Compositions containing aminoalkylalkoxydisiloxane compounds and aminoalkylalkoxyoligosiloxane compounds and methods for producing the same

Abstract

Provided is a composition comprising: an aminoalkyl alkoxy disiloxane compound represented by general formula (1) [where R1 represents a divalent hydrocarbon group, R2 and R3 represent a monovalent hydrocarbon group, each A independently represents a group represented by general formula (2) (where R4 and R5 each independently represent a hydrogen atom or a monovalent hydrocarbon group and may bond with each other to form a ring structure, excluding cases where R4 and R5 are both a hydrogen atom), and each n is independently 0 or 1]; and an aminoalkyl alkoxy oligosiloxane compound represented by general formula (3) (where R1 to R3, A, and n are the same as above, m represents an integer of 1-6, and X represents R2 or OR3). The composition exhibits good properties.

Description

[Technical Field]

[0001] The present invention relates to compositions containing aminoalkylalkoxydisiloxane compounds and aminoalkylalkoxyoligosiloxane compounds, and to methods for producing the same. [Background technology]

[0002] The aminoalkylalkoxysilane compound is useful as a silane coupling agent, a surface treatment agent, a resin additive, a resin modifier, a paint additive, or the like. Known examples of such aminoalkylalkoxysilane compounds include organoxysilane compounds having a primary amino group, such as aminopropyltrimethoxysilane, organoxysilane compounds having a secondary amino group, such as N-phenylaminopropyltrimethoxysilane, and organoxysilane compounds having a tertiary amino group, such as dimethylaminopropyltrimethoxysilane.

[0003] Aminoalkylalkoxysilane compounds (hereinafter referred to as "monomer compounds") can undergo hydrolysis and condensation to yield the corresponding aminoalkylalkoxydisiloxane compounds (hereinafter referred to as "disiloxane compounds"), aminoalkylalkoxytrisiloxane compounds (hereinafter referred to as "trisiloxane compounds"), and further hydrolysis and condensation products (hereinafter, the hydrolysis and condensation products from trisiloxane compounds to octasiloxanes are collectively referred to as "oligosiloxane compounds"). These hydrolysis and condensation products have a higher molecular weight than monomer compounds, making them less volatile and easier to handle. Furthermore, they generate fewer volatile compounds (VOCs) per unit mass than monomer compounds, which reduces their impact on the environment and human health. Additionally, polymerization increases the number of reactive sites and functional groups within the molecule, potentially providing favorable properties for the above-mentioned applications.

[0004] For example, in Patent Document 1, a disiloxane compound is synthesized by hydrolyzing and condensing an aminoalkylalkoxysilane compound, followed by distillation and purification. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-193976 Summary of the Invention [Problem to be solved by the invention]

[0006] In Patent Document 1, since the alkoxysilyl group in the monomer compound is a trialkylmonoalkoxysilyl group, when a hydrolysis condensation reaction is carried out, in principle, only a disiloxane compound having no alkoxysilyl group is obtained. For this reason, there is no description of condensates of trisiloxane compounds or higher, and the usefulness of including such compounds is not made clear.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition containing an aminoalkylalkoxydisiloxane compound and an aminoalkylalkoxyoligosiloxane compound that exhibit good properties, as well as a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive research aimed at solving the above problems, the present inventors discovered that, in the process of producing and isolating an aminoalkylalkoxydisiloxane compound, a composition containing a small amount of an aminoalkyloligosiloxane compound can be obtained, despite the substantial difference in boiling point, and that compositions containing an aminoalkylalkoxydisiloxane compound and an aminoalkyloligosiloxane compound exhibit superior properties to aminoalkylalkoxysilane compounds and aminoalkylalkoxydisiloxane compounds in general uses of this type of compound, such as surface treatment, and thus completed the present invention.

[0009] That is, the present invention is 1. The following general formula (1) [ka] [In the formula, R 1 each independently represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and R 2 and R 3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and each A independently represents a group represented by the following general formula (2): [ka] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom, and may be bonded to each other to form a ring structure, but R 4 and R 5 Except when both are hydrogen atoms.) and n is independently 0 or 1. and an aminoalkylalkoxydisiloxane compound represented by the following general formula (3): [ka] (In the formula, R 1 ~R 3 , A and n have the same meanings as above, m is an integer of 1 to 6, and X is R 2 OR 3 represents.) and an aminoalkylalkoxyoligosiloxane compound represented by the formula: 2. The composition of 1, wherein the content (area ratio) of the aminoalkylalkoxyoligosiloxane compound is 0.05 to 20% based on the total amount of the aminoalkylalkoxydisiloxane compound and the aminoalkylalkoxyoligosiloxane compound. 3. The following general formula (4) [ka] (In the formula, R 1 ~R 3, A and n have the same meanings as above. to obtain an aminoalkylalkoxydisiloxane compound represented by the general formula (1), an aminoalkylalkoxyoligosiloxane compound represented by the general formula (3), an aminoalkylalkoxysilane compound represented by the general formula (4), and an aminoalkylalkoxysilane compound represented by the following general formula (5): [ka] (In the formula, R 3 represents the same meaning as above.) The method for producing the composition of claim 1 or 2, wherein the mixture containing the alcohol compound represented by the formula: to provide. [Effects of the Invention]

[0010] The composition of the present invention is less volatile than monomer compounds, generates fewer VOCs per unit mass, and contains a small amount of aminoalkyl oligosiloxane compound in addition to aminoalkyl alkoxy disiloxane compounds, which increase the number of reactive sites and functional groups in the molecule. Therefore, compared to monomer compounds and disiloxane compounds, the composition exhibits better properties when used in a variety of applications. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be specifically described below. The composition of the present invention contains an aminoalkylalkoxydisiloxane compound represented by the following general formula (1) (hereinafter also referred to as compound (1)) and an aminoalkylalkoxyoligosiloxane compound represented by the following general formula (3) (hereinafter also referred to as compound (3)).

[0012] [ka]

[0013] In the above general formulas (1) and (3), R 1each independently represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. R 1 The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and octamethylene; branched alkylene groups such as methylethylene (propylene) and methyltrimethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as propenylene, butenylene, hexenylene, and octenylene; branched alkenylene groups such as isopropenylene and isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylenemethylene. Among these, from the viewpoint of ease of procurement of raw materials, a linear alkylene group is preferred, and a linear alkylene group having 1 to 3 carbon atoms is more preferred.

[0014] In the above general formulas (1) and (3), R 2 and R 3 each independently represents 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 group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and thexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl; and aryl groups such as phenyl. Among these, from the viewpoint of ease of procurement of raw materials, a linear alkyl group is preferred, and a linear alkyl group having 1 to 3 carbon atoms is more preferred.

[0015] In the above general formulas (1) and (3), each A independently represents a group represented by the following general formula (2).

[0016] [ka]

[0017] In the above general formula (2), R 4 and R 5 are each independently a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, which may contain an oxygen atom or a nitrogen atom, and R 4 and R 5 cannot both be hydrogen atoms. R 4 and R 5 The monovalent hydrocarbon group may be linear, branched, or cyclic, and 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; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, thexyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, butenyl, pentenyl, and octenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl.

[0018] Also, R 4 and R 5 may be bonded to each other to form a ring structure represented by the following general formula (7) together with the nitrogen atom.

[0019] [ka]

[0020] In general formula (7), R 4 and R 5When R forms a ring, the number of carbon atoms contained in the ring is preferably 3 to 6. 4 and R 5 and preferably form a linear alkylene group having 3 to 6 carbon atoms. In addition, this alkylene chain may contain -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), etc. Examples of the linear alkylene group having 3 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms include the above-mentioned R 1 and R 2 Examples of the groups include the same as those exemplified in the above. Examples of such a ring structure include a piperidine ring, a pyrrolidine ring, a piperazine ring, a methylpiperazine ring, and a morpholine ring.

[0021] In the general formula (3), X is R 2 OR 3 and R 2 and R 3 As for the above R 2 and R 3 The same can be mentioned. Furthermore, m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1. If m exceeds 6, the viscosity increases, making handling difficult.

[0022] In the general formulae (1) and (3), each n is independently 0 or 1.

[0023] Specific examples of compound (1) include 1,3-bis(diethylaminopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dimethylaminopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dibutylaminopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(butylaminopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(octylaminopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(phenylaminopropyl)-1,1, 3,3-Tetramethoxydisiloxane, 1,3-bis(morpholinopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(piperazinopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(methylpiperazinopropyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(diethylaminopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dimethylaminopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dibutylaminopropyl)-1,1 ,3,3-tetraethoxydisiloxane, 1,3-bis(butylaminopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(octylaminopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(phenylaminopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(morpholinopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(piperazinopropyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(methylpiperazinopropyl)-1,1 ,3,3-tetraethoxydisiloxane, 1,3-bis(diethylaminomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dimethylaminomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dibutylaminomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(butylaminomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(octylaminomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(phenylaminomethyl)-1,1,3,3-Tetramethoxydisiloxane, 1,3-bis(morpholinomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(piperazinomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(methylpiperazinomethyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(diethylaminomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dimethylaminomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dibutylaminomethyl)-1,1,3,3-tetraethoxydisiloxane tetraethoxydisiloxane, 1,3-bis(butylaminomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(octylaminomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(phenylaminomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(morpholinomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(piperazinomethyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(methylpiperazinomethyl)-1,1,3,3-tetraethoxydisiloxane 1,3-bis(diethylaminooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dimethylaminooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(dibutylaminooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(butylaminooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(octylaminooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(phenylaminooctyl)-1,1,3,3- Tetramethoxydisiloxane, 1,3-bis(morpholinooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(piperazinooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(methylpiperazinooctyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(diethylaminooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dimethylaminooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(dibutylaminooctyl)-1,1,3,3-Tetraethoxydisiloxane, 1,3-bis(butylaminooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(octylaminooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(phenylaminooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(morpholinooctyl)-1,1,3,3-tetraethoxydisiloxane, 1,3-bis(piperazine) 1,3-bis(aminoalkyl)1,1,3,3-tetraalkoxydisiloxane compounds such as 1,3-bis(diethylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane and 1,3-bis(dimethylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane; -1,3-dimethyldisiloxane, 1,3-bis(dibutylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, 1,3-bis(butylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, 1,3-bis(octylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, 1,3-bis(phenylaminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane Examples of suitable 1,3-bis(aminoalkyl)-1,3-dialkoxy-1,3-dialkyldisiloxane compounds include 1,3-bis(aminoalkyl)-1,3-dialkoxy-1,3-dialkyldisiloxane compounds such as 1,3-bis(morpholinopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, 1,3-bis(piperazinopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, and 1,3-bis(methylpiperazinopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane.

[0024] Specific examples of compound (3) include 1,3,5-tris(diethylaminopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(dimethylaminopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(dibutylaminopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(butylaminopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, and 1,3,5-tris(phenylaminopropyl)-1,1,3,5,5-pentamethoxytrisiloxane. 1,3,5-tris(morpholinopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(piperazinopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(methylpiperazinopropyl)-1,1,3,5,5-pentamethoxytrisiloxane, 1,3,5-tris(diethylaminopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(dimethylaminopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1 ,3,5-Tris(dibutylaminopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(butylaminopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(phenylaminopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(morpholinopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(piperazinopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane xane, 1,3,5-tris(methylpiperazinopropyl)-1,5-dimethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(diethylaminopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(dimethylaminopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(dibutylaminopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(butylaminopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(phenylaminopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(morpholinopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(piperazinopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(methylpiperazinopropyl)-1,1,3,5,5-pentaethoxytrisiloxane, 1,3,5-tris(diethylaminopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris (dimethylaminopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(dibutylaminopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(butylaminopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(phenylaminopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(morpholinopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3, Trisiloxane compounds such as 5-tris(piperazinopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane, 1,3,5-tris(methylpiperazinopropyl)-1,5-diethoxy-1,3,5-trimethyltrisiloxane; 1,3,5,7-tetrakis(diethylaminopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(dimethylaminopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(dibutylaminopropyl)-1 ,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(butylaminopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(phenylaminopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(morpholinopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(piperazinopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-Tetrakis(methylpiperazinopropyl)-1,1,3,5,7,7-hexamethoxytetrasiloxane, 1,3,5,7-tetrakis(diethylaminopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(dimethylaminopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(dibutylaminopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(butylaminopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane 1,3,5,7-tetrakis(methylpiperazinopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(phenylaminopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(morpholinopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(piperazinopropyl)-1,7-dimethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(methylpiperazinopropyl)-1,7-dimeth 1,3,5,7-tetrakis(diethylaminopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(dimethylaminopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(dibutylaminopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(butylaminopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5 ,7-Tetrakis(phenylaminopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(morpholinopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(piperazinopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(methylpiperazinopropyl)-1,1,3,5,7,7-hexaethoxytetrasiloxane, 1,3,5,7-tetrakis(diethylaminopropyl)-1,7-diethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(dimethylaminopropyl)-1,7-diethoxy1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(dibutylaminopropyl)-1,7-diethoxy1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(butylaminopropyl)-1,7-diethoxy1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(phenylaminopropyl)-1,7-diethoxy1,3,5,7-tetramethyl Tetrasiloxane compounds such as 1,3,5,7-tetrakis(morpholinopropyl)-1,7-diethoxy-1,3,5,7-tetramethyltetrasiloxane, 1,3,5,7-tetrakis(piperazinopropyl)-1,7-diethoxy-1,3,5,7-tetramethyltetrasiloxane, and 1,3,5,7-tetrakis(methylpiperazinopropyl)-1,7-diethoxy-1,3,5,7-tetramethyltetrasiloxane; 1,3,5,7,9-pentakis(diethylaminopropyl)-1,1,3,5,7,9,9-heptamethoxy 1,3,5,7,9-pentakis(dimethylaminopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-pentakis(dibutylaminopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-pentakis(butylaminopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-pentakis(phenylaminopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-Pentakis(morpholinopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-Pentakis(piperazinopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-Pentakis(methylpiperazinopropyl)-1,1,3,5,7,9,9-heptamethoxypentasiloxane, 1,3,5,7,9-Pentakis(diethylaminopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(dimethylaminopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(dibutylaminopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(butylaminopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(phenylaminopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1, 3,5,7,9-pentakis(morpholinopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(piperazinopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(methylpiperazinopropyl)-1,9-dimethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(diethylaminopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3, 5,7,9-pentakis(dimethylaminopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(dibutylaminopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(butylaminopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(phenylaminopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(mol 1,3,5,7,9-pentakis(piperazinopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(methylpiperazinopropyl)-1,1,3,5,7,9,9-heptaethoxypentasiloxane, 1,3,5,7,9-pentakis(diethylaminopropyl)-1,9-diethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(dimethylaminopropyl)-1,9-diethoxy 1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(dibutylaminopropyl)-1,9-diethoxy 1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(butylaminopropyl)-1,9-diethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(phenylaminopropyl)-1,9-diethoxy-1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-Pentakis(morpholinopropyl)-1,9-diethoxy-1 Pentasiloxane compounds such as 1,3,5,7,9-pentamethylpentasiloxane, 1,3,5,7,9-pentakis(piperazinopropyl)-1,9-diethoxy1,3,5,7,9-pentamethylpentasiloxane, and 1,3,5,7,9-pentakis(methylpiperazinopropyl)-1,9-diethoxy1,3,5,7,9-pentamethylpentasiloxane;1,3,5,7,9,11-Hexakis(diethylaminopropyl)-1,1,3,5,7,9,11,11-octamethoxyhexasiloxane, 1,3,5,7,9,11-Hexakis(phenylaminopropyl)-1,1,3,5,7,9,11,11-octamethoxyhexasiloxane, 1,3,5,7,9,11-Hexakis(morpholinopropyl)-1,1,3,5,7,9,11,11-octamethoxyhexasiloxane, 1,3,5,7,9, 11-Hexakis(diethylaminopropyl)-1,11-dimethoxy-1,3,5,7,9,11-hexamethylhexasiloxane, 1,3,5,7,9,11-Hexakis(phenylaminopropyl)-1,11-dimethoxy-1,3,5,7,9,11-hexamethylhexasiloxane, 1,3,5,7,9,11-Hexakis(morpholinopropyl)-1,11-dimethoxy-1,3,5,7,9,11-hexamethylhexasiloxane, 1,3,5 ,7,9,11-Hexakis(diethylaminopropyl)-1,1,3,5,7,9,11,11-octaethoxyhexasiloxane, 1,3,5,7,9,11-Hexakis(phenylaminopropyl)-1,1,3,5,7,9,11,11-octaethoxyhexasiloxane, 1,3,5,7,9,11-Hexakis(morpholinopropyl)-1,1,3,5,7,9,11,11-octaethoxyhexasiloxane, 1,3,5,7,9,11-Hexakis Hexasiloxane compounds such as sakis(diethylaminopropyl)-1,11-diethoxy-1,3,5,7,9,11-hexamethylhexasiloxane, 1,3,5,7,9,11-hexakis(phenylaminopropyl)-1,11-diethoxy-1,3,5,7,9,11-hexamethylhexasiloxane, and 1,3,5,7,9,11-hexakis(morpholinopropyl)-1,11-diethoxy-1,3,5,7,9,11-hexamethylhexasiloxane;1,3,5,7,9,11,13-heptakis(diethylaminopropyl)-1,1,3,5,7,9,11,13,13-nonamethoxyheptasiloxane, 1,3,5,7,9,11,13-heptakis(phenylaminopropyl)-1,1,3,5,7,9,11,13,13-nonamethoxyheptasiloxane, 1,3,5,7,9,11,13-heptakis(morpholinopropyl)-1,1,3,5,7,9,11,13,13-nonamethoxyheptasiloxane, 1,3,5,7,9,1 1,13-heptakis(diethylaminopropyl)-1,13-dimethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane, 1,3,5,7,9,11,13-heptakis(phenylaminopropyl)-1,13-dimethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane, 1,3,5,7,9,11,13-heptakis(morpholinopropyl)-1,13-dimethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane, 1,3,5 ,7,9,11,13-heptakis(diethylaminopropyl)-1,1,3,5,7,9,11,13,13-nonaethoxyheptasiloxane, 1,3,5,7,9,11,13-heptakis(phenylaminopropyl)-1,1,3,5,7,9,11,13,13-nonaethoxyheptasiloxane, 1,3,5,7,9,11,13-heptakis(morpholinopropyl)-1,1,3,5,7,9,11,13,13-nonaethoxyheptasiloxane, 1,3,5,7,9,11,13- Heptasiloxane compounds such as heptakis(diethylaminopropyl)-1,13-diethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane, 1,3,5,7,9,11,13-heptakis(phenylaminopropyl)-1,13-diethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane, and 1,3,5,7,9,11,13-heptakis(morpholinopropyl)-1,13-diethoxy-1,3,5,7,9,11,13-heptamethylheptasiloxane;1,3,5,7,9,11,13,15-Octakis(diethylaminopropyl)-1,1,3,5,7,9,11,13,15,15-decamethoxyoctasiloxane, 1,3,5,7,9,11,13,15-Octakis(phenylaminopropyl)-1,1,3,5,7,9,11,13,15,15-decamethoxyoctasiloxane, 1,3,5,7,9,11,13,15-Octakis(morpholinopropyl)-1,1,3,5,7,9,11,13,15,15-decamethoxyoctasiloxane, 1,3,5,7,9,11,13,15- Octakis(diethylaminopropyl)-1,15-dimethoxy-1,3,5,7,9,11,13,15-octamethyloctasiloxane, 1,3,5,7,9,111,3,5,7,9,11,13,15-octakis(phenylaminopropyl)-1,15-dimethoxy-1,3,5,7,9,11,13,15-octamethyloctasiloxane, 1,3,5,7,9,11,13,15-octakis(morpholinopropyl)-1,15-dimethoxy-1,3,5,7,9,11,13,15-octamethyloctasiloxane, 1,3,5,7, 9,11,13,15-Octakis(diethylaminopropyl)-1,1,3,5,7,9,11,13,15,15-decaethoxyoctasiloxane, 1,3,5,7,9,11,13,15-Octakis(phenylaminopropyl)-1,1,3,5,7,9,11,13,15,15-decaethoxyoctasiloxane, 1,3,5,7,9,11,13,15-Octakis(morpholinopropyl)-1,1,3,5,7,9,11,13,15,15-decaethoxyoctasiloxane, 1,3,5,7,9,11,13,15-Octakis(diethylaminopropyl)-1,1,3,5,7,9,11,13,15,15-decaethoxyoctasiloxane Examples of the octasiloxane compounds include 1,3,5,7,9,11,13,15-octakis(phenylaminopropyl)-1,15-diethoxy-1,3,5,7,9,11,13,15-octamethyloctasiloxane, 1,3,5,7,9,111,3,5,7,9,11,13,15-octakis(morpholinopropyl)-1,15-diethoxy-1,3,5,7,9,11,13,15-octamethyloctasiloxane, and the like.

[0025] These oligosiloxane compounds are R 1 ~R 3 As long as A and A are the same, that is, only the value of m is different, they may be used alone or as a mixture of two or more kinds.

[0026] In the composition of the present invention, the content (area ratio) of compound (3) is not particularly limited, but is preferably 0.05 to 20%, more preferably 0.1 to 15%, and even more preferably 0.5 to 10%, of the total amount of compound (1) and compound (3). If the content is less than 0.05%, the composition may not exhibit sufficient properties when used in various applications. If the content is more than 20%, high-temperature treatment to isolate a predetermined amount of compound (3) may cause coloration, which may cause problems when used in various applications. As described above, the composition of the present invention is a composition in which an aminoalkylalkoxydisiloxane compound is the main component, and therefore there is no need to apply higher temperatures than necessary during isolation. As a result, the resulting composition is less prone to coloration derived from amino groups, and no generation of monomer compounds or loss of purity due to disproportionation reactions is observed. The above area ratio is a peak area ratio obtained by gas chromatography analysis (hereinafter also referred to as "GC analysis") or gel permeation chromatography analysis (hereinafter also referred to as "GPC analysis").

[0027] Next, a method for producing the composition of the present invention will be described. The composition of the present invention can be obtained by a production method including the steps of hydrolyzing and condensing an aminoalkylalkoxysilane compound (hereinafter also referred to as compound (4)) represented by the following general formula (4) to obtain a mixture of compounds (1), (3), and (4) and an alcohol compound represented by the following general formula (5), followed by distillation.

[0028] [ka] (In the formula, R 1 ~R 3, A, X, m and n have the same meanings as above.)

[0029] Specific examples of compound (4) include trialkoxysilane compounds such as dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, 1, butylaminopropyltrimethoxysilane, octylaminopropyltrimethoxysilane, phenylaminopropyltrimethoxysilane, morpholinopropyltrimethoxysilane, piperazinopropyltrimethoxysilane, methylpiperazinopropyltrimethoxysilane, diethylaminopropyltriethoxysilane, dimethylaminopropyltriethoxysilane, dibutylaminopropyltriethoxysilane, butylaminopropyltriethoxysilane, octylaminopropyltriethoxysilane, phenylaminopropyltriethoxysilane, morpholinopropyltriethoxysilane, piperazinopropyltriethoxysilane, and methylpiperazinopropyltriethoxysilane; diethylaminopropylmethyltriethoxysilane; Examples of alkyl dialkoxysilane compounds include alkyldimethoxysilane, dimethylaminopropylmethyldimethoxysilane, dibutylaminopropylmethyldimethoxysilane, butylaminopropylmethyldimethoxysilane, octylaminopropylmethyldimethoxysilane, phenylaminopropylmethyldimethoxysilane, morpholinopropylmethyldimethoxysilane, piperazinopropylmethyldimethoxysilane, methylpiperazinopropyltrimethoxysilane, diethylaminopropylmethyldiethoxysilane, dimethylaminopropylmethyldiethoxysilane, dibutylaminopropylmethyldiethoxysilane, butylaminopropylmethyldiethoxysilane, octylaminopropylmethyldiethoxysilane, phenylaminopropylmethyldiethoxysilane, morpholinopropylmethyldiethoxysilane, piperazinopropylmethyldiethoxysilane, and methylpiperazinopropylmethyldiethoxysilane.

[0030] The conditions for the hydrolysis and condensation reaction of compound (4) are not particularly limited. The hydrolysis and condensation reaction can be carried out by adding water to compound (4) in the presence of a solvent or a catalyst as needed, and heating and stirring as needed. The amount of water used in the hydrolysis condensation reaction is not particularly limited, but from the viewpoint of suppressing the formation of condensation products of trisiloxane or higher, the amount of water used is preferably 0.05 to 0.5 moles, and more preferably 0.1 to 0.4 moles, per mole of compound (4). When water is added, it may be added as a mixed solvent of the solvent and water from the viewpoint of suppressing the progress of local reactions. The solvent may be either a protic polar solvent such as methanol or ethanol, or an aprotic polar solvent such as acetonitrile, tetrahydrofuran, or dimethylformamide. The solvent may be mixed, for example, by first mixing compound (4) with the solvent, and then adding water or a mixture of water and the solvent.

[0031] The hydrolysis and condensation reaction of compound (4) proceeds even without a catalyst, but the reaction time can be shortened by using a catalyst. The catalyst used is not particularly limited, but examples include acidic compounds such as hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid, acetic acid, and methanesulfonic acid; basic compounds such as ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide; salts of weak acids and strong bases such as sodium acetate; salts of strong acids and weak bases such as ammonium sulfate; and metal compounds such as tin compounds, titanium compounds, and aluminum compounds. These catalysts may be used alone or in combination. The reaction temperature in the hydrolysis condensation reaction is not particularly limited, but is preferably 0 to 100°C, more preferably 20 to 70°C. The reaction time for the hydrolysis condensation reaction is not particularly limited, but is preferably 0.5 to 8 hours, more preferably 0.5 to 4 hours.

[0032] After the hydrolysis and condensation reaction, the resulting reaction liquid is distilled. The distillation apparatus is not particularly limited, but from the viewpoint of ensuring a content of compound (3) that will provide desired properties when used in various applications, a distillation apparatus having a theoretical plate number of 1 to 20, preferably 1 to 10, and even more preferably 1 to 5 can be used. Here, the theoretical plate number refers to an index that represents the performance of an apparatus that performs separation by utilizing the difference in distribution cost of a substance between two phases, a stationary phase and a mobile phase. The reflux ratio in the distillation is preferably 0.0 to 2.0, more preferably 0.0 to 1.5, and even more preferably 0.0 to 1.0, from the viewpoint of ensuring a content of compound (3) that will provide desired properties when used in various applications. [Example]

[0033] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, purity is determined by GC analysis or GPC analysis. The apparatus and conditions for GC analysis and GPC analysis are as follows: [GC analysis] Gas chromatograph: GC-2014 (Shimadzu Corporation) Packed column: Silicone SE-30 (GL Sciences, Inc.) Detector:TCD Detector temperature: 300℃ Inlet temperature: 300℃ Temperature program: 70°C (0 min) → 10°C / min → 300°C (10 min) Carrier gas: Helium (50 ml / min) Injection volume: 1μl [GPC analysis] Device: HLC-8420GPC EcoSEC Elite-WS (Tosoh Corporation) Column: Shodex GPC KF-G 4A (Showa Denko K.K.) Shodex GPC KF-404 HQ (Showa Denko Co., Ltd.) Shodex GPC KF-402.5 HQ (Showa Denko Co., Ltd.) Detector: RI Eluent: tetrahydrofuran (THF) Flow rate: 0.35ml / min Column thermostat temperature: 40℃ Standard material: polystyrene

[0034] [Example 1-1] Preparation of a composition containing 1,3-bis(diethylaminopropyl)-1,1,3,3-tetramethoxydisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 706.2 g (3.000 mol) of diethylaminopropyltrimethoxysilane, to which 16.2 g (0.900 mol) of water was added dropwise, followed by stirring at 70°C for 3 hours. The resulting reaction liquid was distilled using a four-theoretical-plate distillation apparatus at a reflux ratio of 0.0, yielding 129.4 g of a colorless, transparent liquid fraction at 148°C / 0.3 kPa. GC analysis of this fraction revealed that it consisted of 99% disiloxane compounds and 1% trisiloxane compounds by area ratio.

[0035] [Example 1-2] Preparation of a composition containing 1,3-bis(morpholinopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 233 g (1.00 mol) of morpholinopropylmethyldimethoxysilane and 1.0 g (0.0052 mol) of a 28% by weight sodium methoxide methanol solution, to which 14.4 g (0.800 mol) of water was added dropwise, followed by stirring at 70°C for 3 hours. The resulting reaction solution was distilled using a distillation apparatus with one theoretical plate at a reflux ratio of 0.0, yielding 43.6 g of a colorless, transparent liquid fraction at 260°C / 0.3 kPa. GPC analysis of this fraction revealed that it consisted, by area ratio, of 82% disiloxane compounds, 11% trisiloxane compounds, and 7% tetrasiloxane compounds.

[0036] [Examples 1-3] Preparation of a composition containing 1,3-bis(diethylaminopropyl)-1,1,3,3-tetramethoxydisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 706.2 g (3.000 mol) of diethylaminopropyltrimethoxysilane, to which a mixture of 150 g of methanol and 16.2 g (0.900 mol) of water was added dropwise, followed by stirring at room temperature for 4 hours. The resulting reaction solution was distilled using a four-theoretical-plate distillation apparatus at a reflux ratio of 0.0, yielding 243.5 g of a colorless, transparent liquid fraction at 168°C / 0.4 kPa. GC analysis of this fraction revealed that it was 99% disiloxane compounds and 1% trisiloxane compounds.

[0037] The compounds used in the following examples and comparative examples are shown below. (1) Silica ZEOSIL 1165MP (manufactured by SOLVAY Japan Co., Ltd.) (2) Aminoalkylalkoxydisiloxane composition Composition 1: Composition obtained in Example 1-1 Composition 2: Composition obtained in Example 1-2 Comparative compound 1: Diethylaminopropyltrimethoxysilane Comparative compound 2: Morpholinopropylmethyldimethoxysilane Comparative compound 3: 1,3-bis(diethylaminopropyl)-1,1,3,3-tetramethoxydisiloxane Comparative compound 4: 1,3-bis(morpholinopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane

[0038] [Examples 2-1 to 2-2, Comparative Examples 2-1 to 2-4] Compositions 1 and 2 and Comparative Compounds 1 to 4 were added to 10 ml of toluene so that the silicon molar concentration was 1 mmol, while avoiding moisture, and the mixture was stirred to prepare a uniform solution. The silica was heated at 105°C under a nitrogen atmosphere for 1 hour. After cooling to room temperature, the silica was added to the previously prepared solution and allowed to stand for 3 hours. The silica was recovered by filtration, then immersed in 20 ml of toluene and ultrasonically cleaned for 30 minutes. The silica was recovered again by filtration and dried under reduced pressure at 100°C / 0.1 kPa to obtain surface-treated silica. The obtained surface-treated silica was subjected to composition analysis by X-ray photoelectron spectroscopy (hereinafter referred to as "XPS composition analysis") to determine the ratio (%) of constituent atoms on the surface of the surface-treated silica. The results are shown in Table 1.

[0039] [Table 1]

[0040] As shown in Table 1, compositions 1 and 2 used in the examples contain disiloxane and trisiloxane compounds obtained by hydrolysis and condensation of monomer compounds, and therefore have a higher proportion of nitrogen atoms and carbon atoms on the silica surface than the compounds used in the comparative examples. This means that the silica surface is treated with a large amount of disiloxane and trisiloxane compounds, which allows the compositions to exhibit sufficient properties when used in a variety of applications.

Claims

1. The following general formula (1) 【Chemistry 1】 [In the formula, R 1 each independently represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms; R 2 and R 3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and each A independently represents a group represented by the following general formula (2): 【Chemistry 2】 (In the formula, R 4 and R 5 each independently represents a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom, and may be bonded to each other to form a ring structure, but R 4 and R 5 Except when both are hydrogen atoms.) and n's each independently represent 0 or 1. and an aminoalkylalkoxydisiloxane compound represented by the following general formula (3): 【Transformation 3】 (In the formula, R 1 ~R 3 , A and n have the same meanings as above, m is an integer of 1 to 6, and X is R 2 or OR 3 Represents.) and an aminoalkylalkoxyoligosiloxane compound represented by the formula: The content (area ratio) of the aminoalkylalkoxyoligosiloxane compound is 0.05 to 20% based on the total amount of the aminoalkylalkoxydisiloxane compound and the aminoalkylalkoxyoligosiloxane compound.

2. The following general formula (4) 【Chemistry 4】 (In the formula, R 1 ~R 3 , A and n have the same meanings as above. to obtain an aminoalkylalkoxydisiloxane compound represented by the general formula (1), an aminoalkylalkoxyoligosiloxane compound represented by the general formula (3), an aminoalkylalkoxysilane compound represented by the general formula (4), and an aminoalkylalkoxysilane compound represented by the following general formula (5): 【Transformation 5】 (In the formula, R 3 represents the same meaning as above.) 2. The method for producing the composition according to claim 1, wherein the mixture containing the alcohol compound represented by the formula (I) is obtained and then distilled.

3. 3. The method for producing the composition according to claim 2, wherein the distillation is carried out using a distillation apparatus having 1 to 20 theoretical plates.

4. The method for producing the composition according to claim 2, wherein the distillation is carried out at a reflux ratio in the range of 0.0 to 2.0.

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