JP2002155093A - Organosilicon compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organosilicon compound which is added to a resin or a rubber, has excellent dispersibility even in kneading with an inorganic material, causes a slight change in viscosity of a resin and a rubber composition before molding and is useful as an interfacial binder, an adhesion improver, a component for a primer composition, etc. SOLUTION: This organosilicon compound is represented by general formula I (R1 and R2 are each a 1-4C monofunctional hydrocarbon group; R3 is a 1-10C bifunctional hydrocarbon group; R4 is a 2-10C bifunctional hydrocarbon group; m is 1-10; n is 1-10; p is 1-4: q is 1, 2 or 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organosilicon compound containing an alkoxysilyl group and a polysulfide group in the molecule and an alkylene oxide group in the molecule, and a method for producing the same.

[0002]

2. Description of the Related Art Compounds containing an alkoxysilyl group and a polysulfide group in a molecule have been known. These compounds are used as an interfacial binder between inorganic materials such as silica, aluminum hydroxide, and talc and thermosetting resins, thermoplastic resins, and organic materials such as rubber, adhesion improvers for organic resins and rubber, and primer compositions. It is used.

[0003] As described above, the sulfide group-containing organosilicon compound is applied to a composite material comprising a resin or rubber and an inorganic material. However, the conventionally known sulfide group-containing organosilicon compound can be used as a resin or rubber. When added and kneaded with inorganic materials, dispersibility is insufficient,
There is a problem that the viscosity of the resin or rubber composition before molding may increase.

On the other hand, an organosilicon compound having an alkoxysilyl group and a polysulfide group in a molecule and an alkylene oxide group in a molecule as in the present invention has not been known.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel organosilicon compound which solves such disadvantages and disadvantages, and a method for producing the same.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a halogenoalkyl group-containing organic compound represented by the following general formula (2) is obtained. By reacting a silicon compound, a halogenated alkylene oxide compound at both ends represented by the following general formula (3), and anhydrous sodium sulfide or anhydrous sodium polysulfide represented by the following general formula (4) with sulfur in some cases. ,
An organosilicon compound represented by the following general formula (1) is obtained, and the organosilicon compound represented by the formula (1) can be dispersed well even when it is added to a resin or rubber and kneaded with an inorganic material. It has the ability to stabilize the viscosity of the resin or rubber before molding, and has been found to be effectively used for various applications such as an interface binder, and has led to the present invention. .

Accordingly, the present invention relates to the following [I]:

[0008]

Embedded image (Wherein, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms,
R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is 2 carbon atoms.
10 to 10 divalent hydrocarbon groups, m is 1 to 10, n is 1 to 1
0, p represents 1-4, and q represents 1, 2, or 3. An organosilicon compound represented by the following general formula (2):

[0009]

Embedded image (Wherein, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms,
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen atom, and q represents 1, 2 or 3. A) a halogenoalkyl group-containing organosilicon compound represented by the following general formula (3): Y— (R ⁴ O) _n —R ⁴ —Y (3) (wherein, R ⁴ is a divalent having 2 to 10 carbon atoms) A hydrocarbon group, Y represents a halogen atom, and n represents 1 to 10.) A halogenated alkylene oxide compound at both ends represented by the following general formula (4): Na ₂ S _r (4) (where r is 1 To 4). The method for producing an organosilicon compound according to [I], comprising reacting anhydrous sodium sulfide or anhydrous polysulfide represented by formula (1) with sulfur, if necessary.

Now, the present invention will be described in further detail. As described above, the organosilicon compound of the present invention is represented by the following general formula (1).

[0011]

Embedded image

In the above formula, R ¹ and R ² represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-
Examples thereof include an alkyl group such as a propyl group, an i-propyl group, and an n-butyl group. Of these, a methyl group and an ethyl group are preferable. R ³ has 1 to 10 carbon atoms, preferably 2 to
6, particularly preferably a divalent hydrocarbon group of 3, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, an n-butylene group, an i-butylene group, a hexylene group, a decylene group, and a phenylene group; Examples include an aralkylene group such as an arylene group and a methylphenylethylene group. R ⁴ represents a divalent hydrocarbon group having 2 to 10, preferably 2 to 4, particularly preferably 2 carbon atoms, for example, an ethylene group, a propylene group, an n-butylene group, an i-butylene group,
Examples include an alkylene group such as a hexylene group and a decylene group, an arylene group such as a phenylene group, and an aralkylene group. m is 1 to 10, preferably 1 to 5, particularly preferably 2 to 4, n is 1 to 10, preferably 1 to 4, particularly preferably 1 or 2, p is 1 to 4, preferably 1 or 2,
Particularly preferably, q represents 1, 2 or 3, preferably 2 or 3, particularly preferably 3. As the compound represented by the general formula (1), the following can be exemplified as typical examples.

[0013]

Embedded image

As described above, such an organosilicon compound has the following general formula (2)

Embedded image (Wherein, R ¹ , R ² , R ³ and q have the same meanings as described above, and X represents a halogen atom), and a halogenoalkyl group-containing organosilicon compound represented by the following general formula (3): Y- (R ⁴ O) _n -R ⁴ -Y (3) (wherein R ⁴ and n have the same meaning as described above, and Y represents a halogen atom). Reaction of an oxide compound, anhydrous sodium sulfide or anhydrous sodium polysulfide represented by the following general formula (4) Na ₂ S _r (4) (where r represents 1 to 4) with sulfur as required By doing so, it can be manufactured.

In this case, as the compound represented by the general formula (2), the following compounds can be exemplified. _{(CH 3 O) 3 Si- (} CH 2) 3 -Cl (CH 3 CH 2 O) 3 Si- (CH 2) 3 -Cl (CH 3 O) 3 Si- (CH 2) 4 -Cl (CH 3 O) ₃ Si— (CH ₂ ) ₆ —Br (CH ₃ O) ₃ Si— (CH ₂ ) ₁₀ —Br

As the compound of the above general formula (3), the following compounds can be exemplified. _{Cl-CH 2 CH 2 OCH 2} CH 2 -Cl Cl- (CH 2 CH 2 O) 2 CH 2 CH 2 -Cl Cl- (CH 2 CH 2 O) 3 CH 2 CH 2 -Cl Cl- (CH 2 CH _{2 O) 4 CH 2 CH 2} -Cl Cl- (CH 2 CH 2 CH 2 O) 2 CH 2 CH 2 CH 2 -Cl Cl- (CH 2 CH 2 CH 2 CH 2 O) 2 CH 2 CH 2 CH 2 C
_{H 2 -Cl Cl- (CH (CH} 3) CH 2 O) 2 CH (CH 3) CH 2
-Cl

Further, examples of the compound represented by the general formula (4) include Na ₂ S, Na ₂ S ₂ , Na ₂ S ₃ and Na ₂ S ₄ .

As a method for producing anhydrous sodium sulfide Na ₂ S of the compound (4), a dehydrated water-containing sodium sulfide may be used. And those obtained by reacting metallic sodium or potassium with sulfur in an anhydrous state. In addition, anhydrous sodium polysulfide may be obtained by dehydrating water-containing sodium polysulfide, or may be obtained by reacting anhydrous sodium sulfide with sulfur in an anhydrous state. Alternatively, one obtained by reacting potassium and sulfur in an anhydrous state may be used.

In reacting the compounds of the above general formulas (2), (3) and (4) and, if necessary, sulfur, the use of a solvent is optional. For example, pentane, hexane, heptane, octane, benzene, toluene , Hydrocarbons such as xylene, alcohols such as methanol and ethanol, ethers such as dibutyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, and amides such as dimethylformamide. The use of alcohols such as methanol and ethanol is particularly preferred.

The reaction temperature at that time is about 0 to 150 ° C., preferably about 50 to 100 ° C. The reaction may be carried out until the sodium sulfide or sodium polysulfide disappears, and is usually about 30 minutes to 20 hours.

The reaction may be carried out in any manner. For example, a mixture of the compounds represented by the general formulas (2) and (3) is prepared by charging the compound represented by the general formula (4) and optionally sulfur and a solvent. May be added dropwise, or after the compound represented by the general formula (2) is added dropwise, the compound represented by the general formula (3) may be added dropwise. Further, the compounds represented by the general formulas (2) and (3) and, if necessary, sulfur and a solvent are charged, and
May be gradually introduced.

The reaction molar ratio of each component is as follows.

The molar ratio between the halogenoalkyl group-containing organosilicon compound represented by the general formula (2) and the alkylene oxide compound having halogen at both terminals represented by the general formula (3) is expressed by the following formula: Compound of general formula (3) = 1
/0.45 to 2, preferably a halogenoalkyl group-containing organosilicon compound represented by the general formula (2) and a halogen group at both terminal halogenated alkylene oxide compounds represented by the general formula (3). The molar ratio of the anhydrous sodium sulfide or the anhydrous sodium polysulfide represented by the formula (4) to sodium is the compound of the general formula (2) + the halogen in the compound of the general formula (3) / the compound of the general formula (4) Sodium in =
It is preferably set to 1 / 0.9 to 1.1. The amount of sulfur to be added is arbitrary, but at least (m-r) moles may be added.

The organosilicon compound of the formula (1) of the present invention is
It is useful as an interface binder between an inorganic material and an organic material, an adhesion improver for an organic resin or rubber, a component for a primer composition, and the like.

[0025]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 250 g of methanol, 78 g (1.0 mol) of anhydrous sodium sulfide, 96 g of sulfur (3 g) were placed in a 1 liter separable flask equipped with a nitrogen gas inlet tube, a thermometer, a Dimroth condenser and a dropping funnel. .
0 mol) and 198.5 g (1.0 mol) of 3-chloropropyltrimethoxysilane and 93.5 g of triethylene glycol dichloride (0.
5 mol) was added dropwise. This dripping required 50 minutes. After completion of dropping, aging was continued for 8 hours. Thereafter, the solution was filtered.

The filtrate was concentrated under reduced pressure with a rotary evaporator to obtain 285.6 g of a brown transparent liquid. This has a viscosity of 83 mm ² / s at 25 ° C. and a refractive index of 25 ° C.
Was 1.5565. Infrared absorption spectrum analysis and 1H NMR spectra analysis the results of this one, the following average compositional formula _{(CH 3 O) 3 Si (} CH 2) 3 -S 4 - (CH 2) 2 O (CH 2) 2 O _{(CH 2) 2 -S 4 -} (CH 2) 3 S
It was confirmed to be a sulfide group-containing alkoxysilane represented by i (OCH ₃ ) ₃ .

Example 2 The reaction was carried out in the same manner as in Example 1 except that 71.5 g (0.5 mol) of diethylene glycol dichloride was used instead of triethylene glycol dichloride used in Example 1, and a brown transparent liquid was obtained. 2
52.1 g were obtained. Its viscosity is 78m at 25 ° C.
m ² / s, the refractive index was 1.5649 at 25 ° C.
Infrared absorption spectrum analysis and the ones, as a result of 1H nuclear magnetic resonance spectrum analysis, the following average compositional formula _{(CH 3 O) 3 Si (} CH 2) 3 -S 4 - (CH 2) 2 O (CH 2) 2 _{-S 4 - (CH 2) 3} Si (OCH 3)
_This was confirmed to be a sulfide group-containing alkoxysilane represented by ₃ .

Example 3 Instead of the 3-chloropropyltrimethoxysilane used in Example 1, 240.5 g (1.0 mol) of 3-chloropropyltriethoxysilane was used.
The reaction was carried out in the same manner as in Example 1 except for changing to l), to obtain 301.5 g of a brown transparent liquid. Infrared absorption spectrum analysis of this compound, and 1H nuclear magnetic resonance spectrum analysis the results of the following average compositional formula _{(CH 3 CH 2 O) 3} Si (CH 2) 3 -S 4 - (CH 2) 2 O (CH 2 _{) 2 O (CH 2) 2} -S 4 - (C
It was confirmed to be a sulfide group-containing alkoxysilane represented by H ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ .

Example 4 In place of 3-chloropropyltrimethoxysilane used in Example 1, 3-chloropropyltriethoxysilane was replaced by 240.5 g (1 mol), and the amount of sulfur used was 32 g (1.0 mol). The reaction was conducted in the same manner as in Example 1 except that
6 g were obtained. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula (CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ -S _2- (CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) ₂ -S _2- (C
It was confirmed to be a sulfide group-containing alkoxysilane represented by H ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ .

Example 5 174 g of anhydrous sodium sulfide instead of the anhydrous sodium sulfide and sulfur used in Example 1
(1.0 mol), except that the reaction was carried out in the same manner as in Example 1 to obtain 297.8 g of a tan transparent liquid. Infrared absorption spectrum analysis of this compound, and 1H nuclear magnetic resonance spectrum analysis the results of Example 1 Similarly, the following average compositional formula _{(CH 3 O) 3 Si (} CH 2) 3 -S 4 - (CH 2) 2 O _{(CH 2) 2 O (CH} 2) 2 -S 4 - (CH 2) 3 S
It was confirmed to be a sulfide group-containing alkoxysilane represented by i (OCH ₃ ) ₃ .

Example 6 A reaction was carried out in the same manner as in Example 1 except that 285 g (1.0 mol) of 6-bromohexyltrimethoxysilane was used instead of 3-chloropropyltrimethoxysilane used in Example 1. Thus, 345 g of a tan transparent liquid was obtained. Infrared absorption spectrum analysis of this compound, and 1H nuclear magnetic resonance spectrum analysis the results of the following average compositional formula _{(CH 3 O) 3 Si (} CH 2) 6 -S 4 - (CH 2) 2 O (CH 2) 2 _{O (CH 2) 2 -S 4} - (CH 2) 6 S
It was confirmed to be a sulfide group-containing alkoxysilane represented by i (OCH ₃ ) ₃ .

Example 7 The amount of the triethylene glycol dichloride used in Example 1 was 187.0 g.
(1.0 mol) and the amount of anhydrous sodium sulfide used is 11
7.0 g (1.5 mol), the amount of sulfur used was 144.0 g
(4.5 mol), except that the reaction was carried out in the same manner as in Example 1 to obtain 332.0 g of a black-brown transparent liquid. As a result of an infrared absorption spectrum analysis and a 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula (CH ₃ O) ₃ Si (CH ₂ ) ₃ -S ₄ -((CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) ₂ -S ₄ ) _2- (C
It was confirmed to be a sulfide group-containing alkoxysilane represented by H ₂ ) ₃ Si (OCH ₃ ) ₃ .

[0034]

The organosilicon compound of the present invention has excellent dispersibility even when added to a resin or rubber and kneaded with an inorganic material, and has an excellent viscosity change of the resin or rubber composition before molding. It is useful as an interfacial binder, an adhesion improver, a component for a primer composition, and the like.

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Claims (2)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms,
R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is 2 carbon atoms.
10 to 10 divalent hydrocarbon groups, m is 1 to 10, n is 1 to 1
0, p represents 1-4, and q represents 1, 2, or 3. An organosilicon compound represented by the formula: 2. The following general formula (2): (Wherein, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms,
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen atom, and q represents 1, 2 or 3. A) a halogenoalkyl group-containing organosilicon compound represented by the following general formula (3): Y— (R ⁴ O) _n —R ⁴ —Y (3) (wherein, R ⁴ is a divalent having 2 to 10 carbon atoms) A hydrocarbon group, Y represents a halogen atom, and n represents 1 to 10.) A halogenated alkylene oxide compound at both ends represented by the following general formula (4): Na ₂ S _r (4) (where r is 1 2. The method for producing an organosilicon compound according to claim 1, wherein the reaction is carried out by reacting anhydrous sodium sulfide or anhydrous polysulfide represented by the formula (1) to (4) with sulfur in some cases.