Hydroxyl-containing organosilicon compounds

Abstract

Provided is a hydroxyl group-containing organosilicon compound represented by general formula (1). (1): (R1 3SiO1 / 2)k(R1 2SiO2 / 2)p(R1SiO3 / 2)q(SiO4 / 2)r [In formula (1), R1 is a group selected from a monovalent hydrocarbon group and a group represented by formula (2), provided that at least one of all R1 groups is a group represented by formula (2). k>0, p≥0, q≥0 and r≥0, provided that k+p+q≥2.] (In formula (2), R2 is a hydrogen atom or a group selected from a monovalent hydrocarbon group and an alkoxy group, and R3 is a hydrogen atom or a methyl group. s is an integer of 0-4, t is an integer of 2-4 and u is a numerical value of 1-3. The broken line represents a bond.)

Description

[Technical Field]

[0001] The present invention relates to a hydroxyl group-containing organosilicon compound, and more specifically to a novel organosilicon compound having an organopolysiloxane group and a hydroxyl group in one molecule. [Background technology]

[0002] Hydroxyl-containing polysiloxanes are used in a variety of applications, such as paint additives and resin modifiers. As a resin modifier, it has been used in, for example, the synthesis of urethane resin by the reaction of hydroxyalkyl group-containing polysiloxane with an isocyanate compound (Patent Documents 1 and 2), the synthesis of polyester resin by the reaction of hydroxyalkyl group-containing polysiloxane with a carboxy compound (Patent Document 3), and the synthesis of polycarbonate resin by the reaction of phenolic hydroxyl group-containing polysiloxane with a carbonate ester compound (Patent Document 4).

[0003] By using a hydroxyl group-containing polysiloxane in the synthesis of a resin, it is possible to improve the heat resistance, cold resistance, water resistance, chemical resistance, impact resistance, electrical properties, gas permeability, and other properties that are characteristic of siloxane. However, in the synthesis of urethane resins, phenolic hydroxyl group-containing polysiloxanes are not used because phenolic hydroxyl groups have low reactivity with isocyanate groups.

[0004] A general-purpose hydroxyalkyl group-containing polysiloxane can be obtained by a hydrosilylation reaction between allyl glycol and hydrogen polysiloxane (Patent Document 5). However, allyl glycol and hydrogenpolysiloxane have low compatibility, so to react them without a solvent, it is necessary to use a large excess of allyl glycol relative to the hydrosilyl groups.

[0005] To overcome this problem, the reactivity can be increased by using an alcohol solvent such as ethanol or 2-propanol during the hydrosilylation reaction. However, by-products are also likely to be produced as a result of a dehydrogenation reaction between the hydroxyl groups in the solvent and the hydrosilyl groups of the hydrogenpolysiloxane.

[0006] Furthermore, hydroxyalkyl group-containing polysiloxanes obtained from allyl glycol and hydrogen polysiloxanes have the problem of low heat resistance. For these reasons, there is a demand for hydroxyl group-containing polysiloxane compounds that are easy to synthesize, produce few by-products, and have high heat resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2001-500912 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-165822 [Patent Document 3] International Publication No. 2012 / 137837 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-246430 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-224060 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel hydroxyl group-containing organosilicon compound which is easy to synthesize, produces few by-products, and has excellent heat resistance. [Means for solving the problem]

[0009] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that a hydroxyl-containing organosilicon compound having a specific structure represented by the following general formula (1) is easy to synthesize, produces few by-products, and has excellent heat resistance, thereby achieving the present invention.

[0010] That is, the present invention is 1. A hydroxyl group-containing organosilicon compound represented by the following general 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 formula (1), R 1 are each independently a group selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms and a group represented by the following formula (2), provided that all R 1 At least one of the groups is a group represented by the following formula (2): k, p, q, and r are, respectively, a number where k>0, a number where p≧0, a number where q≧0, and a number where r≧0, provided that k+p+q≧2. The bonding order of each siloxane unit shown in parentheses is arbitrary. [ka] (In formula (2), R 2 are each independently a hydrogen atom or a group selected from a monovalent hydrocarbon group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and R 3 represents a hydrogen atom or a methyl group; s represents an integer of 0 to 4, t represents an integer of 2 to 4, and u represents a number of 1 to 3; the dashed line represents a bond.) 2. The hydroxyl group-containing organosilicon compound according to 1, wherein the group represented by formula (2) is any one of the groups represented by the following formulas (3) to (5): [ka] (In the formula, t and u are the same as above. The dashed lines represent bonds.) 3. In the formula (1), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 13. The hydroxyl group-containing organosilicon compound according to 1 or 2, wherein 2 to 5 of the groups are groups represented by formula (2): 4. The hydroxyl group-containing organosilicon compound according to any one of 1 to 3, which is an addition reaction product of an organohydrogenpolysiloxane represented by the following general formula (6) and a compound containing a hydroxyl group and an aliphatic unsaturated group represented by the following general formula (7): (R 4 3SiO 1 / 2 ) k (R 4 2SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (SiO 4 / 2 ) r (6) (In formula (6), R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that all R 4 At least one of the groups is a hydrogen atom. k, p, q, and r are the same as above. The bonding order of the siloxane units shown in parentheses is arbitrary. [ka] (In formula (7), R 2 , R 3 , s, t, and u are the same as above.) 5. The hydroxyl group-containing organosilicon compound according to 4, wherein the compound containing a hydroxyl group and an aliphatic unsaturated group represented by the formula (7) is any one of the compounds represented by the following formulas (8) to (10): [ka] (wherein t and u are the same as above). 6. In the formula (6), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 4 6. The hydroxyl group-containing organosilicon compound according to 4 or 5, wherein 2 to 5 of the groups are hydrogen atoms. to provide. [Effects of the Invention]

[0011] The organosilicon compounds of the present invention have highly reactive hydroxyl groups and are highly heat resistant. Moreover, they can be efficiently obtained while suppressing the formation of by-products, making them useful as synthetic raw materials and modifiers for various resins. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. [Hydroxyl group-containing organosilicon compound] The hydroxyl group-containing organosilicon compound of the present invention is represented by the following general 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)

[0013] In formula (1), R 1 are each independently a group selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms and a group represented by the following formula (2), provided that all R 1 At least one of the groups is an organic group represented by the following formula (2), but preferably all R 1 Two to five of the groups are organic groups represented by the following formula (2).

[0014] [ka] (In formula (2), the dashed lines represent bonds.)

[0015] R 1The monovalent hydrocarbon group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms; an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms; and an aralkyl group having 7 to 10 carbon atoms. R 1 Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among these, R 1 is preferably a methyl group, an ethyl group, or a phenyl group.

[0016] In equation (2), R 2 are each independently a hydrogen atom or a group selected from monovalent hydrocarbon groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms. R 2 The monovalent hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and specific examples thereof include R 1 Among the groups exemplified in 1, the same straight-chain or branched groups having 1 to 5 carbon atoms can be mentioned, and among these, a methyl group, an isopropyl group, and a t-butyl group are preferred. R 2 The alkoxy group having 1 to 5 carbon atoms is preferably one having 1 to 3 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentoxy, etc. Of these, methoxy and ethoxy are preferred. R 3 is a hydrogen atom or a methyl group.

[0017] In formula (2), s is an integer of 0 to 4, and preferably an integer of 0 to 2. t is an integer of 2 to 4, preferably 2 or 3. The symbol u is a number from 1 to 3, and the repeating unit in the parentheses to which u is added may be a chemically single repeating unit or a combination of different repeating units whose average value is a number from 1 to 3. When u is 0, the hydroxyl group is phenolic, and the reactivity with, for example, an isocyanate group is reduced, so u is 1 or more. A combination of different repeating units is also not included when u is 0. Furthermore, when u exceeds 3, heat resistance is reduced, so a combination of u of 4 or more is also not included, and u is a number from 1 to 3. It is particularly preferred that the repeating unit in the parentheses to which u is added is a chemically single repeating unit.

[0018] Examples of the group represented by formula (2) include, but are not limited to, those represented by the following formulas:

[0019] [ka] (In the formula, t and u are the same as above. The dashed lines represent bonds.)

[0020] Among these, those represented by the following formulas (3) to (5) are preferred. [ka] (In the formula, t and u are the same as above. The dashed lines represent bonds.)

[0021] Specific examples of the groups represented by the formulas (3) to (5) include, but are not limited to, the groups represented by the following formulas: Among these, the groups represented by the formulas (3a), (4a) to (4e), and (5a) are preferred. [ka] (In the formula, the dashed lines represent bonds.)

[0022] In formula (1), k, p, q, and r are numbers such that k>0, p≧0, q≧0, and r≧0, respectively, where k+p+q≧2. k is preferably a number from 2 to 5, and more preferably a number from 2 to 4. p is preferably a number from 2 to 100, and more preferably a number from 5 to 80. q is preferably a number of 0 to 3, more preferably a number of 0 to 2, and even more preferably 1 or 2. r is preferably a number of 0 to 3, more preferably 0 or 1, and even more preferably 0. k+p+q is preferably a number that satisfies k+p+q≧5, and more preferably a number that satisfies k+p+q≧8. The bonding order of the siloxane units shown in the parentheses is not particularly limited, and they may be bonded randomly or may form a block structure.

[0023] The hydroxyl group-containing organosilicon compound of the present invention is a compound represented by the formula (1), in which k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 1 It is preferable that 2 to 5 of the groups are groups represented by the formula (2), k is a number of 2 to 4, p is a number of 5 to 80, q is a number of 0 to 2, r is 0, and all R 1 It is more preferable that two or three of the groups are groups represented by the above formula (2). The group represented by formula (2) may be present at either a molecular chain terminal (one terminal or both terminals), in the middle of the molecular chain, or both terminals, but is preferably present at least at a molecular chain terminal (one terminal or both terminals), and more preferably at both molecular chain terminals.

[0024] As the hydroxyl group-containing organosilicon compound of the present invention, those represented by the following formula are particularly preferred. [ka] (In the formula, n is a number of n≧0, and k, p, and q are the same as above.)

[0025] The weight-average molecular weight of the hydroxyl group-containing organosilicon compound of the present invention is preferably 400 to 15,000, more preferably 600 to 10,000, even more preferably 600 to 8,000, and particularly preferably 600 to 5,000. Note that this weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the following conditions. [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: 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 (0.3% by mass THF solution)

[0026] The kinematic viscosity of the hydroxyl group-containing organosilicon compound of the present invention is preferably 40 to 10,000 mm 2 / s, and more preferably 50 to 5,000 mm 2 The kinematic viscosity is measured at 25°C using a Cannon-Fenske viscometer according to JIS Z 8803:2011.

[0027] [Manufacturing method] The hydroxyl group-containing organosilicon compound of the present invention can be obtained, for example, by hydrosilylation of an organohydrogenpolysiloxane represented by the following general formula (6) with a compound having a hydroxyl group and an aliphatic unsaturated group (allyl group or methallyl group) represented by the following general formula (7).

[0028] (a) Organohydrogenpolysiloxane As the organohydrogenpolysiloxane, one represented by the following formula (6) is used. (R 4 3SiO 1 / 2 ) k (R 4 2SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (SiO 4 / 2 ) r (6)

[0029] In equation (6), R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that all R 4 At least one of the groups is a hydrogen atom, but all R 4 Preferably, 2 to 5 atoms in the group are hydrogen atoms. R 4 As the monovalent hydrocarbon group, R 1 Among these, a methyl group, an ethyl group, and a phenyl group are preferred. k, p, q and r are the same as above. The bonding order of the siloxane units shown in the parentheses is not particularly limited, and they may be bonded randomly or may form a block structure.

[0030] The organohydrogenpolysiloxane is a polysiloxane represented by the formula (6), in which k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 4 It is preferable that 2 to 5 atoms in the group are hydrogen atoms, k is a number of 2 to 4, p is a number of 5 to 80, q is a number of 0 to 2, r is 0, and all R 4 It is more preferable that two or three of the groups are hydrogen atoms. Furthermore, hydrogen atoms may be present at either a molecular chain terminal (one terminal or both terminals), or in the middle of the molecular chain, or may be present at both terminals. However, hydrogen atoms are preferably present at least at a molecular chain terminal (one terminal or both terminals), and more preferably at both molecular chain terminals.

[0031] Specific examples of organohydrogenpolysiloxanes represented by the formula (6) include 1,1,3,3-tetramethyldisiloxane, dimethylpolysiloxanes terminally blocked with dimethylhydrogensiloxy groups, methylhydrogenpolysiloxanes terminally blocked with dimethylhydrogensiloxy groups, methylhydrogensiloxane-dimethylsiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, methylhydrogensiloxane-diphenylsiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, methylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, and (CH3)3SiO 1 / 2 Units and (CH3)2HSiO 1 / 2 Units and (CH3)2SiO Units and CH3SiO 3 / 2 A copolymer consisting of units, (CH3)2HSiO 1 / 2 Units and (CH3)2SiO Units and CH3SiO 3 / 2 A copolymer consisting of units, (CH3)2HSiO 1 / 2 Units and (C6H5)2SiO units and (CH3)2SiO units and CH3SiO 3 / 2 A copolymer consisting of the unit (CH3)(C6H5)HSiO 1 / 2 Units and (CH3)2SiO Units and CH3SiO 3 / 2 A copolymer consisting of units, (CH3)2HSiO 1 / 2 (CH3)2SiO units and C6H5SiO units 3 / 2 These may be used alone or in combination of two or more. Among these, 1,1,3,3-tetramethyldisiloxane, dimethylpolysiloxane terminated at both ends with dimethylhydrogensiloxy groups, (CH3)2HSiO 1 / 2Units and (CH3)2SiO Units and CH3SiO 3 / 2 Copolymers consisting of units are preferred.

[0032] (b) Compounds containing hydroxyl groups and aliphatic unsaturated groups On the other hand, as the compound having a hydroxyl group and an aliphatic unsaturated group, a compound represented by the following formula (7) is used.

[0033] [ka] (In formula (7), R 2 , R 3 , s, t, and u are the same as above.)

[0034] Expressed in equation (7), compound Examples of the compound include, but are not limited to, those represented by the following formula: These may be used alone or in combination of two or more.

[0035] [ka] (wherein t and u are the same as above).

[0036] Among these, those represented by the following formulas (8) to (10) are preferred. [ka] (wherein t and u are the same as above).

[0037] Represented by the formulas (8) to (10) compound Specific examples of include, but are not limited to, groups represented by the following formulae: Among these, those represented by formulae (8a), (9a) to (9e), and (10a) are preferred.

[0038] [ka]

[0039] The compound having a hydroxyl group and an aliphatic unsaturated group represented by formula (7) can be obtained, for example, by the following method. When a phenol compound having an allyl group in the molecule, such as orthoallylphenol or eugenol (2-methoxy-4-allylphenol), which is readily available as a commercial product, is used as a starting material, the product can be obtained by subjecting the phenolic hydroxyl group to an addition reaction with a predetermined amount of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or the like, or a mixture thereof, using a known method.

[0040] Furthermore, for example, when a phenolic compound such as phenol, 2,6-dimethylphenol, 2,4-di-t-butylphenol, or 2,6-di-t-butylphenol is used as a starting material, first, by a known method, these phenolic compounds are reacted with an allyl halide compound such as allyl bromide, allyl chloride, or methallyl chloride under basic conditions to obtain allyl (or methallyl) phenyl ether. Next, a thermal rearrangement reaction of the allyl group is carried out to obtain allylated (or methallylated) phenol, which is then subjected to an addition reaction with a predetermined amount of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or the like, or a mixture thereof, in the same manner as described above, to obtain the desired product. Since the thermal rearrangement reaction of the allyl group occurs at the ortho or para position, in order to obtain a highly pure product, it is more preferable to use a compound in which only one of the ortho and para positions is vacant, such as 2,6-dimethylphenol, 2,4-di-t-butylphenol, or 2,6-di-t-butylphenol.

[0041] In the reaction of the organohydrogenpolysiloxane with the compound having a hydroxyl group and an aliphatic unsaturated group, the amount of the compound having a hydroxyl group and an aliphatic unsaturated group to be reacted is preferably such that the number of moles of the aliphatic unsaturated group (allyl group or methallyl group) contained in the compound having a hydroxyl group and an aliphatic unsaturated group is in excess relative to the number of moles of the hydrosilyl groups contained in the organohydrogenpolysiloxane. For example, the ratio of moles of aliphatic unsaturated groups to 1 mole of hydrosilyl groups is preferably 1 to 5 moles, more preferably 1 to 2 moles, and even more preferably 1 to 1.5 moles. If the ratio is less than 1 mole, the amount of aliphatic unsaturated groups may be insufficient, making dehydrogenation more likely to occur. On the other hand, if the ratio exceeds 5 moles, a large amount of unreacted compounds having hydroxyl groups and aliphatic unsaturated groups may remain in the reaction system, which may be uneconomical.

[0042] The hydrosilylation reaction between the organohydrogenpolysiloxane of formula (6) and the compound of formula (7) having a hydroxyl group and an aliphatic unsaturated group is preferably carried out in the presence of a catalyst, but the catalyst is not particularly limited, and any conventionally known addition reaction catalyst can be used. Specific examples of the catalyst include platinum group metals such as platinum (including platinum black), palladium, rhodium, and ruthenium, and metal catalysts containing these platinum group metals, gold, nickel, cobalt, etc. Among these, platinum group metal catalysts containing platinum, palladium, or rhodium are particularly preferred. Specific examples of catalysts containing platinum, palladium, or rhodium include PtCl4, HPtCl6·6H2O, Pt-ether complexes, Pt-olefin complexes, PdCl2(PPh3)2, PdCl2(PhCN)2, RhCl2(PPh3)3 (wherein Ph is a phenyl group), platinum chloride, complexes of chloroplatinic acid or chloroplatinate with vinyl group-containing siloxanes, etc. These catalysts may be used alone or as a mixture of two or more. Of these, more preferred are platinum-containing metal catalysts, and particularly preferred is Karstedt's catalyst (a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and chloroplatinic acid neutralized with sodium bicarbonate). If necessary, these catalysts can be used after diluting with a solvent such as an alcohol, an aromatic compound, a hydrocarbon, a ketone, or a basic solvent.

[0043] The amount of catalyst is not particularly limited as long as it is a catalytic amount, which is an amount sufficient to cause the addition reaction to proceed, and is, for example, 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, in terms of the main metal atom of the metal catalyst, per 100 parts by mass of hydrogenpolysiloxane. The catalyst may be added in its entirety from the beginning of the reaction, or may be added in portions during the reaction. Even a low amount of catalyst can sufficiently promote the reaction. However, if the amount of catalyst is too small, the reaction rate may become too slow, so the amount is preferably equal to or greater than the lower limit. On the other hand, if the amount of catalyst is too large, the reaction rate will not be significantly improved, which may be uneconomical.

[0044] If the resulting hydroxyl-containing siloxane contains a large amount of residual metal catalyst, it will cause discoloration. Therefore, the amount of residual metal catalyst is preferably small. In the production method of the present invention, the amount of metal catalyst contained in the resulting hydroxyl-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, calculated as the amount of main metal atom per 100 parts by mass of the siloxane. After the addition reaction is complete, the remaining metal catalyst may be removed by adsorption using activated carbon or the like.

[0045] The hydrosilylation reaction of the organohydrogenpolysiloxane of the present invention with a compound having a hydroxyl group and an aliphatic unsaturated group is characterized in that it can be carried out without using a solvent, unlike known methods for synthesizing hydroxyalkyl group-containing polysiloxanes. However, a solvent may be used as needed, provided that the object of the present invention is not impaired. Specific examples of the solvent include toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, dimethylformamide (DMF), and acetonitrile. When a solvent is used, it may or may not be distilled off after the addition reaction is completed.

[0046] The reaction temperature for hydrosilylation is preferably 20 to 200° C., more preferably 40 to 180° C., and even more preferably 60 to 150° C. The reaction time is preferably within 20 hours, more preferably within 12 hours, and even more preferably within 8 hours.

[0047] This production method makes it possible to efficiently obtain organosilicon compounds having highly reactive hydroxyl groups in the molecule.

[0048] The hydroxyl group-containing organosilicon compound of the present invention has highly reactive hydroxyl groups in the molecule and is useful in a variety of applications, for example, as a raw material for synthesizing polyester resins, urethane resins, etc., and as a paint additive. [Example]

[0049] EXAMPLES 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. In the following examples, the kinematic viscosity is a value measured at a temperature of 25°C using a Cannon-Fenske viscometer according to the method described in JIS Z 8803:2011. The hydroxyl value is a value measured according to JIS K 0070:1992.

[0050] [Example 1] After replacing the atmosphere in the flask with nitrogen, 186.9 g of an unsaturated alcohol compound represented by the following formula (11) and 0.10 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 363.0 g of methylhydrogenpolysiloxane represented by the following formula (12) was added dropwise over 35 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 2.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 497.0 g of a hydroxyl-containing organopolysiloxane represented by the following formula (13). The appearance is colorless and transparent, and the kinematic viscosity is 125mm 2 / s, and the hydroxyl value was 112 mgKOH / g.

[0051] [ka]

[0052] [Example 2] After replacing the atmosphere in the flask with nitrogen, 446.9 g of an unsaturated alcohol compound represented by the following formula (14) and 0.23 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 60°C. To this was added dropwise 742.8 g of the methylhydrogenpolysiloxane represented by the above formula (12) over 22 minutes. After the dropwise addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 5.9 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 1074.2 g of a hydroxyl-containing organopolysiloxane represented by the following formula (15). The appearance is colorless and transparent, and the kinematic viscosity is 372mm 2 / s, and the hydroxyl value was 105 mgKOH / g.

[0053] [ka]

[0054] [Example 3] After the atmosphere in the flask was replaced with nitrogen, 231.1 g of an unsaturated alcohol compound, a mixture of a compound represented by the following formula (16) and a compound represented by the following formula (17) (the content ratio of the compound of formula (16) to the compound of formula (17) was formula (16) / formula (17) = 86 / 14 mol %), and 0.11 g of Karstedt catalyst (platinum concentration 0.5 mass %) were added and heated to 70°C. 363.0 g of the methylhydrogenpolysiloxane represented by the formula (12) was added dropwise over 44 minutes. After the dropwise addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted material was distilled off under reduced pressure (220°C / 400 Pa). 3.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. It was then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 536.0 g of a hydroxyl-containing organopolysiloxane represented by the following formula (18). The ratio of primary hydroxyl groups to secondary hydroxyl groups in the product was the same as the ratio of the compounds of formula (16) and formula (17). The appearance is colorless and transparent, and the kinematic viscosity is 283mm 2 / s, and the hydroxyl value was 92.2 mgKOH / g.

[0055] [ka]

[0056] [Example 4] After replacing the atmosphere in the flask with nitrogen, 160.0 g of an unsaturated alcohol compound represented by the following formula (19) and 0.07 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 219.0 g of the methylhydrogenpolysiloxane represented by the above formula (12) was added dropwise over 38 minutes. After the dropwise addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 2.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 340.6 g of a hydroxyl-containing organopolysiloxane represented by the following formula (20). The appearance is colorless and transparent, and the kinematic viscosity is 408mm 2 / s, and the hydroxyl value was 98.7 mgKOH / g.

[0057] [ka]

[0058] [Example 5] After replacing the atmosphere in the flask with nitrogen, 203.0 g of an unsaturated alcohol compound represented by the following formula (21) and 0.11 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 325.2 g of the methylhydrogenpolysiloxane represented by the above formula (12) was added dropwise over 20 minutes. After the dropwise addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 2.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 467.1 g of a hydroxyl-containing organopolysiloxane represented by the following formula (22). The appearance is colorless and transparent, and the kinematic viscosity is 290mm 2 / s, and the hydroxyl value was 109 mgKOH / g.

[0059] [ka]

[0060] [Example 6] After replacing the atmosphere in the flask with nitrogen, 143.0 g of the unsaturated alcohol compound represented by formula (14) and 0.04 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 60°C. 43.9 g of 1,1,3,3-tetramethyldisiloxane was added dropwise over 30 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 1.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 150.2 g of a hydroxyl-containing organopolysiloxane represented by the following formula (23). The appearance is colorless and transparent, and the kinematic viscosity is 3,500mm2 / s, and the hydroxyl value was 203 mgKOH / g.

[0061] [ka]

[0062] [Example 7] After replacing the atmosphere in the flask with nitrogen, 216.0 g of the unsaturated alcohol compound represented by formula (14) and 0.20 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 798.0 g of methylhydrogenpolysiloxane represented by formula (24) below was added dropwise over 10 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 5.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 923.4 g of a hydroxyl-containing organopolysiloxane represented by the following formula (25). The appearance is colorless and transparent, and the kinematic viscosity is 218mm 2 / s, and the hydroxyl value was 55.7 mgKOH / g.

[0063] [ka]

[0064] [Example 8] After replacing the atmosphere in the flask with nitrogen, 90.0 g of the unsaturated alcohol compound represented by formula (14) and 0.14 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 621.0 g of methylhydrogenpolysiloxane represented by formula (26) below was added dropwise over 10 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 3.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 650.2 g of a hydroxyl-containing organopolysiloxane represented by the following formula (27). The appearance is colorless and transparent, and the kinematic viscosity is 242mm 2 / s, and the hydroxyl value was 30.4 mgKOH / g.

[0065] [ka]

[0066] [Example 9] After replacing the atmosphere in the flask with nitrogen, 103.5 g of the unsaturated alcohol compound represented by formula (14) and 0.22 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 80°C. 1012.6 g of methylhydrogenpolysiloxane represented by formula (28) below was added dropwise over 5 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 5.6 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 1020.3 g of a hydroxyl-containing organopolysiloxane represented by the following formula (29). The appearance is colorless and transparent, and the kinematic viscosity is 244mm 2 / s, and the hydroxyl value was 23.0 mgKOH / g.

[0067] [ka]

[0068] [Example 10] After replacing the atmosphere in the flask with nitrogen, 49.1 g of the unsaturated alcohol compound represented by the above formula (11) and 372.0 g of the methylhydrogenpolysiloxane represented by the following formula (30) were charged and heated to 80° C. To this, 0.10 g of Karstedt catalyst (platinum concentration 0.5% by mass) was added, and the mixture was stirred at 110° C. for 3 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 2.1 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 385.3 g of a hydroxyl-containing organopolysiloxane represented by the following formula (31). The appearance is colorless and transparent, and the kinematic viscosity is 173mm 2 / s, and the hydroxyl value was 38.0 mgKOH / g.

[0069] (H(CH3)2SiO 1 / 2 ) 3.0 ((CH3)2SiO 2 / 2 ) 56.5 (CH3SiO 3 / 2 ) 1.0 (30) [ka]

[0070] [Example 11] After replacing the atmosphere in the flask with nitrogen, 182.3 g of the unsaturated alcohol compound represented by formula (14) and 0.30 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 80°C. 1296.0 g of methylhydrogenpolysiloxane represented by formula (32) below was added dropwise over 10 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off by heating under reduced pressure (220°C / 400 Pa). 7.4 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 1404.0 g of a hydroxyl-containing organopolysiloxane represented by the following formula (33). The appearance is colorless and transparent, and the kinematic viscosity is 231mm 2 / s, and the hydroxyl value was 33.0 mgKOH / g.

[0071] [ka]

[0072] [Example 12] After replacing the atmosphere in the flask with nitrogen, 80.8 g of the unsaturated alcohol compound represented by the formula (21) and 0.25 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 80°C. 762.7 g of the methylhydrogenpolysiloxane represented by the formula (28) was added dropwise over 5 minutes. After the addition was completed, the mixture was stirred at 110°C for an additional 2 hours. Subsequently, unreacted materials were distilled off under reduced pressure (230°C / 400 Pa). 4.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After filtration using a filter plate (NA-500, manufactured by Advantec Co., Ltd.), 776.0 g of a hydroxyl-containing organopolysiloxane represented by the following formula (34) was obtained. The appearance is colorless and transparent, and the kinematic viscosity is 191mm 2 / s, and the hydroxyl value was 24.5 mgKOH / g.

[0073] [ka]

[0074] [Comparative Example 1] After replacing the atmosphere in the flask with nitrogen, 88.2 g of allyl glycol, 56.0 g of 2-propanol, and 0.12 g of Karstedt catalyst (platinum concentration 0.5% by mass) were added and heated to 70°C. 224.0 g of methylhydrogenpolysiloxane represented by formula (12) was added dropwise over 40 minutes. After the addition was completed, the mixture was stirred for an additional 4 hours under reflux of 2-propanol. Subsequently, unreacted materials were distilled off by heating under reduced pressure (120°C / 400 Pa). 1.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours. After that, the mixture was filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 272.5 g of a hydroxyl-containing organopolysiloxane represented by the following formula (35). The appearance is colorless and transparent, and the kinematic viscosity is 30.0mm. 2 / s, and the hydroxyl value was 116 mgKOH / g.

[0075] [ka]

[0076] 2 g of each of the hydroxyl-containing organopolysiloxanes obtained in Examples 1 to 5 and Comparative Example 1 was weighed into a 50 mL beaker and heated in air at 120°C for one week, after which the weight-average molecular weight and the rate of change were measured. The method for measuring the weight-average molecular weight was as described above. As shown below, the hydroxyl-containing organopolysiloxane of the present invention exhibits excellent heat resistance, with only a small change in weight-average molecular weight after heating at 120°C for one week.

[0077] [Table 1]

Claims

1. The following general formula (1) (R 1 3 SiO 1 / 2 ) k (R 1 2 SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1) [In formula (1), R 1 are each independently a group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms and groups represented by the following formulas (3) to (5), provided that all R 1 At least one of the groups is any of the groups represented by the following formulas (3) to (5). k, p, q, and r are, respectively, a number where k>0, a number where p≧0, a number where q≧0, and a number where r≧0, provided that k+p+q≧2. The bonding order of the siloxane units shown in parentheses is arbitrary. 【Chemistry 1】 (wherein t is an integer of 2 to 4, and u is a number of 1 to 3. The dashed lines represent bonds.) and represented by the following general formula (6): (R 4 3 SiO 1 / 2 ) k (R 4 2 SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (SiO 4 / 2 ) r (6) (In formula (6), R 4 s are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that at least one of all R 4 groups is a hydrogen atom. k, p, q, and r are the same as defined above. The bonding order of the siloxane units shown in parentheses is arbitrary.) and organohydrogenpolysiloxanes represented by the following formulas (8) to (10) corresponding to the above formulas (3) to (5): 【Chemistry 2】 (In the formula, t and u are the same as defined above.) 2. A hydroxyl group-containing organosilicon compound which is an addition reaction product with any compound containing a hydroxyl group and an aliphatic unsaturated group, represented by the following formula:

2. In the formula (1), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 1 2. The hydroxyl group-containing organosilicon compound according to claim 1, wherein 2 to 5 of the groups are groups represented by any one of formulas (3) to (5).

3. In the formula (6), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and all R 4 3. The hydroxyl group-containing organosilicon compound according to claim 1, wherein 2 to 5 of the groups are hydrogen atoms.

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