] were mixed with 3.72 parts by mass of allyl glycol and 0.04 parts by mass of a toluene solution of sodium bicarbonate chlorplatinate neutralized vinylsiloxane complex (platinum content 0.5% by mass), and the mixture was heated and stirred at 120°C for 4 hours. Then, impurities were removed at 150°C and 1 mmHg, and 0.2 parts by mass of activated carbon were added. The mixture was stirred at 20°C for 1 hour, and the activated carbon was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain the product. The obtained product 29 Analysis using Si-NMR revealed that n2>0, n3≧0, n4≧0, n5≧0, and n2+n3+n4+n5≧1, and therefore n2 / (n2+n3+n4+n5)=0.933. Furthermore, the percentage change in weight-average molecular weight after heating at 120°C for one week, as measured in the same manner as in Example 1, was 4169%, and the remaining percentage was 97%.

[0045] The results of Examples 1-4 and Comparative Examples 1-3 are summarized in Table 1. As shown in Table 1, the hydroxyalkyl group-containing polysiloxanes of Examples 1-4 exhibit high heat resistance because the change in weight-average molecular weight before and after heating at 120°C is small and the retention rate is high.

[0046] [Table 1]

Claims

1. A hydroxyalkyl group-containing polysiloxane represented by the following formula (6), having a weight-average molecular weight of 300 to 4,000. (R 1 3 SiO 1 / 2 ) k (R 2 2 SiO 2 / 2 ) p (R 2 SiO 3 / 2 ) q （６） [In the above formula, R 1 These are, independently of each other, monovalent hydrocarbon groups having 1 to 20 carbon atoms and groups selected from the following formulas (2) to (5): -CH 2 -CH 2 -Y-OH or -CH 2 -CH 2 -Y-O-* （２） -O-Y-CH=CH 2 (3) -O-Y'-CH=CH-CH 3 (4) -O-Y-CH 2 -CH 2 -* (5) (In the above formula, Y is a divalent hydrocarbon group having 6 to 20 carbon atoms, Y' is a divalent hydrocarbon group having 5 to 19 carbon atoms, and the asterisk * indicates a bond point that directly bonds to a silicon atom in another hydroxyalkyl group-containing polysiloxane molecule.) R 2 These are, independently of each other, monovalent hydrocarbon groups having 1 to 20 carbon atoms. When the number of bases shown in equation (2) is n2, the number of bases shown in equation (3) is n3, the number of bases shown in equation (4) is n4, and the number of bases shown in equation (5) is n5, then n2 > 0, n3 ≥ 0, n4 ≥ 0, n5 ≥ 0, n2 + n3 + n4 + n5 ≥ 1, and 0.97 < n2 / (n2 + n3 + n4 + n5) ≤ 1.

0. Furthermore, k is the number of values ​​where k > 0, p ≥ 0, and q ≥ 0, where k + p + q ≥ 2. Note that the bonding order of each siloxane unit shown in the parentheses above is arbitrary.

2. The hydroxyalkyl group-containing polysiloxane according to claim 1, wherein the weight-average molecular weight is 600 to 4,000.

3. The following formula (8) (R 3 3 SiO 1 / 2 ) k (R 2 2 SiO 2 / 2 ) p (R 2 SiO 3 / 2 ) q (8) (In the above formula, R 3 R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, independently of each other. 3 Of these, one or more are hydrogen atoms. 2 (k, p, and q are the same as above.) The organohydrogen polysiloxane represented by the following formula (9) CH 2 =CH-Y-OH (9) (In equation (9) above, Y is the same as above.) A method for producing a hydroxyalkyl group-containing polysiloxane according to claim 1 or 2, comprising hydrosilylation reaction with an alkenyl alcohol represented by in the presence of a catalyst.

4. The manufacturing method according to claim 3, comprising carrying out a hydrosilylation reaction at 100-120°C for 4-6 hours, followed by removing impurities at 140-150°C and 1-2 mmHg.

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