Process for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound

Abstract

To provide a method for producing an alkoxysilyl alkylaminoalkyl-modified polysiloxane compound which reaches a sufficient reaction rate at a low temperature in a short time, and yet has a low polymer content and good storage stability, while being suppressed in coloration.SOLUTION: The present invention provides a method for producing a compound represented by general formula (3) by reacting a specific silanol-modified polysiloxane compound with a cyclic silazane compound having a specific alkoxysilyl group [R1-R3 are monovalent hydrocarbon groups; R4 is a divalent hydrocarbon group optionally including a sulfur atom or the like; q is 0 or 1, r is 0, 1 or 2. Y is a substituent represented by general formula (4) or R13Si].SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound.

Background Art

[0002] Aminoalkyl-modified polysiloxane compounds (hereinafter also referred to as "amino-modified silicones") are used in various applications such as resin modifiers, fiber treatment agents, cosmetic raw materials, and paint additives by utilizing the reactivity of amino groups.

[0003] Amino-modified silicones can be synthesized by various methods. For example, Patent Document 1 discloses a method for obtaining both-terminal amino-modified silicone by dealcoholization condensation of a both-terminal silanol-modified polysiloxane compound and an aminoalkylalkoxysilane compound.

[0004] In addition, by reacting an amino-modified silicone with a haloalkylalkoxysilane compound, an amino-modified silicone having an alkoxysilylalkyl group as a substituent on nitrogen can be obtained. For example, Patent Document 2 discloses a method for obtaining both-terminal alkoxysilylmethylaminopropyl-modified polysiloxane, which is a compound having an α-alkoxysilyl structure introduced as a substituent on nitrogen, by reacting both-terminal amino-modified silicone with chloromethyltriethoxysilane.

[0005] Furthermore, Patent Document 3 discloses a method for obtaining an amino-modified silicone having an alkoxysilylalkyl group as a substituent on nitrogen by reacting an amino-modified silicone with 3-glycidyloxypropyltrimethoxysilane, which is an alkoxysilane compound having an epoxy group.

[0006] Such an amino-modified silicone having an alkoxysilylalkyl group as a substituent on nitrogen can form a cured film by hydrolytic condensation of the alkoxysilyl group site. Also, a film can be formed by co-hydrolytic condensation of an amino-modified silicone having an alkoxysilylalkyl group with a condensation-curable silicone compound or the like. Thereby, it is considered that water repellency and flexibility derived from the polysiloxane moiety of the amino-modified silicone can be imparted to the cured film of the condensation-curable silicone compound. Furthermore, a polysiloxane-modified resin can be synthesized by mixing an amino-modified silicone having an alkoxysilylalkyl group with a resin having a functional group capable of reacting with an amino group. This modified resin is considered to be useful because it can impart not only the properties derived from the polysiloxane moiety but also the effect of improving adhesion derived from the alkoxysilyl group.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] In order to obtain an amino-modified silicone having an alkoxysilylalkyl group as a substituent on nitrogen by the method described in Patent Document 1, a silanol-modified polysiloxane compound and a bis(alkoxysilylalkyl)amine such as bis(trimethoxysilylpropyl)amine may be subjected to dealcoholization condensation. However, in this method, it is difficult to selectively proceed the condensation reaction with only one alkoxysilyl group of the bis(alkoxysilylalkyl)amine, and both trialkoxysilyl groups of the bis(alkoxysilylalkyl)amine may react with the silanol groups of the silanol-modified polysiloxane compound. Further, although it is necessary to extract the alcohol generated as the reaction proceeds, the amount of alcohol generated is small relative to the weight of the reaction solution, and the alcohol cannot be sufficiently extracted unless the temperature is higher than the boiling point of the alcohol. For this reason, there is a problem that the product is likely to be colored.

[0009] In the case of the method described in Patent Document 2, since triethylamine hydrochloride is generated as the reaction proceeds, it is separated by filtration. However, since a part of triethylamine hydrochloride dissolves in the target product and is contained as chloride ions, there is a problem that it is likely to be colored in a series of processes of synthesis, isolation and storage. Further, since the reaction between the primary amino group of the both-end amino-modified silicone and chloromethyltriethoxysilane proceeds non-selectively, the amino groups in the molecule are obtained not only as the desired alkoxysilylmethylaminopropyl group which is a secondary amino group, but also as a mixture with the bis(alkoxysilylmethyl)aminopropyl group which is a tertiary amino group and the aminopropyl group which is a primary amino group. Among these, the bis(alkoxysilylmethyl)aminopropyl group which is a tertiary amino group has a hydrolyzable silyl group but does not have an NH structure, so it cannot form a covalent bond with a reactive resin or the like. On the other hand, the aminopropyl group which is a primary amino group does not have an alkoxysilyl group, so there is a possibility of causing deterioration of curability.

[0010] The production method of the both-end alkoxysilylalkylaminoalkyl-modified polysiloxane compound described in Patent Document 3 uses the ring-opening reaction of an epoxy group by an amino group, so there is no problem of crawl ions as in the method of Patent Document 2. However, in the reaction using an epoxy group and an amino group, as the reaction proceeds, the epoxy group opens to form a hydroxy group. This hydroxy group may condense intermolecularly or intramolecularly with an alkoxysilyl group derived from an alkoxysilane compound having an epoxy group, leading to polymerization. For this reason, insoluble components may be generated, causing turbidity, or the storage stability may deteriorate. In addition, since the reaction between the epoxy group and the amino group proceeds non-selectively in the same manner as the reaction of Patent Document 2, it is obtained as a mixture of compounds containing primary, secondary, or tertiary amino groups, and has the same problem as Patent Document 2.

[0011] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing an alkoxysilylalkylaminoalkyl-modified polysiloxane compound that reaches a sufficient reaction rate at low temperature and in a short time, has a low content of polymer, good storage stability, and suppressed coloring.

Means for Solving the Problems

[0012] As a result of intensive studies to solve the above problems, the present inventors have found that in the reaction between a silanol-modified polysiloxane compound and a cyclic silazane compound having an alkoxysilyl group, the silanol group of the silanol-modified polysiloxane compound and the cyclic silazane moiety of the cyclic silazane compound having an alkoxysilyl group react selectively, and an alkoxysilylalkylaminoalkyl-modified polysiloxane compound can be obtained without generating by-products, thereby completing the present invention.

[0013] That is, the present invention is 1. The following general formula (1)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0014] According to the present invention, since the reaction proceeds in a short time without generating by-products, an alkoxysilylalkylaminopropyl-modified polysiloxane compound can be easily obtained. In addition, in the process, since it is not exposed to high temperatures, a high-quality alkoxysilylalkylaminopropyl-modified polysiloxane compound can be obtained. Furthermore, the obtained alkoxysilylalkylaminopropyl-modified polysiloxane compound, in principle, always has an NH structure for the amino group in the molecule and always has an alkoxysilylalkyl group, so the reactivity of the amino group can be ensured and the effect of the alkoxysilyl group can be obtained.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Mode for Carrying Out the Invention

[0016] Hereinafter, the present invention will be specifically described. The method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (3) of the present invention (hereinafter referred to as "compound (3)") is a silanol-modified polysiloxane compound represented by the following general formula (1) (hereinafter referred to as "compound (1)") and a cyclic silazane compound having an alkoxysilyl group represented by the following general formula (2) (hereinafter referred to as "compound (2)") are reacted.

[0017]

Chemical formula

[0018] In the above general formulas (1) and (3), R 1is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R 1 As the monovalent hydrocarbon group of 1 , any of linear, branched, and cyclic forms may be used. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, from the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, an n-propyl group, a vinyl group, and a phenyl group are preferable.

[0019] Also, the monovalent hydrocarbon group of R 1 may have some or all of the hydrogen atoms substituted with fluorine atoms or chlorine atoms. Specific examples of the monovalent hydrocarbon group substituted with these include fluoroalkyl groups such as (3,3,3-trifluoro)propyl group; and chloroalkyl groups such as chloromethyl group and chloropropyl group.

[0020] In the above general formula (1), X is a hydrogen atom or R 1 3 Si-, and R 1 represents the same meaning as described above.

[0021] Specific examples of the compound (1) include 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-vinyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-chloromethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-chloropropyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5-hexavinyl-7,7,7-trimethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5-hexaphenyl-7,7,7-trimethyltetrasiloxane, 1-hydroxy-1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5,7,7-hexamethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7-heptavinyl-7,7-dimethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7-heptamethyl-7,7-diphenyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octaphenyl-7-methyl-tetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7,7-nonaphenyltetrasiloxane, α-hydroxy-ω-methylpolydimethylpolysiloxane, α-hydroxy-ω-vinylpolydimethylpolysiloxane, α-hydroxy-ω-chloromethyldimethylpolysiloxane, α-hydroxy-ω-chloropropyldimethylpolysiloxane, α-hydroxy-ω-phenyldimethylpolysiloxane and other 1-hydroxypolysiloxane compounds; 1,7-dihydroxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,7-dihydroxy-1,1,3,3,5,5,7-heptamethyl-7-vinyltetrasiloxane, 1,7-dihydroxy-1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5,7,7-pentamethyltetrasiloxane, α,ω-dihydroxydimethylpolysiloxane and other dihydroxypolysiloxane compounds; and dialkylsilanediols such as dibutylsilanediol, diphenylsilanediol, and dicyclopentylsilanediol.

[0022] In the above general formulas (2) and (3), R 2 and R 3 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R 2 and R 3 The monovalent hydrocarbon groups may be linear, branched, or cyclic. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; and aryl groups such as phenyl group. Among these, a methyl group and an ethyl group are preferred from the viewpoint of easy availability of raw materials.

[0023] Also, R 4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, which may contain a sulfur atom, a silicon atom, an ester bond, or a urea bond. R 4 The divalent hydrocarbon groups may be linear, branched, or cyclic. Specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene groups; branched alkylene groups such as methylethylene and methyltrimethylene groups; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene groups; linear alkenylene groups such as propenylene, butenylene, hexenylene, and octenylene groups; branched alkenylene groups such as isopropenylene and isobutenylene groups; arylene groups such as phenylene group; and aralkylen groups such as methylenephenylene, methylenephenylenemethylene, and methylenephenyleneethylene groups. Among these, from the viewpoint of easy availability of raw materials, a linear alkylene group is preferred, and a linear alkylene group having 1 to 6 carbon atoms is more preferred.

[0024] R 4Specific examples of the divalent hydrocarbon group when it contains a sulfur atom include a thioalkylene group, an alkylenethioalkylene group, and the like. R 4 Specific examples of the divalent hydrocarbon group when it contains a silicon atom include an alkylenedialkylsilylalkylene group and a substituent represented by the following general formula (5). These alkylene groups include the same groups as those exemplified above, but a linear alkylene group having 1 to 6 carbon atoms is preferred.

[0025]

Chemical formula

[0026] In general formula (5), R 4’ each independently represents an oxygen atom or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. However, the total number of carbon atoms contained in two R 4’ is the same as that of R 4 Specific examples of this divalent hydrocarbon group include the same groups as those exemplified for R 4 above.

[0027] R 4 Examples of the divalent hydrocarbon group when it contains an ester bond include a substituent represented by the following general formula (6). Examples of the divalent hydrocarbon group when it contains a urea bond include a substituent represented by the following general formula (7). 4 When R

[0028]

Chemical formula

[0029] In general formulas (6) and (7), R 4 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. However, the total number of carbon atoms in two R 4The total number of carbon atoms contained therein is R 4 and is the same as R 4 As the divalent hydrocarbon group of “”, R 4 Among the groups exemplified by, those having 1 to 10 carbon atoms are mentioned. In general formula (7), R 5 is a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The monovalent hydrocarbon group of R 5 includes substituents similar to R 1 and a hydrogen atom is preferred particularly from the viewpoint of ease of raw material procurement.

[0030] In general formulas (2) and (3), q is 0 or 1, and r is 0, 1 or 2.

[0031] Specific examples of the compound (2) include 2,2-dimethoxy-N-(trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-[(trimethoxysilyl)ethyldimethylsiloxydimethylsilyl(methyl)propyl]-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-[(trimethoxysilyl)ethyldimethylsiloxydimethylsilyl(methyl)propyl]-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(3-trimethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(3-triethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(3-trimethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(3-triethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(3-trimethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(3-trimethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(3-triethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(3-triethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylethyldimethylsiloxydimethylsilylpropyl(methyl))-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(1,1,1-trimethoxy-3,3,5,5,7,7-hexamethyltetrasiloxydimethylsilylpropyl)-1-aza-2-silacyclopentane and other cyclic silazane compounds having a trialkoxysilylalkyl group; 2,2-dimethoxy-N-(methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(methyldimethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(methyldiethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(methyldiethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(3-methyldimethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,Cyclic silazane compounds having an alkyldialkoxysilylalkyl group such as 2 - diethoxy - N - (3 - methyldiethoxysilylpropoxycarbonylethyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (3 - methyldimethoxysilylpropoxycarbonyl(methyl)ethyl) - 1 - aza - 2 - silacyclopentane, 2,2 - diethoxy - N - (3 - methyldiethoxysilylpropoxycarbonyl(methyl)ethyl) - 1 - aza - 2 - silacyclopentane; 2,2 - dimethoxy - N - (dimethylmethoxysilylmethyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (dimethylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (dimethylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (dimethylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (dimethylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (diethylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (diethylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (diethylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (diethylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (diphenylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2,2 - dimethoxy - N - (diphenylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (diphenylmethoxysilylhexyl) - 1 - aza - 2 - silacyclopentane, 2 - methoxy - 2 - methyl - N - (diphenylmethoxysilyloctyl) - 1 - aza - 2 - silacyclopentane, 2,2 - diethoxy - N - (dimethylethoxysilylmethyl) - 1 - aza - 2 - silacyclopentane and other cyclic silazane compounds having a dialkylalkoxysilylalkyl group, etc. can be mentioned.,

[0032] Compound (2) can be produced by known methods described in, for example, JP-A-2011-102267.

[0033] In the above general formula (3), Y is a substituent represented by the following general formula (4) or R 1 3 Si(R 1 represents the same meaning as described above.)

[0034] [Chemical formula] (In the formula, R 2 ~R 4 , q and r represent the same meaning as described above.)

[0035] In the production method of the present invention, the mixing ratio of compound (1) and compound (2) is not particularly limited, but compound (2) is preferably 1 to 2 moles, more preferably 1 to 1.5 moles, and even more preferably 1 to 1.2 moles per mole of the silanol group in compound (1).

[0036] In the reaction, compound (2) may be added to compound (1), or compound (1) may be added to compound (2). The reaction temperature is not particularly limited, but from the viewpoint of the stability of the product, it is preferably 0 to 200°C, more preferably 0 to 150°C, and even more preferably 10 to 60°C. The reaction time is also not particularly limited, but from the viewpoint of the stability of the product, it is preferably 5 minutes to 40 hours, more preferably 10 minutes to 20 hours, and even more preferably 10 minutes to 5 hours. The above reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon in order to prevent dehydration condensation of compound (1) and hydrolysis of compound (2) or (3).

[0037] The above reaction proceeds even without a solvent, but a solvent can also be used. Specific examples of the solvent include aliphatic hydrocarbon solvents having 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents having 6 to 10 carbon atoms such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; silicone solvents such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more kinds.

[0038] Isolation and purification of the compound (3) obtained in the above reaction can be appropriately selected from ordinary purification methods in organic synthesis such as vacuum stripping, various chromatographies, treatment using adsorbents such as activated carbon, and filtration.

[0039] Specific examples of the compound (3) include 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(3-triethoxysilylpropylaminopropyl)-1,1-diethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-trimethoxysilylpropyloctyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-triethoxysilylpropylaminopropyl)-1,1-diethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-triethoxysilylpropylaminopropyl)-1-ethoxy-1,3,3,5,5,7,7,9,9,9-decamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-vinylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-chloromethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-chloropropylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7-hexavinyl-9,9,9-trimethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7-hexaphenyl-9,9,9-trimethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,5,7-tris(3,3,3-trifluoropropyl)-3,5,7,9,9,9-hexamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9-heptavinyl-9,9-Dimethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9-heptamethyl-9,9-diphenylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octaphenyl-7-methyl-pentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonaphenylpentasiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-methylpolydimethylpolysiloxane, α-(3-triethoxysilylpropylaminopropyl)-α,α-diethoxy-ω-methylpolydimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-vinylpolydimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-chloromethyldimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-chloropropyldimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-phenyldimethylpolysiloxane, etc., where Y is R, 1 31-(Alkoxysilylalkylaminopropyl)polysiloxane compounds in the case of Si; 1,11-bis(3-trimethoxysilylpropylaminopropyl)-1,1,11,11-tetramethoxy-3,3,5,5,7,7,9,9-octamethylhexasiloxane, 1,11-bis(3-triethoxysilylpropylaminopropyl)-1,1,11,11-tetraethoxy-3,3,5,5,7,7,9,9-octamethylhexasiloxane, 1,11-bis(3-trimethoxysilylpropylaminopropyl)-1,1,11,11-tetramethoxy-3,3,5,5,7,7,9-heptamethyl-9-vinyl-hexasiloxane, 1,11-bis(3-trimethoxysilylpropylaminopropyl)-1,1,11,11-tetramethoxy-3,5,7-tris(3,3,3-trifluoropropyl)-3,5,7,9,9-pentamethylhexasiloxane, α,ω-bis(3-trimethoxysilylpropylaminopropyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω-bis(3-triethoxysilylpropylaminopropyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(8-trimethoxysilylpropy laminooctyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω-bis(8-triethoxysilylpropylaminooctyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(trimethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω-bis(triethoxysilylpropylaminomethyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(dimethylmethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω-bis(dimethylethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane and the like, and α,ω-bis(alkoxysilylalkylaminopropyl)polysiloxane compounds and the like in the case where Y is of the general formula (4) are exemplified.

Examples

[0040] Hereinafter, the present invention will be described more specifically by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0041] [Synthesis Example 1] Synthesis of 2,2-dimethoxy-N-(trimethoxysilyloctyl)-1-aza-2-silacyclopentane [Chemical Formula] (In the formula, Me represents a methyl group. The same applies hereinafter.)

[0042] The inside of a four-necked glass flask equipped with a stirrer, thermometer, distillation column, and reflux condenser was purged with nitrogen, and 122 g (0.296 mol) of (trimethoxysilylpropyl)-(trimethoxysilyloctyl)amine, 132 g of toluene, and 0.75 g (0.0050 mol) of trifluoromethanesulfonic acid were added and refluxed. To this mixture, 58.4 g (0.311 mol) of N-trimethylsilyl-N-methylaniline was added and stirred, and the generated trimethylmethoxysilane was withdrawn using a distillation column together with toluene until the reaction temperature reached 150°C. The obtained reaction solution was distilled to obtain 66 g of a fraction having a boiling point of 170°C / 0.5 kPa (yield 58%). IR and 1 1H-NMR analysis were performed. The results are shown in FIGS. 1 and 2.

[0043] [Synthesis Example 2] Synthesis of 2-ethoxy-2-methyl-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane [Chemical Formula] (In the formula, Et represents an ethyl group. The same applies hereinafter.)

[0044] The interior of a four-necked glass flask equipped with a stirrer, a thermometer, a distillation column, and a reflux condenser was purged with nitrogen, and 162 g (0.348 mol) of (methyldiethoxysilylpropyl)-(triethoxysilyloctyl)amine, 114 g of toluene, and 1.0 g (0.0067 mol) of trifluoromethanesulfonic acid were added, followed by refluxing. To this mixture, 68.5 g (0.382 mol) of N-trimethylsilyl-N-methylaniline was added and stirred, and the generated trimethylethoxysilane was extracted using the distillation column together with toluene until the reaction temperature reached 150 °C. The obtained reaction solution was distilled to obtain 110 g of a fraction having a boiling point of 177 °C / 0.2 kPa (yield 75%). IR and 1 1H-NMR analyses of the obtained fraction were performed. The results are shown in Figures 3 and 4.

[0045] [Synthesis Example 3] Synthesis of 2-methoxy-2-methyl-N-(trimethoxysilylpropylthioethyl)-1-aza-2-silacyclopentane [Chemical formula]

[0046] The interior of a four-necked glass flask equipped with a stirrer, a thermometer, a distillation column, and a reflux condenser was purged with nitrogen, and 86.0 g (0.221 mol) of (methyldimethoxysilylpropyl)-(trimethoxysilylpropylthioethyl)amine, 110 g of toluene, and 0.4 g (0.003 mol) of trifluoromethanesulfonic acid were added, followed by refluxing. To this mixture, 44.0 g (0.245 mol) of N-trimethylsilyl-N-methylaniline was added and stirred, and the generated trimethylmethoxysilane was extracted using the distillation column together with toluene until the reaction temperature reached 140 °C. The obtained reaction solution was distilled to obtain 54 g of a fraction having a boiling point of 140-150 °C / 0.4 kPa (yield 69%). IR and 1 1H-NMR analyses of the obtained fraction were performed. The results are shown in Figures 5 and 6.

[0047] [Synthesis Example 4] Synthesis of 2,2-diethoxy-N-triethoxysilylmethyl-1-aza-2-silacyclopentane [Chemical formula]

[0048] The inside of a four-necked glass flask equipped with a stirrer, a thermometer, and a reflux condenser was purged with nitrogen, and 126.1 g (40% by mass THF solution, 0.2752 mol) of sodium hexamethyldisilazide was charged and cooled to 5 °C. 99.3 g (0.250 mol) of (triethoxysilylmethyl)(triethoxysilylpropyl)amine was added dropwise thereto over 1 hour, and the mixture was stirred at the same temperature for 1 hour. When the reaction solution was analyzed by GC-MS, it was found that 2,2-diethoxy-N-triethoxysilylmethyl-1-aza-2-silacyclopentane was produced at a reaction rate of 97%. Further, after filtering the obtained reaction solution, it was distilled, and 54.0 g of 2,2-diethoxy-N-triethoxysilylmethyl-1-aza-2-silacyclopentane was obtained as a fraction having a boiling point of 105 °C / 0.4 kPa. For the obtained compound, IR, 1 1H-NMR analysis was performed. The results are shown in FIGS. 7 and 8. Note that the above reaction rate was determined by the following calculation from the area values of the raw material and the product by gas chromatography analysis (hereinafter also referred to as GC analysis). (Area value of product) / (Area value of raw material + Area value of product) × 100

[0049] [Example 1-1] Synthesis of 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane [Chemical formula]

[0050] The interior of a four-necked glass flask equipped with a stirrer, a thermometer, and a reflux condenser was purged with nitrogen, and 10 g (0.032 mol) of 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane (A) was charged. To this, 9.9 g (0.032 mol) of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was added dropwise from a dropping funnel, and the mixture was stirred at room temperature for 1 hour. When the reaction solution was analyzed by gas chromatography (hereinafter referred to as "GC analysis"), the residues of 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane and 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane were not confirmed, and the target compound (B) was produced. Incidentally, when the reaction rate based on 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane was calculated according to the following formula, it was 96%. Also, when the production rate of the by-product (C) was calculated according to the following formula, it was 1%. Reaction rate: [(GC area value of B + GC area value of C) / (GC area value of A + GC area value of B + GC area value of C)] × 100 Production rate of (C): GC area value of C / (GC area value of B + GC area value of C)

[0051] [Comparative Example 1-1] Synthesis of 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane [Chemical formula]

[0052] The reaction was carried out in the same manner as in Example 1-1 except that 11 g (0.032 mol) of bis(3-trimethoxysilylpropyl)amine was used instead of 9.9 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane. When the reaction solution was analyzed by GC, the target compound (B) was produced, but 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane and bis(3-trimethoxysilylpropyl)amine remained. Also, when calculating the reaction rate based on 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane in the same manner as in Example 1-1, it was 89%, and the production rate of by-product (C) was 39%.

[0053] [Comparative Example 1-2] Synthesis of 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane The reaction solution obtained in Comparative Example 1-1 was heated to 130 °C, and methanol generated as the reaction proceeded was removed from the system. The distillation of methanol was continued until the reaction temperature reached 155 °C, and then it was cooled to room temperature. At this point, when the reaction solution was subjected to GC analysis in the same manner as in Example 1-1, and the reaction rate was calculated based on 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, it was 100%, and the production rate of by-product (C) was 33%. From the above, 18 g of 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane (Compound 8) was obtained as a yellow transparent liquid.

[0054] [Example 1-2] Synthesis of both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound 1 [Chemical formula]

[0055] The interior of a four-necked glass flask equipped with a stirrer, a thermometer, and a reflux condenser was purged with nitrogen, and 225 g (0.15 mol as silanol) of silanol-modified polydimethylsiloxane having a number average molecular weight of 3000 by gel permeation chromatography (hereinafter referred to as "GPC") was charged and stirred. To this, 51.0 g (0.165 mol) of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was added from a dropping funnel, and the mixture was stirred at room temperature for 1 hour. The reaction solution was analyzed by GC, and when the disappearance of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was confirmed, the reaction was terminated. Also, when IR analysis of the product was performed, the peak derived from silanol had disappeared. From the above, 268.5 g of the both-terminal alkoxysilylpropylaminopropyl-modified polysiloxane compound 1 was obtained as a colorless transparent liquid.

[0056] [Example 1-3] Synthesis of both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound 2

Chemical formula

[0057] The reaction was carried out in the same manner as in Example 1-2, except that 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced with 63.0 g (0.165 mol) of 2,2-diethoxy-N-triethoxysilylpropyl-1-aza-2-silacyclopentane. When IR analysis of the product was performed, the peak derived from silanol had disappeared, and 286.5 g of the both-terminal alkoxysilylpropylaminopropyl-modified polysiloxane compound 2 was obtained as a colorless transparent liquid.

[0058] [Example 1-4] Synthesis of both-terminal alkoxysilylalkylaminooctyl-modified polysiloxane compound 3

Chemical formula

[0059] The reaction was carried out in the same manner as in Example 1-2, except that the amount of the silanol-modified polydimethylsiloxane used was changed to 15.0 g (0.0100 mol as silanol), and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced by 4.1 g (0.011 mol) of 2,2-dimethoxy-N-trimethoxysilyloctyl-1-aza-2-silacyclopentane. When IR analysis of the product was performed, the peak derived from silanol disappeared, and 18 g of the both-terminal alkoxysilylalkylaminooctyl-modified polysiloxane compound 3 was obtained as a colorless transparent liquid.

[0060] [Example 1-5] Synthesis of both-terminal alkoxysilylalkylaminooctyl-modified polysiloxane compound 4

Chemical formula

[0061] The reaction was carried out in the same manner as in Example 1-2, except that the amount of the silanol-modified polydimethylsiloxane used was changed to 15 g (0.010 mol as silanol), and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced by 4.8 g (0.011 mol) of 2-ethoxy-2-methyl-N-triethoxysilyloctyl-1-aza-2-silacyclopentane. When IR analysis of the product was performed, the peak derived from silanol disappeared, and 19 g of the both-terminal alkoxysilylalkylaminooctyl-modified polysiloxane compound 4 was obtained as a colorless transparent liquid.

[0062] [Example 1-6] Synthesis of both-terminal alkoxysilylalkylaminoalkyl-modified polysiloxane compound 5

Chemical formula

[0063] The reaction was carried out in the same manner as in Example 1-2, except that the amount of silanol-modified polydimethylsiloxane used was changed to 15 g (0.010 mol as silanol), and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced by 3.9 g (0.011 mol) of 2-methoxy-2-methyl-N-trimethoxysilylpropylthioethyl-1-aza-2-silacyclopentane. When IR analysis of the product was performed, the peak derived from silanol disappeared, and 18 g of a both-terminal alkoxysilylpropylaminoalkyl-modified polysiloxane compound 5 was obtained as a colorless transparent liquid.

[0064] [Example 1-7] Synthesis of both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound 6

Chemical formula

[0065] The reaction was carried out in the same manner as in Example 1-2, except that the silanol-modified polydimethylsiloxane was replaced by 50 g (0.10 mol as silanol) of a silanol-modified polydimethylsiloxane having a number average molecular weight of 1000 by GPC, and the amount of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane used was changed to 32.5 g (0.105 mol). When IR analysis of the product was performed, the peak derived from silanol disappeared, and 81 g of a both-terminal alkoxysilylpropylaminopropyl-modified polysiloxane compound 6 was obtained as a colorless transparent liquid.

[0066] [Example 1-8] Synthesis of both-terminal alkoxysilylalkylaminomethyl-modified polysiloxane compound 7

Chemical formula

[0067] The reaction was carried out in the same manner as in Example 1-2, except that the amount of the silanol-modified polydimethylsiloxane was changed to 15 g (0.010 mol as silanol), and 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced with 3.9 g (0.011 mol) of 2,2-diethoxy-N-triethoxysilylmethyl-1-aza-2-silacyclopentane. When IR analysis of the product was performed, the peak derived from silanol disappeared, and 18 g of the both-terminal alkoxysilylpropylaminomethyl-modified polysiloxane compound 7 was obtained as a colorless transparent liquid.

[0068] [Comparative Example 1-3] Synthesis of both-terminal alkoxysilylalkylaminomethyl-modified polysiloxane compound 9

Chemical formula

[0069] According to Patent Document 2, the inside of a four-necked glass flask equipped with a stirrer, a thermometer, and a reflux condenser was purged with nitrogen, and 80 g (0.053 mol as amino group) of amino-modified polydimethylsiloxane, 7.7 g (0.076 mol) of triethylamine, and 40 g of toluene were charged and heated to 90°C. To this, 15 g (0.072 mol) of chloromethyltriethoxysilane was added dropwise from a dropping funnel, and the mixture was stirred at the same temperature for 20 hours. At this point, when the reaction solution was analyzed by GC, chloromethyltriethoxysilane remained. The obtained reaction solution was filtered to remove the triethylamine hydrochloride generated by the reaction, and the residue was washed with toluene. Then, toluene was removed from the filtrate to obtain a brown transparent both-terminal alkoxysilylalkylaminomethyl-modified polysiloxane compound 9.

[0070] [Comparative Example 1-4] Synthesis of both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound 10

Chemical formula

[0071] According to Patent Document 3, the inside of a four-necked glass flask equipped with a stirrer, a thermometer, and a reflux condenser was purged with nitrogen, and 75 g (0.050 mol as amino groups) of amino-modified polydimethylsiloxane was charged and heated to 100 °C. To this, 18.8 g (0.050 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise from a dropping funnel, and the mixture was stirred at the same temperature for 12 hours. GC analysis showed that a small amount of 3-glycidoxypropyltrimethoxysilane remained. Without performing any further operations, a colorless slightly turbid alkoxysilylalkylaminopropyl-modified polysiloxane compound 10 was obtained.

[0072] From the results of Examples 1-1 to 1-8, it can be seen that in the reaction between the silanol-modified polysiloxane compound and the cyclic silazane compound having an alkoxysilyl group, the silanol site and the cyclic silazane site react at room temperature in a short time. In particular, from the results of Example 1-1, Comparative Example 1-1, and Comparative Example 1-2, it can be seen that the formation rate of by-products is small and the reaction proceeds highly selectively. On the other hand, in the reaction between the silanol-modified polysiloxane compound and bis(alkoxysilylalkyl)amine in Comparative Example 1-1 and Comparative Example 1-2, the reaction rate was not sufficient at room temperature and the raw materials remained. In order to increase the reaction rate, alcohol had to be removed by heating. However, despite reacting at a high temperature for a long time, one of the raw materials remained in Comparative Example 1-3 and Comparative Example 1-4.

[0073] [Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-3] Each of the both-terminal alkoxysilylalkylaminomethyl-modified polysiloxane compounds 1 to 10 obtained in Examples 1-2 to 1-8 and Comparative Examples 1-2 to 1-4 was placed in a sample bottle so as to prevent moisture from entering, and the inside was purged with nitrogen. This was allowed to stand at room temperature (25 °C) for 1 month, and changes in appearance and hue were visually confirmed and compared with the reaction solution immediately after the reaction. The results are shown in Table 1.

[0074]

Table 1

[0075] As shown in Table 1, for the both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compounds 1 to 7 of the present invention obtained in Examples 1-2 to 1-8, even after one month had passed after production, no changes were observed in terms of appearance, properties, and fluidity. On the other hand, for the both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound obtained in Comparative Example 1-2, since it was exposed to high temperature during production, the product became colored (Comparative Example 2-1). For the both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound obtained in Comparative Example 1-3, since it was a production method in which chloride ions were generated, significant coloring was observed during the reaction (Comparative Example 2-2). Also, for the both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound obtained in Comparative Example 1-4, although no coloring was observed, it was turbid, suggesting the formation of a polymer. The both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound after one month had solidified and lost its fluidity. It is considered that the alcohol generated by the ring-opening of the epoxy group condensed intramolecularly and intermolecularly, resulting in an increase in viscosity and solidification (Comparative Example 2-3).

Claims

1. A silanol-modified polysiloxane compound represented by the following general formula (1) and a cyclic silazane compound having an alkoxysilyl group represented by the following general formula (2) are reacted to produce an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (3). 【Chemical 1】 (wherein, R 1 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X represents a hydrogen atom or R 1 3 Si(R 1 represents the same meaning as described above.), and p is an integer of 1 to 1000.) A method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (3) by reacting a silanol-modified polysiloxane compound represented by the following general formula (1) with a cyclic silazane compound having an alkoxysilyl group represented by the following general formula (2). [Chemical Formula 2] (wherein, R 2 and R 3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 4 represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a sulfur atom, a silicon atom, an ester bond or a urea bond, q is 0 or 1, and r is 0, 1 or 2.) A method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (3) by reacting a silanol-modified polysiloxane compound represented by the following general formula (1) with a cyclic silazane compound having an alkoxysilyl group represented by the following general formula (2). 【Chemical Formula 3】 [wherein, R 1 to R 4 , p, q and r have the same meanings as described above, and Y is represented by the following general formula (4) 【Chemical 4】 (wherein, R 2 ~ R 4 , q and r represent the same meanings as described above.) The substituent represented by or R 1 3 Si(R 1 represents the same meaning as described above.) represents.] A method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (3).

2. The production method of the alkoxysilylalkylaminopropyl-modified polysiloxane compound according to Claim 1, wherein the mixing ratio of the silanol-modified polysiloxane compound represented by the general formula (1) and the cyclic silazane compound having an alkoxysilyl group represented by the general formula (2) is 1.0 to 1.2 moles of the cyclic silazane compound having an alkoxysilyl group per 1 mole of the silanol group in the silanol-modified polysiloxane compound.

3. The above-mentioned R 4 The method for producing an alkoxysilylalkylaminopropyl-modified polysiloxane compound according to claim 1, wherein R is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a sulfur atom (excluding a methylene group).

Images