JPH04149185A - Unsaturated organosilicon compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R is (substituted) monofunctional hydrocarbon; Y is hydrolyzable group selected from halogen, alkoxy and aryloxy]. EXAMPLE:1,3-Bis(trichlorosilyl)-2-methylpropane. USE:For improving adhesiveness, reliability, mechanical characteristics, electrical characteristics, water resistance and water vapor resistance of organic-inorganic composite material such as semiconductor sealing material, etc., and reducing cost by adding a large amount of inorganic filler. PREPARATION:3-Chloro-2-chloromethylpropene shown by formula II is made to react with a hydrohalogenosilane compound shown by formula III (X is halogen) in the presence of a catalytic amount of a copper compound by using a tertiary amine as a hydrogen chloride scavenger to give a compound shown by formula I wherein group Y is halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an unsaturated organosilicon compound useful for improving the adhesion of organic-inorganic composite materials.

[Technical background of the invention and its problems]

Examples of organosilicon compounds used to improve the adhesiveness of organic-inorganic composite materials include vinyltrimethoxysilane, allyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.
Various silane cambling agents are known, such as glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. However, since all of these organosilicon compounds have one hydrolyzable silyl group, they have the disadvantage that it is difficult to obtain sufficient adhesive strength. Therefore, for the purpose of improving adhesiveness, a compound having a plurality of hydrolyzable silyl groups has been desired.

[Purpose of the invention]

An object of the present invention is to provide a novel organosilicon compound having two hydrolyzable silyl groups that is useful for improving the adhesion of organic-inorganic composites.

(Structure of the Invention) The present inventor has completed the present invention as a result of intensive studies to achieve the above object.

That is, the present invention is based on the general formula % formula %) (wherein, R is a substituted or unsubstituted monovalent hydrocarbon group; Y is a hydrolyzable group selected from a halogen atom, an alkoxy group, and an aryloxy group; n is a (represents an integer from 0 to 3).

In the compound (1) of the present invention, R is a substituted or unsubstituted monovalent hydrocarbon group. Examples of R include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cyclopentyl;
Cycloalkyl groups such as 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 group, chlorophenyl group, 3,3,3-trifluoropropyl group, cyanoethyl group in which the hydrogen atom bonded to the carbon atom of the monovalent hydrocarbon group is partially substituted with a halogen atom, cyano group, etc. Such substituted hydrocarbon groups are exemplified. 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.

In the compound (1) of the present invention, Y is a hydrolyzable group, for example, a halogen atom such as chlorine, bromine, or iodine;
Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, methoxyethoxy group, n-butoxy group, 5e
Examples include alkoxy groups such as c-butoxy, i-butoxy, t-butoxy, and cyclohexyloxy; and aryloxy groups such as phenoxy. Among these, a chlorine atom is preferred in terms of ease of synthesis, and a methoxy group is preferred in terms of practical stability and appropriate reactivity.

In the compound (1) of the present invention, n is the number of hydrolyzable groups Y, and is an integer of 0 to 3. When the compound (1) of the present invention is used to improve the adhesion of organic-inorganic composite materials, n is 1
-3 is preferable, and 3 is especially desirable.

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

Among the compounds (1) of the present invention, those in which Y is a halogen atom can be produced by the following method.

That is, 3-10 rho 2-chloromethylpropene C)I,
=C(CHICl)2 (II) and -
A hydrohalogenosilane compound represented by the formula (wherein R and n are the same as above, and X is a halogen atom) is mixed with a tertiary amine as a hydrogen chloride scavenger in the presence of a catalytic amount of a copper compound. It can be obtained by a method of reacting as This chemical reaction formula is shown in formula (1).

R1-n CHz-C(CHzCI)z + 2H3iXll+
2B(II) (III) R3-7 1,000 C) Iz=C(CHzSiX,)z +
28'HC1(1)(Ia) (In the formula, I?, Or an aryloxy group can be produced by the following method.

That is, the compound (Ia) obtained by reaction formula (1) and the compound having active hydrogen represented by the formula % (in the formula, Y is an alkoxy group or an aryloxy group) are dehalogenated. Obtained by a method of hydrogenation reaction. This chemical reaction formula is shown in formula (2).

R3-,1 C)12=c(CH25iX1.)Z + 2
ny-.

(Ia) (TV)R3-,1-> CHz=C(CHzSiYn)z+
2n Hχ (2) (Ib) (In the formula, R, It is a known substance, and 3
- A method of chlorinating chloro-2-methylpropene with sulfuryl chloride (European Patent No. 159508) or a method of acting chlorine gas on methylenecyclopropane (R, Koester, S, Arora, P, B
ringer ; Justus Liebigs An
n, CheIll,, 10.16]9 (1973
)) etc.

In reaction formula (1), the hydrohalogenosilane compound (III) used as a raw material is also a known substance. Examples of the hydrohalogenosilane compound (III) include hydrochlorosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, diethylchlorosilane, and phenyldichlorosilane; hydrobromosilanes such as tribromosilane and methyldibromosilane; Silane; and hydroiodosilane such as triiodosilane are exemplified.

Among these, trichlorosilane is particularly preferred in terms of availability of raw materials, reactivity, and the like.

In reaction formula (1), examples of the tertiary amine used as a hydrogen chloride scavenger include triethylamine, tributylamine, pyridine, and N.

Examples include N-dimethylaniline. Among these, triethylamine is particularly preferred in terms of reactivity.

In reaction formula (1), the copper compounds used in the catalyst include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous oxide, cupric oxide, and sulfuric acid. Examples include copper. Among these, cuprous chloride is particularly preferred in terms of availability and catalytic activity. The amount of catalyst used is not particularly limited, but 3-chloro-2-chloromethylpropene (II
) is preferably in the range of 0.01 mol % or more and less than 10 mol %. If it is less than 0.01 mol %, the reactivity is slow and a good yield cannot be achieved in a short period of time. On the other hand, 10
Even if more than mol% is used, there is no particular effect of adding it.

In reaction formula (1), although an organic solvent is not essential, since amine hydrochloride is produced by the reaction, the reaction is usually carried out in the presence of an organic solvent. Such organic solvents are preferably inert to the reactants;
For example, aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; Esters such as acetate; ketones such as acetone, methyl ethyl ketone; and acetonitrile, dimethylformamide,
Examples include aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, and hexamethylphosphoric triamide. Further, these organic solvents can be used alone or in combination of two or more. 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 1000% by weight based on the total weight of the reactants.

In reaction formula (1)', 3-chloro-2-chloromethylpropene (II), a hydrohalogenosilane compound (I
Although the proportions of [[) and tertiary amine to be used are not particularly limited, it is economically preferable to use stoichiometric amounts for the reaction.

In the reaction of reaction formula (1), a catalyst, a tertiary amine, and an organic solvent are placed in a reaction vessel, and 3-chloro-2-chloromethylpropene (II) and hydrohalogenosilane (II) are added to the reaction vessel.
) is preferably added dropwise in small quantities in order to control the reaction.
It is carried out at a temperature range of 0°C, preferably 0 to 50°C. The pressure during the reaction is not particularly limited, but normal pressure is usually applied.The reaction time depends on the reaction conditions, but is usually 001~
10 hours is sufficient.

In reaction formula (2), the active hydrogen-containing compound (IV) used as a raw material includes, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, methoxyethyl alcohol, n-butyl alcohol, 5ec- Alcohols such as butyl alcohol, i-butyl alcohol, t-butyl alcohol, and cyclohexyl alcohol; and phenol are exemplified. Among these, methyl alcohol is preferably used.

In Reaction Formula (2), the use of an organic solvent is not essential, but when used, the matters regarding organic solvents explained in Reaction Formula (1) can be applied.

In the reaction of Reaction Formula (2), the compound (I a) obtained by Reaction Formula (1) and an organic solvent as needed are placed in a reaction vessel, and a stoichiometric amount of the active hydrogen-containing compound (I
It is preferable to carry out the reaction by dropping V). More preferably, in order for the reaction to proceed smoothly, it is desirable to remove the hydrogen halide produced as a by-product, for example, by reducing the pressure of the reaction system, or introducing an inert gas such as nitrogen gas or helium gas into the reaction system. Alternatively, it is preferable to add a stoichiometric amount of a hydrogen halide scavenger to the reaction system. As such a hydrogen halide scavenger, the same hydrogen chloride scavenger as explained in reaction formula (1) can be applied.

This reaction is carried out at -20°C to 100°C, preferably from 0 to 60°C.
It is carried out in the temperature range of °C. The pressure during the reaction is not particularly limited, but normal pressure or reduced pressure is preferred.

Although the reaction time depends on the reaction conditions, 0.5 to 24 hours is usually sufficient.

Isolation and purification of the compound (I) of the present invention from the reaction mixture obtained by Reaction Formula (1) and Reaction Formula (2) can be performed by methods commonly used in the field of organic synthetic compounds. For example, it is possible to isolate the target substance by distillation under reduced pressure.

〔Effect of the invention〕

Since the compound (I) of the present invention has a plurality of hydrolyzable silyl groups that react or interact with the surface of an inorganic material, it improves the adhesiveness and reliability of organic-inorganic composite materials such as semiconductor encapsulating materials. Effective for improvement. 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.

Furthermore, the compound (1) of the present invention has a molecular structure similar to allylsilane compounds such as allyltrimethoxysilane, which is known as a very important reactant in highly selective precision organic synthesis. It is also considered to be extremely useful in synthetic chemistry.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to examples, but the scope of the present invention is not limited only to the following examples.

Example 1 Synthesis of 1.3-bis(trichlorosilyl)-2-methylenepropane A 500 cal flask equipped with a stirrer, temperature needle, addition funnel, reflux condenser and ice bath was charged with 0 cuprous chloride.
．． 5g (0,005 mol), triethylamine 50.
5 g (0.5 mol) and 100 g of diethyl ether were charged, and stirring was started.

To this, a mixed solution of 31.3 g (0.25 mol) of 3-chloro-2-chloromethylpropene and 68.0 g (0.5 mol) of trichlorosilane was added from a dropping funnel at a liquid temperature of 20 to 3 mol.
The mixture was added dropwise over 1 hour while being appropriately cooled to 0°C. After the dropwise addition was completed, the solution was stirred for 2 hours at a temperature of 20"C, and the raw material 3-chloro-2 was analyzed by gas chromatography.
- It was confirmed that the peak of chloromethylpropene had almost disappeared.

Next, triethylamine hydrochloride was filtered, washed with 50 g of diethyl ether, and the filtrate was distilled to a boiling point of 120-1.
As a result of fractionating the fraction at 22° C./'1 Torr, 56.5 g (yield 70.0%) of 1,3-bis(trichlorosilyl)-2-methylenepropane was obtained as a colorless transparent liquid.

The results of gas chromatography analysis, elemental analysis, infrared absorption spectrum analysis, and In 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.

・Gas chromatography analysis: 94.0% ・Elemental analysis: Actual value Si; 17.29% C; 14.98% H
;1.92% C1; 65.81% calculated value 54
; 17.39% C; 14.88% H; 1.87%
C1; 65.86% Infrared 1 yield spectrum analysis (liquid film method) dual wave number (c+w-') Attribution 3050-2850 (,-R 1630C=C ・'H nuclear magnetic resonance absorption analysis (90MHz, CDCl3
(middle): Position Chemical shift δ (ppm) Integrated intensity Multiplicity a 5.00 2) 1
sb 2.35 4Hs Example 2 1.3-Bis(trimethoxysilyl)-2-methylenepropane In a flask of internal volume 11 equipped with a stirrer, thermometer, addition funnel, reflux condenser and ice bath, Example 1, 1,3-bis(trichlorosilyl)-2-methylenepropane 48.4
g (0.15 mol) and 200 g of n-hexane were charged, stirring was started, and the liquid temperature was cooled to 10°C.

To this, add 28.8 g of methyl alcohol (
0.9 mol) and 71.2 g (0.9 mol) of pyridine
The mixed solution was added dropwise over 1 hour while maintaining the liquid temperature at 10 to 20°C. After dropping, the liquid temperature is 20°C.
After stirring for 2 hours at
, 3-bis(trichlorosilyl)-2-methylenepropane was confirmed to have disappeared.

Next, the by-produced pyridine hydrochloride was filtered, and a fraction with a boiling point of 128-131°C/16 Torr was collected by vacuum distillation. As a result, 1,3-bis(trimethoxysilyl)-2-methylene was obtained as a colorless transparent liquid. 26.9 g of propane was obtained.

This was a yield of 60.0% based on 1,3-bis(trichlorosilyl)-2-methylenepropane.

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 the molecular structure of the following formula.

b c ・Gas chromatography analysis: 93.9% ・Elemental analysis: Actual value Si; 23.60% C; 36.20%)
1 ; 8.10% 0 ; 32.10% calculated value
Si; 23.70% C; 36.13% H; 8.0
8% 0; 32.09%・Infrared absorption spectrum analysis (liquid film method): Wave number (cm-') Attribution 3050~2850 C-R 1640C=C 1100~1080 Si-0CR3・"H nuclear magnetic resonance absorption Analysis (90MHz, in CDC15)
:Position Chemical shift δ (ppm) Integrated intensity Multiplicity a 4.80 28
sb 1.10 4H
sC3,5018Hs

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group; Y is a halogen atom, an alkoxy group, or an aryloxy group. An unsaturated organosilicon compound represented by a selected hydrolyzable group; n is an integer of 0 to 3.