JPH03188085A - Silane having chloroalkyl group - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I [R is (substituted)monovalent hydrocarbon; Y is alkoxy, OH or halogen; n is 1-3]. EXAMPLE:A compound of formula II. USE:Useful for improvement of adhesion of organic-inorganic composite materials. PREPARATION:With 3-chloro-2-chloromethylpropene of formula III, a silane compound (e.g. trichlorosilane) of formula IV is reacted in the presence of a catalyst (preferably complex compound of metal belonging to VIII group of periodic table) preferably at 40-150 deg.C for 0.1-50hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a novel silane compound having a loloalkyl group, which is effective for improving the adhesion of organic-inorganic composite materials.

(Prior art) Examples of organosilicon compounds used to improve the adhesiveness of organic-inorganic composite materials include γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Various silane coupling agents are known, such as silane, γ-meccryloxybrobyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane, but these silanes have one carbon functional group, so However, a silicon compound having two carbon functional groups has been desired since it cannot be used as a crosslinking agent between organic polymers and also for the purpose of improving adhesiveness.

(Problems to be Solved by the Invention) The purpose of the present invention is to
An object of the present invention is to provide a novel silane compound having a difunctional chloroalkyl group that is useful for improving the adhesiveness of inorganic composite materials.

[Structure of the Invention] (Means for Solving the Problems) The present invention provides a method for solving the problems of (wherein n represents an integer of 1 to 3) A silane having a chloroalkyl group.

In the compound (1) of the present invention, the monovalent hydrocarbon group of R includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Alkyl groups such as dodecyl; cycloalkyl groups such as dichlorpentyl and cyclohexyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; aryl groups such as phenyl and tolyl; alkenyl groups such as vinyl and allyl. ; and chloromethyl, chlorophenyl substituted with halogen atom, amino group, cyano group, etc.
Examples include substituted hydrocarbon groups such as 3,3,3-trifluoropropyl, aminoethyl, and cyanoethyl. Among these, a saturated hydrocarbon group having 1 to 4 carbon atoms, particularly a methyl group, is preferred because it is easy to obtain raw materials and synthesize.

Y is a hydrolyzable group, and includes halogen atoms such as chlorine and bromine; methoxy, ethoxy, n-propoxy, i-propoxy, methoxyethoxy, n-butoxy, 5ec-butoxy, i-butoxy, t-butoxy, cyclo Examples include alkoxy groups such as hexyloxy and phenoxy, and hydroxyl groups. Among these, a chlorine atom is particularly preferred in terms of ease of synthesis, and a methoxy group and an ethoxy group are particularly preferred in terms of practical stability and appropriate reactivity.

n is an integer of 1 to 3, and when the compound (I) of the present invention is used to improve the adhesiveness of an organic-inorganic composite material, n is preferably 3.

An example of the method for producing compound (1) of the present invention will be explained below.

That is, as shown in reaction formula (1), 3-chloro-2-chloromethylpropene (II) and a silane compound (Ill)
The compound (r) of the present invention can be obtained by addition reaction with
can be manufactured.

x-n (CI2CH-1ac=cH* + H3i-Yl
l(II) (III)3-
n → (CI2CHa)-CHCHi-3i-Yn (1
)(I) (In the formula, R and n are the same as above.) In addition, 3-chloro-2-chloromethylpropene (I) used as a raw material
I) is a known substance, and is described in the method of chlorinating 3-chloro-2-methylpropene with sulfuryl chloride (European Patent No. 15).
9508 specification) or a method in which chlorine gas is applied to methylenecyclopropane (R, Koester, S, A
rora, P. Binger: Justus Lie
bigs Ann, Chem, l 011619
(1973)).

Similarly, the raw material silane compound (III) is also a known substance. Examples of the silane compound (III) include monohydrogenhalogenosilanes such as trichlorosilane, tribromosilane, methylchlorosilane, dimethylchlorosilane, ethyldichlorosilane, diethylchlorosilane, and phenyldichlorosilane; and trimethoxysilane, triethoxysilane, Examples include monohydrodiene alkoxysilanes such as methyldimethoxysilane and dimethylethoxysilane. Among these, trichlorosilane and methyldichlorosilane are particularly preferred in terms of availability of raw materials, ease of synthesis, reactivity, and the like.

In the addition reaction formula (1), the ratio of compound (II) and silane compound (III) to be used is not particularly limited, but
Since 1 mol of the hydrosilyl group of the silane compound (nt) reacts with 1 mol of the vinyl group of the compound (IF), it is economically preferable to use equimolar amounts of both.

As a catalyst for this addition reaction, a complex compound of a metal of Group I of the periodic table is used, and a platinum compound obtained by dissolving chloroplatinic acid in alcohol or a carbonyl compound, or a complex compound of various olefins and platinum or rhodium is preferably used. It will be done. The amount of the complex compound used is not particularly limited, but it is preferably in the range of loppm or more and less than 2000 ppm as platinum atoms relative to the amount of compound (II) used.
If the amount is less than 2,000 ppm, the reaction will be slow and a good yield cannot be achieved in a short period of time, and even if it is used in an amount of 2,000 ppm or more, there will be no particular effect.

In addition, this addition reaction involves preparing compound (II) and a catalyst,
A method of heating to a predetermined temperature and dropping the silane compound (III) to react is preferable in terms of reaction control.

The reaction temperature of this addition reaction is usually 10 to 250°C, preferably 40 to 150°C. The reaction time varies from 0.1 to 50 hours depending on the amount of catalyst used, reaction temperature, raw material molar ratio, etc. 9 This reaction can be carried out either under normal pressure or under elevated pressure.

Furthermore, in the addition reaction formula (1), the use of an organic solvent is not essential, but if used, an aliphatic hydrocarbon such as hexane or heptano; an alicyclic hydrocarbon such as cyclohexane; diethyl ether. It is possible to use ethers such as: aromatic hydrocarbons such as benzene, toluene, xylene: and halogenated hydrocarbons such as 1,2-dichloroethane. The amount of the organic solvent used is not particularly limited, but it is preferably in the range of 10% by weight or more and 500% by weight based on the total weight of the reactants.

In addition, as a method for producing the compound (1) of the present invention, the reaction formula (
1), as well as general formula (IV
) to the chlorosilane compound of the present invention represented by the general formula (
A method of subjecting a compound having active hydrogen represented by V) to a substitution reaction may also be mentioned.

This method is shown in reaction formula (2).

1-n (CI2CHz)z CHCHg-3I Cl2n
+(IV) Y-H (V) R8-□ ” (Cj2CHw)* CHCHg-S i −
Yn + (I) n HCQ (2) (wherein R, Y and n are the same as above) Examples of the compound (V) having active hydrogen include methyl alcohol, ethyl alcohol, n-propyl alcohol, i - Alcohols such as propyl alcohol, methoxyethyl alcohol, n-butyl alcohol, 5ee-butyl alcohol, i-butyl alcohol, t-butyl alcohol, cyclohexyl alcohol; and phenol. Among these, methyl alcohol and ethyl alcohol are preferably used.

In substitution reaction formula (2), in order to proceed smoothly with the reaction, it is desirable to use a hydrogen chloride scavenger equivalent to the theoretical equivalent, and as a hydrogen chloride scavenger, a tertiary amine such as pyridine, triethylamine, or tributylamine is used. preferable.

In substitution reaction formula (2), it is not essential to use an organic solvent, but if it is used, addition reaction formula (1)
The matters regarding organic solvents explained in Section 2 apply.

In addition, in this substitution reaction, a chlorosilane compound (rv) and, if desired, an organic solvent are charged into a reaction vessel, and a mixture consisting of a compound (V) having a theoretical equivalent of active hydrogen and a hydrogen chloride scavenger is added to the reaction vessel at a temperature of 10°C to 50°C. A method in which the reaction is carried out dropwise at a temperature of 0.degree. C. is preferable in terms of reaction control.

The compound of the present invention (1
) can be isolated and purified by techniques commonly used in the field of organic synthetic chemistry; for example, the target substance can be isolated by vacuum distillation.

[Effects of the Invention] Since the compound of the present invention has two substituents that react or interact with the organic matrix resin, it improves the adhesiveness and reliability of organic-inorganic composite materials such as semiconductor encapsulants. It is effective in improving Furthermore, in organic-inorganic composite materials, effects such as improved mechanical properties, improved electrical properties, improved water and moisture resistance, improved workability, and cost reduction due to high content of inorganic fillers can be expected.

(Example) The present invention will be described in more detail below with reference to Examples. Note that the scope of the present invention is not limited only to the following examples.

Example 1 2.0 parts of a solution of 0.5 parts of chloroplatinic acid dissolved in 25 parts of Improper Tools was placed in a flask with an internal volume of lβ equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and an oil bath. and 125 parts of 3-chloro-2-chloromethylpropene were charged, stirring was started, and the liquid temperature was heated to 70°C.

135.5 parts of trichlorosilane was added dropwise to the solution through a dropping funnel over 1 hour while appropriately cooling the solution to a temperature of 80 to 90°C. After dropping, the liquid temperature is 80℃.
The mixture was heated and stirred at ℃ for 2 hours, and it was confirmed by gas chromatography analysis that the raw materials had almost disappeared.

Boiling point 115-117℃/16 after cooling and vacuum distillation
As a result of separating the Torr fraction, 2-
Chloromethyl-3-chloropropyltrichlorosilane 2
08.4 parts (yield 80.0%) were obtained.

The results of gas chromatography analysis, elemental analysis, infrared absorption spectrum analysis, and 1H nuclear magnetic resonance absorption analysis of this product were as follows, and it was confirmed that it had the molecular structure of the following formula.

a b C Cβs S 1- CHm CH(CH* CI2)
!・Gas chromatography analysis: Purity 95.3% ・Elemental analysis: Actual value S i ; 10.75% C, 18.47%
H, 2,69% Cβ, 68.09% Calculated value S i: 10.78% C; 18.45
%H, 2,71% Cff: 68.06% Infrared absorption spectrum analysis (liquid film method): Wave number (cm-')
Assignment 2940 C=H 830C-CI H nuclear magnetic resonance absorption analysis (90 MHz, in CDCl3)
:Position Chemical shift δfppml Integral intensity Multiplicity a 0.9-1.2 2Hdb 2.
1-2.5 1HmC3,6-3.8 4Hd Example 2 Internal volume 2 with stirrer, thermometer, addition funnel, reflux condenser and ice bath! 207.0 of the 2-chloromethyl-3-chloropropyltrichlorosilane from Example 1 was added to the flask.
and 700 g of n-hexane and started stirring.
The solution was cooled to a temperature of 0°C.

A mixed solution of 76.8 parts of methanol and 189.6 parts of pyridine was added dropwise to the solution from a dropping funnel over 1 hour while maintaining the liquid temperature at 0 to 20°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, and gas chromatography analysis revealed that 2.
It was confirmed that -chloromethyl-3-3-chloropropyltrichlorosilane had disappeared.

After separating the by-produced pyridine hydrochloride, a fraction with a boiling point of 127-129°C/17 Torr was separated by vacuum distillation, and as a result, 169.9 parts of 2-chloromethyl-3-chloropropyltrimethoxysilane was obtained as a colorless transparent liquid. I got it. This was a yield of 86.0% based on 2-chloromethyl-3-chloropropyltrichlorosilane.

The results of gas chromatography analysis, elemental analysis, infrared absorption spectrometry analysis, (l) (nuclear magnetic resonance absorption analysis and mass spectrometry analysis) of this product were as follows, and it was confirmed that it had the molecular structure of the following formula.

a bcd (CH,Ol,S i -CH,CH(CH,C℃)2
・Gas chromatography analysis: Purity 97.3% ・Elemental analysis: Actual value Si: 11.39% C; 34.00
%H: 6.50% O; 19.43% CI2; 2
8.68% Calculated value S i: 11.36% C;
34. Old%) (:6.53% 0: 19.42%
CI2: 2g, 68%・Infrared absorption spectrum analysis (
Liquid film method): Wavenumber (cm-') Attribution 2940 C-H 1100-1080 5i-OCH.

830, C-Cβ'H nuclear magnetic resonance absorption analysis (90MHz, in CDCh)
:Position Chemical shift δ(ppml Integrated intensity Multiplicity a 3.5 9Hsb O
,7~0.9 2Hdc 2.1~2.5
18 md 3.6~3.8 4H
d・Mass spectrum analysis (m/e): 246 (M
1 Example 3 The reaction proceeded in the same manner as in Example 1 except that 115.0 parts of methyldichlorosilane was used as the chlorosilane.

Then, after cooling, the boiling point is 111-116℃ by distillation under reduced pressure.
As a result of fractionating the fraction at /l 6 Torr, 168.0 parts of 2-chloromethyl-3-chloropropylmethyldichlorosilane (yield 70.0%) was obtained as a colorless transparent liquid.

The results of gas chromatography analysis, elemental analysis, infrared absorption spectrum analysis, and 1H nuclear magnetic resonance absorption analysis of this product were as follows, and it was confirmed that it had the molecular structure of the following formula.

bcd CH.

(1, S 1-CH, CH=(CH, CI2+.

・Gas chromatography analysis: Purity 95.0% ・Elemental analysis: Actual value Si: 11.73% C; 25.02
%H; 4.18% CI2; 59.07% calculated value S
i; 11.70%C; 25.02%H; 4
．． 20% CI2: 59.08%・Infrared absorption spectrum analysis (liquid film method): Wave number (am-') Attribution 2940 C-H l 240 S 1- CHs830
C-Cl2H nuclear magnetic resonance absorption analysis (90 MHz, in CDCh):
Position Chemical shift δ (ppm) Integrated intensity Multiplicity a
0.5 3Hsb O19~
1.2 2Hd c 2.1~2.5 1Hmd 3.6
~3.8 4Hd Example 4 The 2-
167.0 parts of chloromethyl-3-chloropropylmethyldichlorosilane and 600 parts of n-hexane were charged, stirring was started, and the liquid temperature was cooled to 0°C.

A mixed solution of 44.8 parts of methanol and 110.6 parts of pyridine was added dropwise to this from a dropping funnel over a period of 0.5 hours while maintaining the liquid temperature at 0 to 20°C.After one drop was added,
The mixture was stirred at room temperature for 2 hours, and gas chromatography analysis confirmed that 2-chloro, methyl-3-chloropropylmethyldichlorosilane had disappeared.

What about by-product pyridine hydrochloride? After the mixture was separated, a fraction with a boiling point of 121 to 122° C./23 Torr was collected by vacuum distillation to obtain 143.9 parts of 2-chloromethyl-3-chloropropylmethyldimethoxysilane as a colorless transparent liquid. This was a yield of 89.0% based on 2-chloromethyl-3-chloropropylmethyldichlorosilane.

The results of gas chromatography analysis, elemental analysis, infrared absorption spectrum analysis, 1H nuclear magnetic resonance absorption analysis, and mass spectrum analysis of this product were as follows, and it was confirmed that it had a linear molecular structure.

a bcde CH.

(CH301,S 1-CH2CH(CH,Cβ)2・
Gas chromatography analysis: Purity 97.7% Elemental analysis: Actual value Si: 12.17% C, 36.36%
H, 6,96% O; 13.85% CI2: 30
．． 66% calculated value S i ; 12.15% C, 36
, 36% H, 6,98% O; 13.84% (1;
30°67%・Infrared absorption spectrum analysis (liquid film method):
Wave number (cm-') Attribution 2940 C-H l 240 S 1- CHa1100~1
080 5i-OCH.

830 C-(1 ・1H nuclear magnetic resonance absorption analysis (90Mt (z, in CDC): Position Chemical shift δ (ppml Integrated intensity Multiplicity a 3.5 6Hsb
0.3 3Hsb O07~0.9
2Hd c 2.1~2.5 18 md
3.6~3.8 4Hd

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R represents a substituted or unsubstituted monovalent hydrocarbon group, and Y is an alkoxy group, hydroxyl group, or halogen atom. , n represents an integer of 1 to 3) A silane having a chloroalkyl group.