JP2016053021A - Alkoxysilanes, and oligosiloxanes and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide alkoxysilanes useful as various functional chemicals, and to provide oligosiloxanes obtained therefrom and method for producing the same.SOLUTION: The alkoxysilanes have a structure where an ethoxy group or a methoxy group, an oxyalkyl group, a thioalkyl group or a halogenoalkyl group are present on the same silicon atom, and can be produced, for example, by reacting silanes having a plurality of ethoxy groups or methoxy groups with an alcohol in the presence of an inorganic solid acid catalyst having a regular pore structure. Further, the oligosiloxanes are obtained by reacting the alkoxysilanes with water, and the reaction can be performed efficiently in coexistence of an acid and the like.SELECTED DRAWING: Figure 1

Description

  The present invention relates to alkoxysilanes, oligosiloxanes obtained by reacting them with water, and methods for producing the same.

Alkoxysilanes include, for example, trialkoxysilanes that are used as silane coupling agents for surface modification of inorganic materials, and tetraalkoxysilanes that are silica, zeolite, ceramics and organic by sol-gel method. -Widely used as a raw material for inorganic hybrid materials. Silanes substituted with organic groups or hydrogen atoms are functional chemicals used as reagents for precision synthesis and synthetic intermediates such as medicine / agrochemicals and electronic materials.
As an alkoxy group such as tri- or tetraalkoxysilane, an ethoxy group or a methoxy group is often used, but alkoxysilanes having other alkoxy groups such as a propoxy group and a butoxy group are also known. However, they usually have a plurality of the same alkoxy groups, and the commercially available compounds are limited to specific ones having a plurality of the same alkoxy groups.
On the other hand, in order to control the reactivity of alkoxysilanes having a plurality of ethoxy groups or methoxy groups or to provide functionality, it is conceivable to substitute a part of ethoxy groups or methoxy groups with other alkoxy groups. Such alkoxysilanes (hereinafter referred to as “partially substituted alkoxysilanes”) are newly introduced while retaining their reactivity because they still have methoxy or ethoxy groups in the molecule. Depending on the alkoxy group, chemical properties such as physical properties such as melting point, boiling point, viscosity, refractive index, hydrophilicity / hydrophobicity, association with other organic molecules, coordination to metal atoms and metal ions, reactivity, etc. It can be expected to control or impart physical properties.

However, there are not many kinds of partially substituted alkoxysilanes yet, and a part of ethoxy group or methoxy group is substituted with a relatively short-chain organic group, such as tetraethoxy or tetramethoxysilane, butoxy group, Partially substituted alkoxysilane having a structure substituted with a specific alkoxy group such as isobutyloxy group, sec-butoxy group, 2- (methacryloxy) ethoxy group, 2- (methacryloxy) propoxy group, glydoxy group, octoxy group, decanoxy group Has been reported (Non-patent Document 1, Patent Documents 1 to 4). On the other hand, an organic group containing an oxyalkyl group or thioalkyl group contains an oxygen atom or a sulfur atom, and therefore, based on the characteristics of these atoms, the polarity of the molecule, solvent solubility, other molecules, metal ions It is considered that the associativeness, coordination, etc. can be controlled. In addition, those containing a halogenoalkyl group can be expected to interact with other molecules or convert to other functional groups based on the properties and reactivity of the halogen atom. However, few partially substituted alkoxysilanes having an oxyalkyl group, a thioalkyl group, or a halogenoalkoxy group have been known.
Further, compared to tetraethoxy or tetramethoxysilane, there is a problem that there are fewer types of partially substituted alkoxysilanes for diethoxy or dimethoxysilane or triethoxy or trimethoxysilane. In particular, one obtained by converting one of the ethoxy groups or methoxy groups of diethoxy or dimethoxysilane having two different organic groups into another alkoxy group has four different substituents. In spite of advantages such as the ability to control the reactivity and the asymmetric center of the silicon atom, which is advantageous for the design of optical / electronic materials and medicine / agrochemicals, there were few production examples. From these facts, as organic groups, partially substituted alkoxysilanes having functional groups such as oxyalkyl groups, thioalkyl groups, halogenoalkyl groups, and partially substituted groups in which all four substituents bonded to silicon atoms are different. As for the type alkoxysilanes, it has been demanded to provide compounds having a certain structure, purity, and the like, and to provide effective use thereof.
On the other hand, oligosiloxanes having a methoxy group or an ethoxy group and other alkoxy groups are compounds having both reactivity based on methoxy groups or ethoxy groups and functionality based on other alkoxy groups.・ It is expected to be used as a raw material for gel materials and organic-inorganic hybrid materials, and as a surface modification / treatment agent. For example, polysiloxanes having an alkoxy group such as a methoxy group and a butoxy group have been known for their production methods and application as curable resins (Patent Document 5). On the other hand, substituents such as oxyalkyl groups, thioalkyl groups, and halogenoalkyl groups have an oxygen atom, a sulfur atom, and a halogen atom, respectively. Oligosiloxanes having functional groups such as oxyalkyl groups, thioalkyl groups and halogenoalkyl groups as organic groups in methoxy groups or ethoxy groups and other alkoxy groups, and methods for producing them Was not known.

Bull. Chem. Soc. Jpn. 61, 4087-4092 (1988).

JP-A-4-295486 JP-A-5-255348 JP-A-5-255349 JP 2004-269465 A JP-A-8-20646

  The present invention has been made in view of the above circumstances, and partially substituted alkoxysilanes having an organic group or the like selected from an oxyalkyl group, a thioalkyl group, and a halogenoalkyl group as an organic group, and the like. The object is to provide the resulting oligosiloxanes.

As a result of intensive studies to solve the above problems, the present inventors have (1) an organic group selected from a methoxy group or ethoxy group-containing silane, an oxyalkyl group, a thioalkyl group, or a halogenoalkyl group. The reaction of the alcohol having proceeds smoothly in the presence of an inorganic solid acid catalyst having a regular pore structure, etc., and corresponding partially substituted alkoxysilanes can be obtained efficiently; (2) It has been found that partially substituted alkoxysilanes give oligosiloxanes having an ethoxy group or a methoxy group and an organic group selected from an oxyalkyl group, a thioalkyl group, or a halogenoalkyl group by condensation polymerization by hydrolysis, The present invention has been completed.
The present invention has the following features.
(1) Since the starting alcohol is easily available, the desired partially substituted alkoxysilanes can be provided at low cost.
(2) A catalyst for a reaction for producing a partially substituted alkoxysilane is easily available, easy to handle, and high in safety. In addition, since the catalyst is solid and the reaction is heterogeneous, it is easy to separate and recover the catalyst.
(3) Condensation polymerization by hydrolysis of partially substituted alkoxysilanes proceeds easily under the same conditions as in the conventional method, and is selected from ethoxy groups or methoxy groups, oxyalkyl groups, thioalkyl groups, or halogenoalkyl groups. It is possible to efficiently provide oligosiloxanes having organic groups and the like.

That is, this application provides the following inventions.
<1> Alkoxysilanes represented by the following general formula (I).
_{^{R 1 p R 2 q Si (}} OR 3) r (OR 4) s (I)
(In the formula (I), p, q and p + q are integers of 0 or more and 2 or less, r and s are integers of 1 or more and p + q + r + s = 4. R ¹ and R ² are each independently of 1 to 10 carbon atoms. An organic group or a hydrogen atom, R ³ is each independently an ethyl group or a methyl group, and R ⁴ is each independently an organic group having 2 to 10 carbon atoms.
Further, the organic group of R ¹ and R ² is an aryl group having 4 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.
In addition, except that p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or carbon It is a halogenoalkyl group of several 2 to 10.
When p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 halogenoalkyl groups, alkyl groups having 3 to 10 carbon atoms, alkenyl groups having 3 to 10 carbon atoms, alkynyl groups having 3 to 10 carbon atoms, aralkyl groups having 5 to 10 carbon atoms, or amino acids having 3 to 10 carbon atoms It is an alkyl group. )
<2> In the organic group of R ¹ and R ² , the aryl group having 4 to 10 carbon atoms is a phenyl group, the alkyl group having 1 to 10 carbon atoms is a methyl group, and the alkenyl group having 2 to 10 carbon atoms. Is a vinyl group, and the oxyalkyl group having 3 to 10 carbon atoms is a 2-methoxyethyl group, a 2-phenoxyethyl group, a (2-tetrahydrofuryl) methyl group, or a 2- (2-methoxyethoxy) ethyl group. In the organic group represented by R ⁴ , the thioalkyl group having 2 to 10 carbon atoms is a 2-mercaptoethyl group, a 2- (methylthio) ethyl group, or a 2- (phenylthio) ethyl group, and has 2 to 10 carbon atoms. The halogenoalkyl group is a 3-chloropropyl group, a 3-bromopropyl group, a 6-chlorohexyl group, or a 6-bromohexyl group, and the alkyl group having 3 to 10 carbon atoms is a butyl group a sec-butyl group, a tert-butyl group, a 2-methylbutyl group, a tert-amyl group, or an octyl group, an alkenyl group having 3 to 10 carbon atoms is a 3-methyl-2-butenyl group, and has 3 to 3 carbon atoms. <1>, wherein the 10 alkynyl group is a propargyl group, the aralkyl group having 5 to 10 carbon atoms is a benzyl group, and the aminoalkyl group having 3 to 10 carbon atoms is a 2- (dimethylamino) ethyl group. Alkoxysilanes.
<3> A composition comprising the alkoxysilane according to <1> or <2>.
<4> The composition according to <3>, wherein the content of the alkoxysilane is 50% by mass or more.
<5> The composition according to <3> or <4>, which is for producing siloxanes or for surface treatment.
<6> A method for producing oligosiloxanes comprising a reaction step of reacting the alkoxysilanes according to <1> with water.
<7> The method for producing an oligosiloxane according to <5>, wherein the reaction step is a step in which an acid or a base coexists.
<8> Oligosiloxanes having a structure represented by the following general formula (II).
_{^{R 1 p R 2 q (R}} 5 O) t Si-O-Si (OR 5) t R 1 p R 2 q (II)
(In the formula (II), p, q and p + q are integers of 0 or more and 2 or less, R ¹ and R ² are each independently an organic group or hydrogen atom having 1 to 10 carbon atoms, R ⁵ is each independently an ethyl group, A methyl group, an organic group having 2 to 10 carbon atoms, or a silyl group, and at least one of R ⁵ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or a 2 to 10 carbon atom. A halogenoalkyl group, an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, an alkynyl group having 3 to 10 carbon atoms, an aralkyl group having 5 to 10 carbon atoms, or an aminoalkyl group having 3 to 10 carbon atoms T is an integer of 1 to 3, and p + q + t = 3.)

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a partially substituted alkoxysilane having an ethoxy group or a methoxy group and an oxyalkyl group, a thioalkyl group, or a halogenoalkyl group, oligosiloxanes obtained therefrom, and a method for producing the same, and a functional material. Has the effect of contributing to the development of

It is a ²⁹ Si-NMR spectrum of the oligosiloxane produced | generated by reaction of alkoxysilane and water ((a): Tri (ethoxy) (2-methoxyethoxy) silane, (b): Tetra (ethoxy) silane).

Hereinafter, the present invention will be described in detail.
The alkoxysilane which is one embodiment of the present invention is represented by the following general formula (I).
_{^{R 1 p R 2 q Si (}} OR 3) r (OR 4) s (I)
In general formula (I), p, q, and p + q are integers of 0 or more and 2 or less, r and s are integers of 1 or more, and p + q + r + s = 4. R ¹ and R ² are each independently an organic group or hydrogen atom having 1 to 10 carbon atoms, R ³ is each independently an ethyl group or methyl group, and R ⁴ is each independently an organic group having 2 to 10 carbon atoms. Further, the organic group of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.
In addition, except that p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or carbon It is a halogenoalkyl group of several 2 to 10.
When p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 halogenoalkyl groups, alkyl groups having 3 to 10 carbon atoms, alkenyl groups having 3 to 10 carbon atoms, alkynyl groups having 3 to 10 carbon atoms, aralkyl groups having 5 to 10 carbon atoms, or amino acids having 3 to 10 carbon atoms It is an alkyl group.
In particular, alkoxysilanes represented by the general formula (I) are used to control hydrophilicity / hydrophobicity, interaction with inorganic atoms, metal cations, etc., conversion to other functional groups and functional groups, photo / electronic materials It is a compound with excellent applicability as an intermediate material for medicine, agrochemicals, and agricultural chemicals. For example, it is used as a raw material for the production of siloxanes, a raw material for surface treatment, a raw material for the production of organic / inorganic hybrid materials by the sol-gel method, etc. In this case, the hydrophilicity and hydrophobicity of the surface can be controlled over a wide range, and various inorganic atoms and metal cations can be captured and adsorbed. In addition, it is possible to exhibit excellent advantages such as being able to achieve multiple functions.
Moreover, as a manufacturing method thereof, for example, a method of reacting a silane having a plurality of ethoxy groups or methoxy groups with an alcohol and substituting a part of the plurality of ethoxy groups or methoxy groups with another alkoxy group is conceivable. Specifically, it can be produced by reacting a silane having an ethoxy group or a methoxy group represented by the following general formula (III) with an alcohol represented by the following general formula (IV).

R ¹ _p R ² _q Si (OR ³ ) _{4- (p + q)} (III)
R ⁴ OH (IV)
In the general formulas (III) and (IV), p and q, R ¹ , R ² , R ³ , and R ⁴ have the same meaning as described above.
As the organic group in R ¹ and R ² of the general formula (I) and the general formula (III), an aryl group having 4 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms Is mentioned.
When R ¹ or R ² is an aryl group having 4 to 10 carbon atoms, a hydrocarbon ring system or a heterocyclic monovalent aromatic organic group can be used. In the case of a hydrocarbon ring organic group, the number of carbon atoms is preferably 6 to 8. Specific examples of these carbocyclic aromatic organic groups include a phenyl group and a naphthyl group.
Moreover, when an aryl group is a heterocyclic organic group, a hetero atom is a sulfur, an oxygen atom, etc., Preferably carbon number is 4-10, More preferably, it is 4-8. Specific examples of these heterocyclic aromatic organic groups include thienyl group, benzothienyl group, furyl group, and benzofuryl group.

On the other hand, when R ¹ or R ² is an alkyl group having 1 to 10 carbon atoms, the carbon number is preferably 1 to 8, more preferably 1 to 6. Specific examples of these alkyl groups include methyl, ethyl, propyl, butyl, sec-butyl, hexyl, cyclohexyl, octyl and decyl groups.

In addition, when R ¹ or R ² is an alkenyl group having 2 to 10 carbon atoms, the carbon number is preferably 2 to 8, more preferably 2 to 6. Specific examples of these alkenyl groups include vinyl group, 2-propenyl group, 3-butenyl group, 5-hexenyl group, 9-decenyl group and the like.

Therefore, specific examples of the silanes of the general formula (III) having the groups R ¹ and R ² include di (methoxy) (methyl) (phenyl) silane, di (methoxy) di (methyl) silane, di (Ethoxy) di (methyl) silane, tri (methoxy) (methyl) silane, tri (ethoxy) (methyl) silane, tri (methoxy) (phenyl) silane, tri (ethoxy) (phenyl) silane, tri (methoxy) ( Vinyl) silane, tri (ethoxy) (vinyl) silane, tri (methoxy) silane, tri (ethoxy) silane, tetra (methoxy) silane, tetra (ethoxy) silane and the like.

On the other hand, in the alcohol of the general formula (IV), R ⁴ is an organic group having 2 to 10 carbon atoms. Further, except when p and q are 1, the organic group is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or a halogenoalkyl group having 2 to 10 carbon atoms. When p and q are 1, the organic group is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, a halogenoalkyl group having 2 to 10 carbon atoms, or 3 to 3 carbon atoms. It is a 10 alkyl group, a C3-C10 alkenyl group, a C3-C10 alkynyl group, a C5-C10 aralkyl group, or a C3-C10 aminoalkyl group.
When R ⁴ is an oxyalkyl group having a prime number of 3 to 10, the carbon number is preferably 3 to 9, and more preferably 3 to 8. Accordingly, specific examples of these groups include 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 6-methoxyhexyl group, 8-methoxyoctyl group, 2-ethoxyethyl group, 2-phenoxy group. An ethyl group, a (2-tetrahydrofuryl) methyl group, a 2- (2-methoxyethoxy) ethyl group, and the like can be given.
Further, when R ⁴ is a thioalkyl group having 2 to 10 carbon atoms, the carbon number is preferably 2 to 8, more preferably 2 to 6. Therefore, specific examples of these groups include 2-mercaptoethyl group, 3-mercaptopropyl group, 4-mercaptobutyl group, 6-mercaptohexyl group, 2- (methylthio) ethyl group, 3- (methylthio) propyl group. , 2- (phenylthio) ethyl group and the like.
Further, when R ⁴ is a halogenoalkyl group having 2 to 10 carbon atoms, the carbon number is preferably 2 to 9, more preferably 2 to 8. Specific examples of these groups include 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, 6-chloro. A hexyl group, 6-bromohexyl group, 8-chlorooctyl group, 8-bromooctyl group, etc. can be mentioned.

On the other hand, when R ⁴ is an alkyl group having 3 to 10 carbon atoms, the carbon number is preferably 3 to 10 and more preferably 3 to 8. Specific examples of these groups include propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, amyl group, tert-amyl group, cyclohexyl group, hexyl group, cyclohexyl group, octyl group, decyl group. Etc.
In addition, when R ⁴ is an alkenyl group having 3 to 10 carbon atoms, the carbon number is preferably 3 to 10 and more preferably 3 to 8. Specific examples of these groups include 2-propenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 5-hexenyl group, 9-decenyl group and the like.
Further, when R ⁴ is an alkynyl group having 3 to 10 carbon atoms, the carbon number is preferably 3 to 10 and more preferably 3 to 8. Specific examples of these groups include propargyl group, 2-butyn-1-yl group, and 3-phenyl-2-propyn-1-yl group.
In addition, when R ⁴ is an aralkyl group having 5 to 10 carbon atoms, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 8. Specific examples of these groups include benzyl group, phenethyl group, 2-phenylpropyl group and the like.
In addition, when R ⁴ is an aminoalkyl group having 3 to 10 carbon atoms, the carbon number is preferably 3 to 10 and more preferably 3 to 8. Specific examples of these groups include 2-aminoethyl group, 2- (dimethylamino) ethyl group, 2- (diethylamino) ethyl group, 3-aminopropyl group, 2- (dimethylamino) propyl group, 4- ( And a dimethylamino) butyl group.

  The molar ratio of the alcohol to the raw silanes can be arbitrarily selected, but considering the yield of the generated silanes relative to the raw silanes, it is usually 0.4 or more and 300 or less, more preferably 0.5 or more. It is 200 or less, More preferably, it is 0.5 or more and 150 or less.

By reaction of the silanes of the above general formula (III) with the alcohols of the above general formula (IV),
_{^{R 1 p R 2 q Si (}} OR 3) r (OR 4) s (I)
Can be produced.
In general formula (I), p, q, r, s, R ³ and R ⁴ have the same meanings as described above, and preferred specific examples of R ³ and R ⁴ include the above general formulas (III) and (IV ) And the like.

Therefore, as R ⁴ , a partially substituted alkoxysilane of the general formula (I) having an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or a halogenoalkyl group having 2 to 10 carbon atoms Preferred examples of the class include (methoxy) (2-methoxyethoxy) (methyl) (phenyl) silane, (methoxy) (2-phenoxyethoxy) (methyl) (phenyl) silane, (methoxy) (2-mercaptoethoxy) ) (Methyl) (phenyl) silane, (methoxy) [2- (methylthio) ethoxy] (methyl) (phenyl) silane, (methoxy) [2- (phenylthio) ethoxy] (methyl) (phenyl) silane, (methoxy) (3-chloropropoxy) (methyl) (phenyl) silane, (methoxy) (3-bromopropoxy) (methyl) (phenyl) silane, (methoxy) (2-methoxyethoxy) di (methyl) silane, (methoxy) ( 2-phenoxyethoxy) di (methyl) silane, (methoxy) (2-mercaptoethoxy) di (methyl) silane, (methoxy) [2- (methylthio) ethoxy] di (phenyl) silane, (methoxy) [2- ( Phenylthio) ethoxy] di (methyl) silane, (methoxy) (3-chloropropoxy) di (methyl) silane, (methoxy) (3-bromopropoxy) di (phenyl) silane, di (methoxy) (2-methoxyethoxy) (Phenyl) silane, (methoxy) di (2-methoxyethoxy) (phenyl) silane, di (methoxy) (2-phenoxyethoxy) (phenyl) silane, (methoxy) di (2-phenoxyethoxy) (phenyl) silane, Di (methoxy) (2-mercaptoethoxy) (phenyl) silane, (methoxy
) Di (2-mercaptoethoxy) (phenyl) silane, di (methoxy) [2- (methylthio) ethoxy] (phenyl) silane, (methoxy) di [2- (methylthio) ethoxy] (phenyl) silane, di (methoxy ) [2- (phenylthio) ethoxy] (phenyl) silane, di (methoxy) (3-chloropropoxy) (phenyl) silane, (methoxy) di (3-chloropropoxy) (phenyl) silane, di (methoxy) (3 -Bromopropoxy) (phenyl) silane, (methoxy) di (3-bromopropoxy) (phenyl) silane, di (ethoxy) (2-methoxyethoxy) (phenyl) silane, (2-methoxyethoxy) di (ethoxy) ( Phenyl) silane, (ethoxy) di (2-methoxyethoxy) (phenyl) silane, di (ethoxy) (2-mercaptoethoxy) (phenyl) silane, (ethoxy) di (2-mercaptoethoxy) (phenyl) silane, di (Ethoxy) (3-bromopropoxy) (phenyl) silane, (ethoxy) di (3-bromopropoxy) (phenyl) silane, di (ethoxy) (2-methoxyethoxy) (vinyl) silane, (ethoxy) di (2 -Methoxyethoxy) (vinyl) silane, di (ethoxy) (2-phenoxyethoxy) (vinyl) silane, (ethoxy) di (2-phenoxyethoxy) (vinyl) silane, di (methoxy) (2-mercaptoethoxy) ( Vinyl) silane, (methoxy) di (2-mercaptoethoxy) (vinyl) silane, di (ethoxy) [2- (methylthio) ethoxy] (vinyl) silane, (ethoxy) di [2- (methylthio) ethoxy] (vinyl ) Silane, di (methoxy) [2- (phenylthio) ethoxy] (vinyl) silane, di (ethoxy) (3-chloropropoxy) (vinyl) silane, (ethoxy) di (3-chloropropoxy) (vinyl) silane, Di (ethoxy) (3-bromide (Propoxy) (vinyl) silane, (ethoxy) di (3-bromopropoxy) (vinyl) silane, tri (methoxy) (2-methoxyethoxy) silane, di (methoxy) di (2-methoxyethoxy) silane, (methoxy) Tri (2-methoxyethoxy) silane, tri (methoxy) (2-phenoxyethoxy) silane, di (methoxy) di (2-phenoxyethoxy) silane, (methoxy) tri (2-phenoxyethoxy) silane, tri (ethoxy) (2-phenoxyethoxy) silane, di (methoxy) di (2-phenoxyethoxy) silane, (methoxy) tri (2-phenoxyethoxy) silane, tri (methoxy) [(2-tetrahydrofuryl) methoxy] silane, di ( Methoxy) di [(2-tetrahydrofuryl) methoxy] silane, (methoxy) tri [(2-tetrahydrofuryl) methoxy] silane, tri (methoxy) [2- (2- Toxiethoxy) ethoxy] silane, di (methoxy) di [2- (2-methoxyethoxy) ethoxy] silane, (methoxy) tri [2- (2-methoxyethoxy) ethoxy] silane, tri (ethoxy) (2-methoxy Ethoxy) silane, di (ethoxy) di (2-methoxyethoxy) silane, (ethoxy) tri (2-methoxyethoxy) silane, tri (ethoxy) (2-phenoxyethoxy) silane, di (ethoxy) di (2-phenoxy) Ethoxy) silane, (ethoxy) tri (2-phenoxyethoxy) silane, tri (ethoxy) (2-phenoxyethoxy) silane, di (ethoxy) di (2-phenoxyethoxy) silane, (ethoxy) tri (2-phenoxyethoxy) ) Silane, tri (ethoxy) [(2-tetrahydrofuryl) methoxy] silane, di (ethoxy) di [(2-tetrahydrofuryl) methoxy] silane, (ethoxy) tri [(2- Tetrahydrofuryl) methoxy] silane, tri (ethoxy) [2- (2-methoxyethoxy) ethoxy] silane, di (ethoxy) di [2- (2-methoxyethoxy) ethoxy] silane, (ethoxy) tri [2- ( 2-methoxyethoxy) ethoxy] silane, tri (methoxy) (2-mercaptoethoxy) silane, di (methoxy) di (2-mercaptoethoxy) silane, (methoxy) tri (2-mercaptoethoxy) silane, tri (methoxy) [2- (methylthio) ethoxy] silane, di (methoxy) di [2- (methylthio) ethoxy] silane, (methoxy) tri [2- (methylthio) ethoxy] silane, tri (methoxy) [2- (phenylthio) ethoxy Silane, di (methoxy) di [2- (phenylthio) ethoxy] silane, (methoxy) tri [2- (phenylthio) ethoxy] silane, tri (methoxy) (3-chloropropoxy) silane Di (methoxy) di (3-chloropropoxy) silane, (methoxy) tri (3-chloropropoxy) silane, tri (methoxy) (3-bromopropoxy) silane, di (methoxy) di (3-bromopropoxy) silane, (Methoxy) tri (3-bromopropoxy) silane, tri (ethoxy) (3-chloropropoxy) silane, di (ethoxy) di (3-chloropropoxy) silane, (ethoxy) tri (3-chloropropoxy) silane, tri (Ethoxy) (3-bromopropoxy) silane, di (ethoxy) di (3-bromopropoxy) silane, (ethoxy) tri (3-bromopropoxy) silane, tri (methoxy) (6-chlorohexoxy) silane, di (methoxy ) Di (6-chlorohexoxy) silane, (methoxy) tri (6-chlorohexoxy) silane, tri (methoxy) (6-bromohexoxy) silane, di (methoxy) di (6 Bromohexoxy) silane, (methoxy) tri (6-bromohexoxy) silane, tri (ethoxy) (6-chlorohexoxy) silane, di (ethoxy) di (6-chlorohexoxy) silane, (ethoxy) tri (6-chlorohexoxy) silane, tri (Ethoxy) (6-bromohexoxy) silane, di (ethoxy) di (6-bromohexoxy) silane, (ethoxy) tri (6-bromohexoxy) silane and the like.

On the other hand, as R ⁴ , an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, an alkynyl group having 3 to 10 carbon atoms, an aralkyl group having 5 to 10 carbon atoms, or an amino group having 3 to 10 carbon atoms Preferable specific examples of the partially substituted alkoxysilane of the general formula (I) having an alkyl group include (methoxy) (butoxy) (methyl) (phenyl) silane, (methoxy) (sec-butoxy) silane, ( (Methoxy) (tert-butoxy) (methyl) (phenyl) silane, (methoxy) (2-methylbutoxy) (methyl) (phenyl) silane, (methoxy) (tert-amyloxy) (methyl) (phenyl) silane, (methoxy ) (Octoxy) (methyl) (phenyl) silane, (methoxy) (3-methyl-2-butenoxy) (methyl) (phenyl) silane, (methoxy) (propargyloxy) (methyl) (phenyl) silane, (methoxy) (Ben Yloxy) (methyl) (phenyl) silane, and (methoxy) [2- (dimethylamino) ethoxy] (methyl) (phenyl) silane.

  When a partially substituted alkoxysilane is produced by reacting a silane having a plurality of ethoxy groups or methoxy groups with an alcohol, if the raw material silane remains, or if all ethoxy groups or methoxy groups are substituted Type alkoxysilane may be produced as a by-product. Depending on the use of the partially substituted alkoxysilane, it is considered that there is no significant effect even if by-products such as raw materials and fully substituted alkoxysilane are mixed. Can be used as a composition as it is. Note that a composition containing the alkoxysilane of the general formula (I) is also an embodiment of the present invention.

  The content of the alkoxysilane of the general formula (I) contained in the composition is 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. Within the above range, the performance and function characteristic of the partially substituted alkoxysilane can be expressed more effectively. Examples of the compounds other than the alkoxysilanes of the general formula (I) contained in the composition include raw material silanes and fully substituted alkoxysilanes in which all of ethoxy groups or methoxy groups are substituted.

  Applications of the composition include raw materials for producing siloxanes and raw materials for surface treatment.

In the reaction of producing the partially substituted alkoxysilane of the general formula (I) by reacting the silane of the general formula (III) with the alcohol of the general formula (IV) Catalysts such as acids or bases can be used.
For example, when an acid is used as the catalyst, a solid acid catalyst that can be easily separated and recovered can be used. Specific examples thereof include solid inorganic substances such as metal salts and metal oxides, and more specifically, protic hydrogen atoms or metal cations (aluminum, titanium, gallium, iron, cerium, scandium, etc.) In addition to zeolite, mesoporous silica, montmorillonite, and the like having silica, silica gel, heteropoly acid, and inorganic solid acid using a carbon-based material as a carrier can be mentioned.
Among these, solid acids such as zeolite, mesoporous silica, and montmorillonite, which are inorganic solid acids having regular pores and / or a layered structure, are preferable in terms of catalytic activity and selectivity for products. Zeolite and montmorillonite-based solid acids are more preferably used. There are no particular restrictions on the type of regular pores and / or layered structure of the inorganic solid acid, but in consideration of the ease of diffusion of the reacting molecules and the generated molecules, the solid acid catalyst having a pore structure The range of the pore diameter is 0.2 to 20 nm, preferably 0.3 to 15 nm, more preferably 0.3 to 10 nm. In the solid acid catalyst having a layered structure, the range of the interlayer distance is 0.2 to 20 nm, preferably 0.3 to 15 nm, more preferably 0.3 to 10 nm.

  When a zeolite is used as an inorganic solid acid catalyst having a regular pore structure, various types of zeolites having basic skeletons such as Y type, beta type, ZSM-5 type, mordenite type, and SAPO type are used. It can be used. Further, USY type known as SUSY type (Super Ultrastable Y), VUSY type (Very Ultrastable Y), SDUSY type (Super delutable ultrastable Y), etc. obtained by secondary treatment of Y type zeolite (Na-Y) (Ultrastable Y, ultra-stable Y type) can also be used preferably (see, for example, “Molecular Sieves”, Advanceds in Chemistry, Volume 121, American Chemical Society, 1973, Chapter 19, etc.).

Of these zeolites, USY type, beta type, and Y type are preferable, and USY type and beta type are more preferable among these zeolites. Moreover, as a zeolite for selectively converting a part of a plurality of ethoxy groups or methoxy groups to other alkoxy groups, USY type and Y type are preferable in terms of reaction rate and selectivity, and USY type is more preferable. preferable.
In these zeolites, various types of zeolites such as Bronsted acid type having a protonic hydrogen atom and Lewis acid type having a metal cation can be used. Among these, the proton type having a protonic hydrogen atom is represented by HY type, H-SDUSY type, H-SUSY type, H-beta type, H-mordenite type, H-ZSM-5 type, etc. Is done. Furthermore, those of ammonium type, _NH 4 -Y _type, NH 4 -VUSY type, NH ₄ - beta, NH ₄ - _mordenite, by firing the NH 4 -ZSM-5 type or the like of the zeolite, the proton type Those converted to can also be used.
Furthermore, about the silica / alumina ratio (substance amount ratio) of zeolite, various ratios can be selected according to the reaction conditions, but it is usually 5 to 1000, preferably 5 to 600, more preferably 5 to 300, More preferably, it is 5-100.

  As these zeolites, various types including commercial products can be used. Specific examples of commercially available products include USZ-type zeolites, such as CBV760, CBV780, CBV720, CBV712, and CBV600, which are commercially available from Zeolis Corporation. Examples of Y-type zeolites are HSZ- 360HOA, HSZ-320HOA, etc. are mentioned. Moreover, as a beta-type zeolite, CP811C, CP814N, CP7119, CP814E, CP7105, CP814CN, CP811TL, CP814T, CP814Q, CP811Q, CP811E-75, CP811E, and CP811C-300 etc. are commercially available from Zeolist. Examples include HSZ-930HOA and HSZ-940HOA, which are more commercially available, and UOP-Beta, which is commercially available from UOP. Further, examples of the mordenite type zeolite include CBV21A and CBV90A commercially available from Zeolis Corporation, HSZ-660HOA, HSZ-620HOA, HSZ-690HOA and the like commercially available from Tosoh Corporation. ZSM-5 type zeolite Examples thereof include CBV5524G, CBV8020, and CBV8014N, which are commercially available from Zeolist.

In addition, in the reaction using microwave irradiation, an organic solid acid having an acidic functional group can be effectively used in addition to the inorganic solid acid. The organic solid acid is a polymer having an acidic functional group. Examples of the acidic functional group include a sulfo group, a carboxy group, and a phosphoryl group. Examples of the polymer include Teflon having a perfluoro side chain. (Registered trademark) skeleton polymer, styrene-divinylbenzene copolymer, and the like. Specific examples include Nafion (Nafion, registered trademark, available from DuPont), Dowex (registered trademark, available from Dow Chemical), Amberlite (Amberlite, registered trademark) having a sulfo group. And Amberlyst (Amberlyst, registered trademark, available from Dow Chemical Company), and the like. More specifically, Nafion NR50, Dowex 50WX2, Dowex 50WX4, Dowex 50WX8, Amberlite IR120, Amberlite IRP-64, Amberlist 15, Amberlist 36, and the like can be given. Furthermore, a catalyst (for example, Nafion SAC-13) in which an organic solid acid such as Nafion is supported on an inorganic material such as silica can be used, and a combination of a plurality of inorganic solid acids and organic solid acids can be used. it can.

Furthermore, novel oligosiloxanes can be produced by obtaining the alkoxysilanes of the general formula (I) by reacting with water.
These oligosiloxanes have the following general formula (II)
_{^{R 1 p R 2 q (R}} 5 O) t Si-O-Si (OR 5) t R 1 p R 2 q (II)
Wherein p, q and p + q are integers of 0 or more and 2 or less, R ¹ and R ² are each independently an organic group having 1 to 10 carbon atoms or a hydrogen atom, and R ⁵ are each independently An ethyl group, a methyl group, an organic group having 2 to 10 carbon atoms, or a silyl group, and at least one of R ⁵ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or 2 carbon atoms. -10 halogenoalkyl groups, C3-C10 alkyl groups, C3-C10 alkenyl groups, C3-C10 alkynyl groups, C5-C10 aralkyl groups, or C3-C10 An aminoalkyl group. t is an integer of 1 to 3, and p + q + t = 3.
Specific examples of R ¹ , R ² , R ⁵ and specific examples of the alkoxysilanes of the general formula (I) used for producing oligosiloxanes include those exemplified above.
In the reaction for producing oligosiloxanes, the molar ratio of water to alkoxysilanes can be arbitrarily selected, but considering the yield of the generated oligosiloxanes relative to alkoxysilanes, etc., the alkoxy group 1 in alkoxysilanes Usually, it is 0.1 or more and 20 or less, more preferably 0.1 or more and 10 or less, and further preferably 0.1 or more and 5 or less.
In addition, the number of silicon in the oligosiloxane is usually 2 or more and 10,000 or less, but preferably 2 or more and 5000 or less, more preferably 2 in view of physical properties such as solubility in a solvent, processability, and handleability. It is 3000 or more.
Alkoxysilanes having a partial structure represented by the general formula (II) have an oxyalkyl group, a thioalkyl group, or a halogenoalkyl group in the raw material alkoxysilane, so that hydrophilic and hydrophobic control, inorganic It is a compound that excels in interaction with atoms and metal cations, conversion to other functional groups and functional groups, etc., for example, used for surface treatment materials, organic / inorganic hybrid materials by the sol-gel method, etc. In some cases, the hydrophilicity / hydrophobicity of the surface can be controlled over a wide range, and various inorganic atoms and metal cations can be captured and adsorbed. It is possible to exhibit excellent advantages such as functionalization.

In the reaction of partially substituted alkoxysilanes with water, oligosiloxanes can be efficiently produced by allowing an acid or base to coexist as a catalyst. As the types of these acids or bases, various conventionally known ones used in general hydrolysis reactions of alkoxysilanes can be used.
For example, specific examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Moreover, the solid acid illustrated by the manufacturing method of partially substituted alkoxysilanes can also be used.
Specific examples of the base include inorganic bases such as ammonium hydroxide, sodium carbonate, and potassium carbonate, and organic bases such as trimethylamine, diethylamine, triethylamine, tripropylamine, tributylamine, dimethylaniline, and pyridine.

  In the production of partially substituted alkoxysilanes and oligosiloxanes, the amount of catalyst relative to the raw material can be arbitrarily determined. For example, the weight ratio is usually about 0.0001 to 10, preferably 0.001 to 8. The degree is more preferably about 0.001 to 6.

These production reactions can be performed in a liquid phase or a gas phase depending on the temperature and pressure at the time of performing the reaction. Moreover, as a form of a reaction apparatus, it can carry out with various forms conventionally known, such as a batch type and a flow type.
The reaction temperature is usually −20 ° C. or higher, preferably −10 to 300 ° C., more preferably −10 to 200 ° C. Moreover, in order to control reactivity, when reacting at room temperature, it is 0-40 degreeC normally as a temperature range of room temperature, Preferably it is 5-40 degreeC, More preferably, it is 10-35 degreeC.
Furthermore, the reaction pressure is usually 0.0001 to 100 atm, preferably 0.001 to 50 atm, and more preferably 0.001 to 10 atm.
The reaction time depends on the amount of the raw material and catalyst, the reaction temperature, the form of the reaction apparatus, etc., but considering productivity and efficiency, it is usually 0.1 to 1200 minutes, preferably 0.1 to 600 minutes. Preferably it is about 0.1 to 300 minutes.

  Further, when the production reaction is carried out in a liquid phase system, it can be carried out with or without a solvent, but when a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane, chlorobenzene, 1,2- or 1 , 3-halogenated hydrocarbons such as 1,3-dichlorobenzene, 1,2,3- or 1,2,4-trichlorobenzene, ethers such as tert-butyl methyl ether, dibutyl ether, etc., except those that react with the raw material These solvents can be used, and a mixture of two or more of them can also be used. Moreover, when performing reaction in a gaseous phase, it can also react by mixing inert gas, such as nitrogen.

  These production reactions can also be performed under microwave irradiation. In this reaction system, the raw material alcohol, water, alkoxysilane, solid acid catalyst, etc. have a relatively large dielectric loss coefficient and absorb microwaves efficiently, so the raw materials and catalysts are activated under microwave irradiation, The reaction can be performed more efficiently.

  In the microwave irradiation reaction, various commercially available devices equipped with contact-type or non-contact-type temperature sensors can be used. The output of microwave irradiation, the type of cavity (multimode, single mode), the form of irradiation (continuous, intermittent), etc. can be arbitrarily determined according to the scale and type of reaction. The frequency of the microwave is usually 0.3 to 30 GHz. Among them, the IMS frequency band allocated for use in the industrial, scientific, and medical fields is preferable, and among them, the 2.45 GHz band, the 5.8 GHz band, and the like are more preferable.

  In the microwave irradiation reaction, in order to heat the reaction system more efficiently, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system. As the kind of the heating material, various conventionally known materials such as activated carbon, graphite, silicon carbide, titanium carbide and the like can be used. Further, a molded catalyst obtained by mixing the catalyst described above and the heating material powder and calcining using an appropriate binder such as sepiolite or holmite can also be used.

Although the production reaction proceeds even in a closed reactor, the reaction becomes more efficient by making the reactor open and continuously removing ethanol or methanol produced as a co-product in the reaction from the reaction system. Can be advanced.

  Further, when a solid catalyst is used in the production reaction, since the solid catalyst is insoluble in the solution, the separation and recovery of the catalyst after the reaction can be easily performed by methods such as filtration and centrifugation. Furthermore, purification of the produced silanes can be easily achieved by means usually used in organic chemistry such as distillation, recrystallization and column chromatography.

  EXAMPLES Next, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to these Examples.

(Example 1)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 1.6 mmol, 2-methoxyethanol (IVa) 3.2 mmol, CBV780 (manufactured by Zeolis) 5 mg of a mixture was placed in a reaction tube at room temperature (25 ° C.). Stir for 10 minutes. As a result of analyzing the product with a gas chromatograph (GC), gas chromatograph mass spectrometer (GC-MS), and nuclear magnetic resonance spectrum analyzer (NMR), the product was partially substituted alkoxysilane (methoxy). (2-Methoxyethoxy) (methyl) (phenyl) silane (Va-1) (= (Ia-1)) and di (2-methoxyethoxy) (methyl) (phenyl) silane (Va- 2) produced with a total yield of 68% (Va-1: Va-2 = 74: 26), and partially substituted alkoxysilane (Ia-1) was produced with a yield of 50%. (See Table 1).

(Examples 2 to 64)
Table 1 shows the results obtained by carrying out the reaction and analysis in the same manner as in Example 1 while changing the reaction conditions (raw materials, catalyst, temperature, time, etc.) and measuring the yield of the product.

Table 2 shows data of mass spectrometry spectra and ²⁹ Si-NMR spectra of partially substituted alkoxysilanes (Ia-1) to (Ian-1) obtained in the above Examples.

In the above production method, it is possible to selectively convert some of the plurality of ethoxy groups or methoxy groups in the raw material silane to other alkoxy groups, and by controlling reaction conditions such as the type of catalyst and temperature Monosubstituted alkoxysilanes can be produced as main products.
As such a catalyst for selective alkoxylation, USY type and Y type zeolite catalysts are preferably used in terms of reaction rate and selectivity, but Y type is more preferable than USY type in reaction rate and yield. In many cases, USY type is more preferably used.
In addition, the reaction conditions such as temperature and time in the selective alkoxylation are appropriately adjusted according to the kind and amount of the raw material and the catalyst. When a zeolite catalyst having a relatively high catalytic activity is used, the reaction temperature is Is usually about 0 to 70 ° C., preferably about 10 to 60 ° C., more preferably about 10 to 50 ° C. When a zeolite catalyst having a relatively low catalytic activity is used, it is usually 50 to 150 ° C., preferably 60 It is about -140 degreeC, More preferably, it is about 70-130 degreeC. The reaction time varies depending on the reaction temperature and the like, but considering the production efficiency, it is usually 0.5 to 600 minutes, preferably 0.5 to 300 minutes, more preferably 0.5 to 180 minutes. Degree.

  In this reaction, when heating is performed, by using microwave irradiation, a raw material such as alcohol or a solid acid catalyst can be heated more efficiently, so compared with a normal external heating method using an oil bath or the like. Reaction can be accelerated and promoted.

  In addition, this reaction proceeds in either a closed system or an open system. However, the reaction is carried out with a co-product such as performing the reaction while flowing an inert gas such as nitrogen in the open system, or performing the reaction in a reduced pressure system. Even when the amount of alcohol to be used is reduced by a method of positively removing ethanol or methanol from the reaction system, the reaction can be carried out efficiently.

  The partially substituted alkoxysilane (I) obtained by the above method is easily separated by operations such as distillation and recrystallization after separating the solid acid catalyst by centrifugation, filtration, etc., as shown in the following examples. It can be isolated and purified.

(Example 65)
A mixture of 240 mmol of tetra (methoxy) silane (IIId), 360 mmol of (2-tetrahydrofuryl) methanol (IVc) and 400 mg of CBV780 (Zeolist) was put in a flask, and an oil bath (R90 manufactured by Riko Kagaku) was placed in a nitrogen atmosphere. And stirred at 40 ° C. for 15 minutes. The solid catalyst was separated by filtration, and the catalyst was washed with 5 mL of hexane. The filtrate and the washing solution were combined and distilled under reduced pressure. As a result, tri (methoxy) [(2-tetrahydrofuryl) methoxy] silane (Vl-1 96 mmol (yield 40%) of (Il-1)) and 72 mmol (yield 30%) of di (methoxy) di [(2-tetrahydrofuryl) methoxy] silane (Vl-2 (Il-2)) were obtained. It was.
The physical property values and spectral data of (Il-1) and (Il-2) were as follows.
(Il-1)
Boiling point: 104-106 ℃ / 10mmHg
¹ H-NMR (CDCl ₃ ): δ 1.65-1.72 (m, 1H, CH), 1.82-1.98 (m, 3H, CH), 3.59 (s, 9H, OCH ₃ ), 3.74-3.79 (m, 3H, OCH ₂ and OCH), 3.84-3.88 (m, 1H, OCH), 3.99-4.04 (m, 1H, OCH)
¹³ C-NMR (CDCl ₃ ): δ 25.7, 27.6, 51.3, 66.0, 68.4, 78.9
²⁹ Si-NMR (CDCl ₃ ): δ -79.6
IR (liquid film): 1459, 1195, 1091, 1003, 831 cm ^-1
(Il-2)
Boiling point: 162-168 ℃ / 10mmHg
¹ H-NMR (CDCl ₃ ): δ 1.59-1.65 (m, 2H, CH), 1.75-1.91 (m, 6H, CH), 3.52 (s, 6H, OCH ₃ ), 3.67-3.73 (m, 6H, OCH ₂ and OCH), 3.76-3.82 (m, 2H, OCH), 3.92-3.97 (m, 2H, OCH)
¹³ C-NMR (CDCl ₃ ): δ 25.5, 27.5, 51.1, 65.8, 68.2, 78.7
²⁹ Si-NMR (CDCl ₃ ): δ -80.6
IR (liquid film): 1458, 1195, 1091, 1002, 832 cm ^-1

Example 66
A mixture of 200 mmol of tetra (methoxy) silane (IIId), 300 mmol of 2- (2-methoxyethoxy) ethanol (IVd) and 350 mg of CBV780 (manufactured by Zeolis) was placed in a flask, and an oil bath (R90 manufactured by Riko Kagaku Co., Ltd.) was placed in a nitrogen atmosphere. ) At 70 ° C. for 15 minutes. The solid catalyst was separated by filtration, and the catalyst was washed with 5 mL of hexane, and then the filtrate and the washing solution were combined and distilled under reduced pressure. As a result, tri (methoxy) [2- (2-methoxyethoxy) ethoxy] silane (Vm -1 (Im-1)) is 80 mmol (yield 40%), and di (methoxy) di [2- (2-methoxyethoxy) ethoxy] silane (Vm-2 (Im-2)) is 40 mmol (yield). 20%).
The physical property values and spectral data of (Im-1) and (Im-2) were as follows.
(Im-1)
Boiling point: 91-93 ℃ / 1.6mmHg
¹ H-NMR (CDCl ₃ ): δ 3.32 (s, 3H, COCH ₃ ), 3.48-3.50 (m, 2H, OCH ₂ ), 3.53 (s, 9H, SiOCH ₃ ), 3.57 (t, J = 5.3 Hz , 2H, OCH ₂ ), 3.59-3.61 (m, 2H, OCH ₂ ), 3.88 (t, J = 5.3 Hz, 2H, OCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 51.1, 58.8, 62.8, 70.4, 71.8, 72.0
²⁹ Si-NMR (CDCl ₃ ): δ -79.6
IR (Liquid film): 1457, 1197, 1093, 968, 834 cm ^-1
(Im-2)
Boiling point: 152-154 ℃ / 1.6mmHg
¹ H-NMR (CDCl ₃ ): δ 3.33 (s, 6H, COCH ₃ ), 3.49-3.52 (m, 4H, OCH ₂ ), 3.55 (s, 6H, SiOCH ₃ ), 3.58 (t, J = 5.3 Hz , 4H, OCH ₂ ), 3.60-3.63 (m, 4H, OCH ₂ ), 3.91 (t, J = 5
.3 Hz, 4H, OCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 51.2, 58.9, 62.8, 70.4, 71.9, 72.0
²⁹ Si-NMR (CDCl ₃ ): δ -80.6
IR (liquid film): 1457, 1356, 1250, 1199, 1094, 972, 834 cm ^-1

(Example 67)
A mixture of 200 mmol of tetra (ethoxy) silane (IIIe), 300 mmol of 2-methoxyethanol (IVa) and 350 mg of CBV780 (manufactured by Zeolis) was placed in a flask, and 110 using an oil bath (R90, manufactured by Riko Kagaku) under a nitrogen atmosphere. Stir at 50 ° C. for 50 minutes. The solid catalyst was separated by filtration, and the catalyst was washed with 5 mL of hexane. The filtrate and the washing solution were combined and distilled under reduced pressure. As a result, tri (ethoxy) (2-methoxyethoxy) silane (Vu-1 (Iu- 1)) is 80 mmol (yield 40%), di (ethoxy) di (2-methoxyethoxy) silane (Vu-2 (Iu-2)) is 40 mmol (yield 20%), (ethoxy) tri (2 10 mmol (yield 5%) of -methoxyethoxy) silane (Vu-3 (Iu-3)) were obtained.
The physical property values, spectral data, etc. of (Iu-1), (Iu-2), and (Iu-3) were as follows.
(Iu-1)
Boiling point: 89-91 ℃ / 10mmHg
¹ H-NMR (CDCl ₃ ): δ 1.22 (t, J = 7.0 Hz, 9H, OCCH ₃ ), 3.37 (s, 3H, OCH ₃ ), 3.50 (t, J = 5.2 Hz, 2H, OCH ₂ ), 3.84 (q, J = 7.0 Hz, 6H, OCH ₂ ), 3.90 (t, J = 5.2 Hz, 2H, OCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.0, 58.9, 59.2, 62.6, 73.5
²⁹ Si-NMR (CDCl ₃ ): δ -82.0
IR (Liquid membrane): 1455, 1391, 1296, 1200, 1169, 1105, 1084, 968, 845, 793 cm ^-1
(Iu-2)
Boiling point: 114-117 ℃ / 10mmHg
¹ H-NMR (CDCl ₃ ): δ 1.22 (t, J = 7.0 Hz, 6H, OCCH ₃ ), 3.37 (s, 6H, OCH ₃ ), 3.50 (t, J = 5.1 Hz, 4H, OCH ₂ ), 3.85 (q, J = 7.0 Hz, 4H, OCH ₂ ), 3.91 (t, J = 5.2 Hz, 4H, OCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.0, 58.9, 59.3, 62.6, 73.5
²⁹ Si-NMR (CDCl ₃ ): δ -82.1
IR (liquid film): 1456, 1392, 1296, 1201, 1104, 1086, 1029, 971, 845, 793 cm ^-1
(Iu-3)
Boiling point: 141 ° C / 10mmHg
¹ H-NMR (CDCl ₃ ): δ 1.20 (t, J = 7.0 Hz, 3H, OCCH ₃ ), 3.34 (s, 9H, OCH ₃ ), 3.48 (t, J = 5.1 Hz, 6H, OCH ₂ ), 3.84 (q, J = 7.0 Hz, 2H, OCH ₂ ), 3.90 (t, J = 5.1 Hz, 6H, OCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.0, 58.8, 59.3, 62.7, 73.4
²⁹ Si-NMR (CDCl ₃ ): δ -82.3

Example 68
A mixture of 220 mmol of tetra (ethoxy) silane (IIIe), 240 mmol of 2-mercaptoethanol (IVe) and 350 mg of CBV780 (manufactured by Zeolis) was placed in a flask, and the oil bath (R90, manufactured by Riko Kagaku) was used under reduced pressure (130 mmHg). And stirred at 70 ° C. for 30 minutes. Further, 160 mmol of (IVe) was added, and the mixture was stirred at 70 ° C. for 30 minutes under reduced pressure (130 mmHg). The solid catalyst was separated by filtration, the catalyst was washed with 5 mL of hexane, and the filtrate and the washing solution were combined and distilled under reduced pressure. As a result, tri (ethoxy) (2-mercaptoethoxy) silane (Vy-1 (Iy- 1)) was 77 mmol (35% yield), and di (ethoxy) di (2-mercaptoethoxy) silane (Vy-2 (Iy-2)) was 100 mmol (yield 4).
5%) and 15 mmol (yield 7%) of (ethoxy) tri (2-mercaptoethoxy) silane (Vy-3 (Iy-3)).
Physical property values, spectral data, etc. of (Iy-1), (Iy-2), and (Iy-3) were as follows.
(Iy-1)
Boiling point: 78-80 ℃ / 2.0mmHg
¹ H-NMR (CDCl ₃ ): δ 1.24 (t, J = 7.0 Hz, 9H, OCCH ₃ ), 1.53 (t, J = 8.4 Hz, 1H, SH), 2.66-2.71 (m, 2H, SCH ₂ ) , 3.85 (q, J = 7.0 Hz, 6H, OCH ₂ ), 3.88 (t, J = 6.6 Hz, 2H, SCCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.1, 26.6, 59.3, 65.3
²⁹ Si-NMR (CDCl ₃ ): δ -82.2
IR (liquid film): 1391, 1298, 1169, 1103, 1081, 967, 835, 792 cm ^-1
(Iy-2)
Boiling point: 118-119 ℃ / 2.0mmHg
¹ H-NMR (CDCl ₃ ): δ 1.24 (t, J = 7.0 Hz, 6H, OCCH ₃ ), 1.52 (t, J = 8.3 Hz, 2H, SH), 2.66-2.71 (m, 4H, SCH ₂ ) , 3.86 (q, J = 7.0 Hz, 4H, OCH ₂ ), 3.89 (t, J = 6.5 Hz, 4H, SCCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.1, 26.6, 59.5, 65.3
²⁹ Si-NMR (CDCl ₃ ): δ -82.7
IR (Liquid membrane): 1390, 1299, 1169, 1099, 968, 835, 794 cm ^-1
(Iy-3)
Boiling point: 148-150 ℃ / 2.0mmHg
¹ H-NMR (CDCl ₃ ): δ 1.22 (t, J = 7.0 Hz, 3H, OCCH ₃ ), 1.51 (t, J = 8.3 Hz, 3H, SH), 2.64-2.70 (m, 6H, SCH ₂ ) , 3.85 (q, J = 7.0 Hz, 2H, OCH ₂ ), 3.89 (t, J = 6.5 Hz, 6H, SCCH ₂ )
¹³ C-NMR (CDCl ₃ ): δ 18.0, 26.5, 59.6, 65.4
²⁹ Si-NMR (CDCl ₃ ): δ -83.2

(Example 69)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 5.0 mmol, butanol (IVl) 19.9 mmol, CBV600 (manufactured by Zeolis) 15 mg in a reaction tube was sealed and sealed at room temperature (23 ° C.). Stir for minutes. After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation using an apparatus, 3.6 mmol (yield 71%) of (methoxy) (butoxy) (methyl) (phenyl) silane (Vae-1 (Iae-1)) was obtained.
The physical property values, spectral data, etc. of (Iae-1) were as follows.
Boiling point: 65-70 ℃ / 0.65mmHg (distillation temperature in short pass distillation)
Elemental analysis: C 63.96, H 8.98 (measured value); C 64.24, H 8.98 (calculated value C ₁₂ H ₂₀ O ₂ Si)
¹ H-NMR (CDCl ₃ ): δ 0.35 (s, 3H, SiCH ₃ ), 0.91 (t, J = 7.3 Hz, 3H, CCH ₃ ), 1.39 (sext, J = 7.3 Hz, 2H, OCCCH ₂ ), 1.58 (quint, J = 7.3 Hz, 2H, OCCH ₂ ), 3.54 (s, 3H,
OCH ₃ ), 3.70-3.79 (m, 2H, OCH ₂ ), 7.33-7.42 (m, 3H, aromatic ring H), 7.59-7.65 (m, 2H, aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -4.7, 13.8, 19.0, 34.7, 50.5, 62.7, 127.8, 130.0, 134.0, 134.3
²⁹ Si-NMR (CDCl ₃ ): δ -16.2
IR (Liquid film): 1592, 1465, 1430, 1387, 1258, 1190, 1121, 1087, 1039, 984, 894, 826, 802, 773, 738, 700, 652, 482, 437 cm ^-1

(Example 70)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 5.0 mmol, sec-butyl alcohol (IVm) 19.7 mmol, CBV780 (manufactured by Zeolis) 15 mg in a reaction tube was sealed and sealed at room temperature (23 ° C. ) For 20 minutes. After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation using an apparatus, 3.3 mmol (yield 65%) of (methoxy) (sec-butoxy) (methyl) (phenyl) silane (Vaf-1 (Iaf-1)) was obtained.
The physical property values and spectral data of (Iaf-1) were as follows.
Boiling point: 60-70 ℃ / 0.7mmHg (distillation temperature in short pass distillation)
Elemental analysis: C 63.95, H 8.93 (measured value); C 64.24, H 8.98 (calculated value C ₁₂ H ₂₀ O ₂ Si)
¹ H-NMR (CDCl ₃ ): δ 0.35 and 0.36 (each s, 3H, SiCH ₃ ), 0.89 and 0.91 (each t, J
= 7.3 Hz, 3H, CCH ₃ ), 1.19 and 1.20 (each d, each J = 6.1 Hz, 3H, CHCH ₃ ), 1.43-1.60 (m, 2H, CH ₂ ), 3.528 and 3.535 (each s, 3H, OCH ₃ ), 3.88-3.97 (m, 1H, OCH), 7.35-7.43 (m, 3H, aromatic ring H), 7.62-7.66 (m, 2H, aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -4.20 and -4.13, 9.99 and 10.05, 23.05 and 23.07, 32.14 and 32.17, 50.5, 70.35 and 70.37, 127.78 and 127.79, 129.9, 134.06 and 134.07, 134.85 and 134.91
²⁹ Si-NMR (CDCl ₃ ): δ -18.1
IR (liquid film): 1592, 1463, 1429, 1376, 1258, 1190, 1171, 1122, 1088, 1053, 1013, 952, 854, 822, 804, 783, 765, 738, 700, 656, 484, 460, 419 cm ^-1

(Example 71)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 3.3 mmol, octanol (IVp) 13.2 mmol, CBV 780 (manufactured by Zeolis) 10 mg of a mixture was put in a reaction tube and sealed, and a microwave irradiation apparatus (Biotage) The resulting mixture was stirred at 110 ° C. for 5 minutes. After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation using an apparatus, 2.2 mmol (yield 68%) of (methoxy) (octoxy) (methyl) (phenyl) silane (Vai-1 (Iai-1)) was obtained.
The physical property values and spectral data of (Iai-1) were as follows.
Boiling point: 90-95 ℃ / 0.3mmHg (distillation temperature in short pass distillation)
Elemental analysis: C 68.90, H 9.77 (measured value); C 68.52, H 10.06 (calculated value C ₁₆ H ₂₈ O ₂ Si)
¹ H-NMR (CDCl ₃ ): δ 0.35 (s, 3H, SiCH ₃ ), 0.88 (t, J = 6.9 Hz, 3H, CCH ₃ ), 1.21-1.37 (m, 10H, OCC (CH ₂ ) ₅ ) , 1.59 (quint, J = 6.9 Hz, 2H, OCCH ₂ ), 3.54 (s, 3H, OCH ₃ ), 3.68-3.78 (m, 2H, OCH ₂ ), 7.34-7.44 (m, 3H, aromatic ring H) , 7.59-7.64 (m, 2H, aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -4.7, 14.1, 22.7, 25.8, 29.3, 29.4, 31.8, 32.5, 50.5, 63.0, 127.8, 130.0, 134.0, 134.3
²⁹ Si-NMR (CDCl ₃ ): δ -16.1
IR (liquid film): 1467, 1429, 1258, 1190, 1121, 1089, 846, 804, 775, 738, 699, 482, 434 cm ^-1

(Example 72)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 5.0 mmol, 3-methyl-2-butenol (IVq) 19.9 mmol, CBV780 (manufactured by Zeolis) 15 mg was put in a reaction tube, sealed, and room temperature. (23 ° C.) for 1 minute. After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation in the apparatus, (methoxy) (3-methyl-2-butenoxy) (methyl) (phenyl) silane (Vaj-1 (I
3.4 mmol (68% yield) of aj-1)) was obtained.
The physical property values and spectral data of (Iaj-1) were as follows.
Boiling point: 85-95 ℃ / 0.5mmHg (distillation temperature in short pass distillation)
¹ H-NMR (CDCl ₃ ): δ 0.36 (s, 3H, SiCH ₃ ), 1.60 (s, 3H, CCH ₃ ), 1.72 (d, J = 1.0 Hz, 3H, CCH ₃ ), 3.56 (s, 3H , OCH ₃ ), 4.23-4.31 (m, 2H, OCH ₂ ), 5.36-5.40 (m, 1H, = CH), 7.36-7.43 (m, 3H, aromatic ring H), 7.62-7.64 (m, 2H, Aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -4.5, 17.8, 25.7, 50.5, 59.7, 123.5, 127.8, 130.0, 134.0, 134.3, 135.0
²⁹ Si-NMR (CDCl ₃ ): δ -15.4
IR (Liquid film): 1679, 1592, 1447, 1430, 1380, 1259, 1191, 1121, 1083, 1065, 1029, 869, 827, 803, 773, 739, 700, 655, 481, 440 cm ^-1

(Example 73)
A mixture of di (methoxy) (methyl) (phenyl) silane (IIIa) 3.3 mmol, benzyl alcohol (IVr) 13.3 mmol, CBV600 (manufactured by Zeolis) 10 mg was put in a reaction tube and sealed, and a microwave irradiation apparatus (bio) The mixture was stirred at 110 ° C. for 3.5 minutes using Taji Initiator). After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation using an apparatus, 1.8 mmol (yield 55%) of (methoxy) (benzyloxy) (methyl) (phenyl) silane (Vak-1 (Iak-1)) was obtained.
The physical property values and spectral data of (Iak-1) were as follows.
Boiling point: 105-110 ℃ / 0.35mmHg (distillation temperature in short pass distillation)
Elemental analysis: C 69.52, H 7.04 (measured value); C 69.72, H 7.02 (calculated value C ₁₅ H ₁₈ O ₂ Si)
¹ H-NMR (CDCl ₃ ): δ 0.39 (s, 3H, SiCH ₃ ), 3.52 (s, 3H, OCH ₃ ), 4.83 (s, 1H, OCH ^a H ^b ), 4.86 (s, 1H, OCH ^a H ^b ), 7.23-7.28 (m, 1H, aromatic ring H), 7.32-7.45 (m, 7H, aromatic ring H), 7.64-7.67 (m, 2H, aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -4.6, 50.6, 64.7, 126.6, 127.2, 127.9, 128.3, 130.2, 133.9, 134.1, 140.4
²⁹ Si-NMR (CDCl ₃ ): δ -15.0
IR (Liquid membrane): 1592, 1496, 1454, 1429, 1379, 1259, 1208, 1190, 1121, 1086, 1028, 853, 809, 777, 738, 698, 659, 581, 482, 438 cm ^-1

(Example 74)
Di (methoxy) (methyl) (phenyl) silane (IIIa) 4.1 mmol, tert-butyl alcohol (IVs) 48.5 mmol, CBV780 (manufactured by Zeolis) 13 mg of a mixture was put in a reaction tube and sealed, and a microwave irradiation device (CEM Discover) was stirred at 70 ° C. for 15 minutes. After separating the catalyst solids by centrifugation and separating the supernatant, the catalyst is washed with hexane (twice with 0.8 mL), and the supernatant and washings are combined and concentrated under reduced pressure, and short pass distillation is performed. As a result of distillation in the apparatus, 2.7 mmol (yield 65%, purity by gas chromatographic analysis) of (methoxy) (tert-butoxy) (methyl) (phenyl) silane (Val-1 (Ial-1)) was 95% or more).
The physical property values and spectral data of (Ial-1) were as follows.
Boiling point: 70-80 ℃ / 2.8mmHg (distillation temperature in short pass distillation)
Elemental analysis: C 63.85, H 8.86 (measured value); C 64.24, H 8.98 (calculated value C ₁₂ H ₂₀ O ₂ Si)
¹ H-NMR (CDCl ₃ ): δ 0.36 (s, 3H, SiCH ₃ ), 1.34 (s, 9H, CCH ₃ ), 3.49 (s, 3H, OCH ₃ ), 7.34-7.41 (m, 3H, aromatic ring H), 7.61-7.66 (m, 2H, aromatic ring H)
¹³ C-NMR (CDCl ₃ ): δ -1.7, 31.9, 50.3, 73.1, 127.7, 129.6, 134.0, 136.4
²⁹ Si-NMR (CDCl ₃ ): δ -23.5
IR (Liquid film): 1470, 1429, 1389, 1365, 1258, 1241, 1198, 1121, 1088, 1056, 1025, 8
36, 808, 785, 754, 738, 714, 700, 625, 483, 442, 420, 409 cm ^-1

  Further, the partially substituted alkoxysilane (I) obtained by the above method can be converted into the corresponding oligosiloxane by reaction with water, as shown in the following examples.

(Example 75)
To 0.15 mmol of tri (ethoxy) (2-methoxyethoxy) silane (Iu-1), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N aqueous hydrochloric acid solution were added, mixed well, and allowed to stand at room temperature for 14 hours. As a result of analyzing the reaction solution with an NMR spectrum analyzer, ethanol and 2-methoxyethanol were produced (ethanol: 2-methoxyethanol = about 2.4: 1, about 45% of the total alkoxy groups reacted with water), It was found that an oligosiloxane having a 2-methoxyethoxy group and an ethoxy group was produced.
The presence of 2-methoxyethoxy group and ethoxy group in the oligosiloxane indicates that the NMR spectrum of the reaction solution is obtained under the same conditions by using tetra (ethoxy) silane instead of tri (ethoxy) (2-methoxyethoxy) silane. It estimated by comparing with the NMR spectrum of the reaction liquid obtained by performing reaction by (FIG. 1). That is, by comparing the ²⁹ Si signal region of oligosiloxane by ²⁹ Si-NMR, the reaction liquid of tetra (ethoxy) silane was −88.68, −88.61, −85.98, and −85.90 ppm. In the reaction solution of tri (ethoxy) (2-methoxyethoxy) silane, in addition to those, −88.75, −88 were observed. .57, −85.77, −85.67, −85.53, and −85.52 ppm, and the like, signals that are considered to be derived from 2-methoxyethoxysilyl groups (Si—OCH ₂ CH ₂ OMe) were observed ( Table 3), suggesting the presence of both ethoxy and 2-methoxyethoxy groups.
Moreover, in the molecular weight measurement by GPC (polystyrene standard), the molecular weight of the produced oligosiloxane was 500 in weight average molecular weight (Mw) and 1.1 in weight average molecular weight / number average molecular weight (Mw / Mn) (Table). 3).
The obtained oligosiloxane solution could be applied onto a substrate such as an inorganic substance, and for example, could be applied onto a glass substrate by a spin coating method (2000 rotations / minute, 60 seconds).

(Example 76)
To 0.15 mmol of di (ethoxy) di (2-methoxyethoxy) silane (Iu-2), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added, mixed well, and then allowed to stand at room temperature for 14 hours. . As a result of analyzing the reaction solution by NMR, ethanol and 2-methoxyethanol were produced (ethanol: 2-methoxyethanol = about 0.8: 1, about 50% of the total alkoxy groups reacted with water), and 2-methoxy It was found that oligosiloxane having an ethoxy group and an ethoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 77)
To 0.15 mmol of tri (methoxy) [(2-tetrahydrofuryl) methoxy] silane (I1-1), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added and mixed well, then at room temperature for 14 hours. I left it alone. As a result of NMR analysis of the reaction solution, methanol and (2-tetrahydrofuryl) methanol were produced (methanol: (2-tetrahydrofuryl) methanol = about 2.4: 1, about 45% of the total alkoxy groups reacted with water). In addition, it was found that an oligosiloxane having a (2-tetrahydrofuryl) methoxy group and a methoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 78)
To 0.15 mmol of di (methoxy) di [(2-tetrahydrofuryl) methoxy] silane (Il-2), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added and mixed well. Left for hours. As a result of analyzing the reaction solution by NMR, methanol and (2-tetrahydrofuryl) methanol were produced (methanol: (2-tetrahydrofuryl) methanol = about 1.9: 1, about 55% of the total alkoxy groups reacted with water). In addition, it was found that an oligosiloxane having a (2-tetrahydrofuryl) methoxy group and a methoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 79)
To 0.15 mmol of tri (methoxy) [2- (2-methoxyethoxy) ethoxy] silane (Im-1), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added and mixed well. Left for 14 hours. As a result of analyzing the reaction solution by NMR, methanol and 2- (2-methoxyethoxy) ethanol were produced (methanol: 2- (2-methoxyethoxy) ethanol = about 2.3: 1, and about 55% of the total alkoxy groups were It was found that an oligosiloxane having a 2- (2-methoxyethoxy) ethoxy group and a methoxy group was produced.
The results of NMR measurement and molecular weight measurement by GPC of the generated oligosiloxane are shown in Table 3.
It was as follows.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 80)
To 0.15 mmol of di (methoxy) di [2- (2-methoxyethoxy) ethoxy] silane (Im-2), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added and mixed well. And left for 14 hours. As a result of analyzing the reaction solution by NMR, methanol and 2- (2-methoxyethoxy) ethanol were produced (methanol: 2- (2-methoxyethoxy) ethanol = about 0.6: 1, about 55% of the total alkoxy groups were It was found that an oligosiloxane having a 2- (2-methoxyethoxy) ethoxy group and a methoxy group was produced.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 81)
0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added to 0.15 mmol of tri (ethoxy) (2-mercaptoethoxy) silane (Iy-1), mixed well, and left at room temperature for 14 hours. As a result of analyzing the reaction solution by NMR, ethanol and 2-mercaptoethanol were produced (ethanol: 2-mercaptoethanol = about 2.2: 1, about 50% of the total alkoxy groups reacted with water) and 2-mercapto. It was found that oligosiloxane having an ethoxy group and an ethoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 82)
To 0.15 mmol of di (ethoxy) di (2-mercaptoethoxy) silane (Iy-2), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added, mixed well, and then allowed to stand at room temperature for 14 hours. . As a result of analyzing the reaction solution by NMR, ethanol and 2-mercaptoethanol were produced (ethanol: 2-mercaptoethanol = about 0.8: 1, about 50% of the total alkoxy groups reacted with water) and 2-mercapto. It was found that oligosiloxane having an ethoxy group and an ethoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 83)
Silane mixture mainly composed of di (methoxy) di (3-chloropropoxy) silane (Iq-2) (Iq-1: Iq-2: Iq-3: IIId: Vq-4) = 28: 38: 23: 7 : 4, total amount of about 0.15 mmol) was added 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N aqueous hydrochloric acid solution, mixed well, and then allowed to stand at room temperature for 14 hours. NMR reaction solution
As a result, methanol and 3-chloropropanol were produced (methanol: 3-chloropropanol = about 0.6: 1, about 60% of the total alkoxy groups reacted with water), and 3-chloropropoxy group and methoxy It was found that an oligosiloxane having a group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

(Example 84)
Silane mixture mainly composed of di (ethoxy) di (3-chloropropoxy) silane (Iaa-2) (Iaa-1: Iaa-2: Iaa-3: IIIe: Vaa-4 = 38: 38: 13: 9 : 2, to a total amount of about 0.15 mmol), 0.45 mL of deuterated acetonitrile and 0.003 mL of 0.25N hydrochloric acid aqueous solution were added, mixed well, and allowed to stand at room temperature for 14 hours. As a result of NMR analysis of the reaction solution, ethanol and 3-chloropropanol were produced (ethanol: 3-chloropropanol = about 1.2: 1, about 55% of the total alkoxy groups reacted with water) and 3-chloro It was found that an oligosiloxane having a propoxy group and an ethoxy group was formed.
The results of NMR measurement and molecular weight measurement by GPC of the produced oligosiloxane were as shown in Table 3.
The obtained oligosiloxane solution can be applied onto a substrate made of an inorganic substance or the like, and can be applied onto a glass substrate by, for example, a spin coating method (2000 rotations / minute, 60 seconds).

The coating film of the oligosiloxane obtained in the above example exhibits physical and chemical characteristics based on the type of alkoxy group in the raw material alkoxysilane.
For example, with respect to hydrophilicity / hydrophobicity, as a result of measuring the contact angle of water, the oligosiloxane containing an oxyalkyl group is in the range of about 20 to 35, and the oligosiloxane containing a thioalkyl group or a halogenoalkyl group is about 40 to 55. Range numbers were obtained. This is because oligosiloxanes obtained from alkoxysilanes containing oxyalkyl groups tend to form hydrophilic films, whereas oligosiloxanes obtained from alkoxysilanes containing thioalkyl groups or halogenoalkyl groups This indicates that there is a tendency to form a film having low hydrophilicity, and is considered useful for controlling the hydrophilicity / hydrophobicity of the surface.
In addition, oligosiloxanes containing oxyalkyl groups and thioalkyl groups can be expected to have excellent properties for capturing and adsorbing various inorganic atoms and metal cations. It can also be expected to improve the performance and multifunctionality by converting to other functional groups and functional groups.

  According to the present invention, alkoxysilanes and oligosiloxanes useful as various functional chemicals or synthetic intermediates thereof can be provided efficiently and safely. Therefore, the utility value of the present invention is high, and its industrial significance is great. It is.

Claims (8)

Alkoxysilanes represented by the following general formula (I).
_{^{R 1 p R 2 q Si (}} OR 3) r (OR 4) s (I)
(In the formula (I), p, q and p + q are integers of 0 or more and 2 or less, r and s are integers of 1 or more and p + q + r + s = 4. R ¹ and R ² are each independently of 1 to 10 carbon atoms. An organic group or a hydrogen atom, R ³ is each independently an ethyl group or a methyl group, R ⁴ is each independently an organic group having 2 to 10 carbon atoms, and the organic groups of R ¹ and R ² are carbon atoms It is a 4-10 aryl group, a C1-C10 alkyl group, or a C2-C10 alkenyl group.
In addition, except that p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or carbon It is a halogenoalkyl group of several 2 to 10.
When p, q, r, and s are all 1, the organic group of R ⁴ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 halogenoalkyl groups, alkyl groups having 3 to 10 carbon atoms, alkenyl groups having 3 to 10 carbon atoms, alkynyl groups having 3 to 10 carbon atoms, aralkyl groups having 5 to 10 carbon atoms, or amino acids having 3 to 10 carbon atoms It is an alkyl group. ) In the organic group of R ¹ and R ² , the aryl group having 4 to 10 carbon atoms is a phenyl group, the alkyl group having 1 to 10 carbon atoms is a methyl group, and the alkenyl group having 2 to 10 carbon atoms is a vinyl group. The oxyalkyl group having 3 to 10 carbon atoms is a 2-methoxyethyl group, a 2-phenoxyethyl group, a (2-tetrahydrofuryl) methyl group, or a 2- (2-methoxyethoxy) ethyl group, In the organic group of R ⁴ , the thioalkyl group having 2 to 10 carbon atoms is a 2-mercaptoethyl group, 2- (methylthio) ethyl group, or 2- (phenylthio) ethyl group, and a halogenoalkyl having 2 to 10 carbon atoms. Group is 3-chloropropyl group, 3-bromopropyl group, 6-chlorohexyl group, or 6-bromohexyl group, and an alkyl group having 3 to 10 carbon atoms is Group, sec-butyl group, tert-butyl group, 2-methylbutyl group, tert-amyl group, or octyl group, an alkenyl group having 3 to 10 carbon atoms is a 3-methyl-2-butenyl group, The alkynyl group having 3 to 10 carbon atoms is a propargyl group, the aralkyl group having 5 to 10 carbon atoms is a benzyl group, and the aminoalkyl group having 3 to 10 carbon atoms is a 2- (dimethylamino) ethyl group. The alkoxysilanes described in 1.   The composition containing the alkoxysilanes of Claim 1 or 2.   The composition according to claim 3, wherein the content of the alkoxysilane is 50% by mass or more.   The composition according to claim 3 or 4, which is used for producing siloxanes or for surface treatment.   A method for producing oligosiloxanes comprising a reaction step of reacting the alkoxysilanes according to claim 1 with water.   The method for producing oligosiloxanes according to claim 6, wherein the reaction step is a step in which an acid or a base coexists. Oligosiloxanes having a structure represented by the following general formula (II).
_{^{R 1 p R 2 q (R}} 5 O) t Si-O-Si (OR 5) t R 1 p R 2 q (II)
(In the formula (II), p, q and p + q are integers of 0 or more and 2 or less, R ¹ and R ² are each independently an organic group or hydrogen atom having 1 to 10 carbon atoms, R ⁵ is each independently an ethyl group, A methyl group, an organic group having 2 to 10 carbon atoms, or a silyl group, and at least one of R ⁵ is an oxyalkyl group having 3 to 10 carbon atoms, a thioalkyl group having 2 to 10 carbon atoms, or a 2 to 10 carbon atom. A halogenoalkyl group, an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, an alkynyl group having 3 to 10 carbon atoms, an aralkyl group having 5 to 10 carbon atoms, or an aminoalkyl group having 3 to 10 carbon atoms T is an integer of 1 to 3, and p + q + t = 3.)

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