JPH0735455B2 - Elastomer composition containing a silane-containing compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an elastomer composition containing a silane-containing compound, and more specifically, it contains a silane-containing compound capable of imparting excellent heat resistance to various elastomers. It relates to an elastomer composition.

[Conventional technology]

The heat-resistant limit temperature of the conventionally known polyolefins is less than 150 ° C., so that silicone rubber or fluororubber has to be used when it is used at a temperature higher than that. These silicone rubber and fluoro rubber are 200
Withstands temperatures above ℃ and has excellent heat resistance,
It has the disadvantage of high cost. Therefore, it does not require heat resistance as much as silicone rubber and fluororubber, but in the application field where the heat resistance of conventional ethylene-α-olefin copolymers is insufficient, it is relatively low cost and 150 to 2
It has been desired to develop a compound capable of imparting heat resistance at 00 ° C.

[Problems to be solved by the invention]

An object of the present invention is to provide an elastomer composition containing a silane-containing compound capable of imparting excellent heat resistance to an elastomer such as polyolefin.

[Means for solving problems]

The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, a reaction condensate obtained by subjecting a specific silane compound and a specific silicone oil to a condensation reaction imparts excellent heat resistance to an elastomer such as a polyolefin. Heading
The present invention has been reached.

That is, the present invention relates to (a) a silane compound having at least one C = C double bond and at least one Si-X group (X is a chlorine atom or a bromine atom) in the molecule,
(B) 1 to 20 parts by weight of a reaction product with a polysiloxane having at least one hydroxyl group and / or amino group in the molecule, and 1 to 20 parts by weight of the reaction product is blended with the silane-containing compound. And an elastomer composition containing the same.

At least one C in the molecule (a) used in the present invention
═C double bond and at least one Si—X group (X is a chlorine atom or a bromine atom) have the general formula I CH ₂ ═CH— (CH ₂ ) n-SiR ¹ mX _3- m (I) (In the formula, n is 1 to 20, preferably 4 to 12 and m is 0.
To an integer of 2, X is a chlorine atom or a bromine atom, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and / or the general formula II. (In the formula, l is an integer of 0 to 2, k is an integer of 0 to 6, X is a chlorine atom or a bromine atom, R ² , R ³ and R ⁴ are the same or different from each other, a hydrogen atom or a carbon number of 1 to A compound represented by (meaning an alkyl group of 5) is preferable.

Examples of the silane compound represented by the general formula I used in the present invention include (2-propenyl) dimethylchlorosilane, (3-butenyl) dimethylchlorosilane, and (4
-Pentenyl) dimethylchlorosilane, (5-hexenyl) dimethylchlorosilane, (6-heptenyl) dimethylchlorosilane, (7-octenyl) dimethylchlorosilane, (2-propenyl) methyldichlorosilane, (3
-Butenyl) methyldichlorosilane, (4-pentenyl) methyldichlorosilane, (5-hexenyl) methyldichlorosilane, (6-heptenyl) methyldichlorosilane, (7-octenyl) methyldichlorosilane, (2
-Propenyl) trichlorosilane, (3-butenyl) trichlorosilane, (4-pentenyl) trichlorosilane, (5-hexenyl) trichlorosilane, (6-heptenyl) trichlorosilane, (7-octenyl) trichlorosilane and the like.

Examples of the silane compound represented by the general formula II used in the present invention include 5-trichlorosilyl-2-norbornene, 5-methyldichlorosilyl-2-norbornene, 5-dimethylchlorosilyl-2-norbornene, and 2
-(5-norbornenyl) ethyltrichlorosilane, 2
-(5-Norbornenyl) ethylmethyldichlorosilane, 2- (5-norbornenyl) ethyldimethylchlorosilane, 2- (5-norbornenyl) propyltrichlorosilane, 2- (5-norbornenyl) propylmethyldichlorosilane, 2- (5-norbornenyl) propyldimethylchlorosilane, 2- (5-norbornenyl) n
-Butyltrichlorosilane, 2- (5-norbornenyl) n-butylmethyldichlorosilane, 2- (5-norbornenyl) n-butyldimethylchlorosilane and the like can be mentioned.

Among the compounds represented by the general formula I and / or II, (5-hexenyl) dimethylchlorosilane, (7-octenyl) dimethylchlorosilane, 5-methyldichlorosilyl-2-norbornene, 5-dimethylchlorosilyl-
2-Norbornene, 2- (5-norbornenyl) ethyldimethylchlorosilane and the like are particularly preferable.

The polysiloxane having at least one hydroxyl group and / or amino group in the molecule (b) used in the present invention is represented by the general formula III (In the formula, p and q are integers of 1 to 10,000, r and s are 0 or 1, Y is a hydroxyl group and / or an amino group, R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different from each other, and an alkyl group having 1 to 6 carbon atoms, a phenyl group or a vinyl group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are mutually The same or different, and means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) is preferable.

As the compound represented by the general formula III, a commercially available silicone oil modified with hydroxyl groups at both ends, a carbinol modified silicone oil with both terminals, an amino modified silicone oil with both terminals and the like can be used. Specifically, for example, polydiphenylsiloxane terminals can be used. Examples thereof include silanol, polydimethylsiloxane terminal silanol, polydimethyldiphenylpolysiloxane terminal diphenylsilanol, polydimethylmethylvinylsiloxane terminal silanol, polydimethylsiloxane terminal carbinol, and the like. Of these, polydimethylsiloxane terminal silanol and polydimethyldiphenylpoly Siloxane terminated silanols are preferred.

The condensation reaction of (a) and (b) in the present invention is preferably carried out at a molar ratio of (a) / (b) = 1/3 to 2. Although the reaction temperature is not particularly limited, it is usually in the temperature range above and below the melting point of any of the compounds (a) and (b) (particularly
10 to 100 ° C.) is preferably used. Generally, a higher reaction temperature is preferable in order to shorten the reaction time. Also (a)
And (b) are directly reacted or diluted with a solvent to be reacted, and the solvent used at this time is toluene,
Benzene is preferred. Also, as the dilution ratio,
It is preferably 5 to 20 (weight ratio) with respect to (a) and (b).
Further, it is preferable to remove HCl and the like generated during the reaction by a method such as nitrogen bubbling.

Further, the silane-containing compound obtained in the present invention can impart excellent heat resistance to those compositions by mixing with an elastomer such as polyolefin. The mixing ratio is preferably 1 to 20 parts by weight based on 100 parts by weight of the elastomer from the viewpoints of heat resistance and hardness of the composition after crosslinking.

As the elastomer, a commercially available elastomer can be used, and specifically, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), polyethylene (PE), polybutene, polyhexene-1, ethylene butene-1 copolymer ( EBM), ethylene butene-1 diene copolymer, acrylic rubber (ACM), hydrogenated-polybutadiene, hydrogenated-polyisoprene, hydrogenated-styrene butadiene rubber, hydrogenated-acrylonitrile butadiene rubber, hydrogenated natural rubber, hydrogenated -Styrene butadiene styrene block copolymer etc. can be mentioned. Among these, polyolefin-based (co) polymers having no unsaturated bond in the main chain, such as EPM, EBM, PE, polybutene, and polyhexene are preferable. Among EPMs, EPMs having an ethylene content of 50% by weight or more are particularly preferable.

Further, in the production of the elastomer composition, a general rubber kneader (for example, Banbury mixer, kneader blender, intermixer, roll, continuous kneader, etc.) or resin extruder is used depending on the type of elastomer. be able to.

Further, the composition is a general rubber compounding agent, that is, a reinforcing agent, a filler, a softening agent, a plasticizer, an activator, a heat stabilizer, an antioxidant, a crosslinking agent, a crosslinking aid, a vulcanization accelerator and the like. It can be blended. Specifically, as the reinforcing agent, carbon black, white carbon, basic magnesium carbonate,
Examples include activated calcium carbonate. Examples of the filler include calcium carbonate, clay, talc and silica, and examples of the softening agent include paraffin oil, naphthene oil, aroma oil and silicone oil. Examples of heat stabilizers and antioxidants include phenol-based, imidazole-based and amino-based heat stabilizers and antioxidants.
Examples of the cross-linking agent include organic peroxides.

A crosslinking assistant is preferably used in the elastomer composition, and examples of the crosslinking assistant include sulfur, p-benzoquinonedioxime, p, p'-dibenzoylquinonedioxime, dinitrosobenzene, and ethyleneglycoldiene. Methacrylate, triallyl isocyanurate, liquid polybutadiene, polybutene, polybutadiene resin and the like can be used.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

The physical property tests in the examples were carried out according to JIS K6301.

A) Synthesis of silane-containing compound 5-methyldichlorosilyl-2-norbornene (reagent:
1 mol of silanol-modified silicone oil (XF40-518, manufactured by Toshiba Silicone Co., Ltd.) at both ends was stirred for 5 hours at 20 ° C., and then bubbling with nitrogen gas for 4 hours to obtain a condensate. Hereinafter, the obtained product is referred to as reaction product-1.

B) Evaluation of Physical Properties Using 100 parts by weight of ethylene propylene rubber (JSREP11 manufactured by Japan Synthetic Rubber Co., Ltd.) and 12 parts by weight of reaction condensate-12, an elastomer composition was obtained by the compounding recipe shown in Table 1. This elastomer composition was prepared by first removing the cross-linking agent from the composition.
It was obtained by kneading with a 250 cc Labo Plastomill at 70 ° C. for 4 minutes and then adding a crosslinking agent using a 4-inch roll machine.
The obtained elastomer composition was pressed at 160 ° C. for 35 minutes.
Press for a minute to crosslink the elastomer composition and
A 2 mm sheet was molded and the physical properties were evaluated. The results of physical property tests are shown in Table 2. The composition containing the silane-containing compound of the present invention showed excellent heat resistance (200 ° C.).

Comparative Example Physical properties were evaluated in the same manner as in Example-1, except that the reaction condensate of the present invention was not used. The results are shown in Table 2, but the heat resistance was poor.

Example 2 Physical properties were evaluated in the same manner as in Example-1, except that 5 parts by weight of the reaction condensate-1 was used in Example-1. The results are shown in Table 2, and the obtained composition showed excellent heat resistance.

Example 3 A) Synthesis of compound containing silane 0.5 mol of amino-modified silicone oil (SF-8417: manufactured by Toray Silicone Co., Ltd.) at both ends was used for 1 mol of 7-octyldimethylchlorosilane (reagent: manufactured by Chisso). A condensation reaction was performed in the same manner as in Example-1A) to obtain a reaction condensate (hereinafter referred to as reaction condensate-2).

B) Evaluation of Physical Properties Using 100 parts by weight of ethylene-propylene-diene rubber (JSREP43: manufactured by Nippon Synthetic Rubber Co., Ltd.) and 10 parts by weight of Reaction Condensate-2, evaluation of physical properties was performed in the same manner as in Example-1B). The results are shown in Table 2, and the obtained composition showed excellent heat resistance.

〔The invention's effect〕

According to the present invention, it is possible to obtain a silane-containing compound that imparts excellent heat resistance to various elastomers, and therefore, the elastomer composition of the present invention can be used in fields requiring high heat resistance, such as electric wire cables. Representative electrical components,
Automotive parts such as hoses, packing, boots, etc.
Alternatively, it can be used for belts and other industrial products.

Claims (2)

[Claims] 1. A silane compound having at least one C═C double bond and at least one Si—X group (X is a chlorine atom or a bromine atom) in the molecule, and (b) the molecule. The reaction product with a polysiloxane having at least one hydroxyl group and / or amino group in the elastomer 10
An elastomer composition containing a silane-containing compound, characterized in that 1 to 20 parts by weight is blended with 0 part by weight. 2. The silane compound of (a) has the general formula I CH ₂ ═CH— (CH ₂ ) n-Si R ¹ m X _3- m (I) (wherein n is an integer of 1 to 20, m Is an integer of 0 to 2, X is a chlorine atom or a bromine atom, R ¹ is a hydrogen atom or a carbon number of 1 to
5 means an alkyl group of 5) and / or the general formula II (In the formula, l is an integer of 0 to 2, k is an integer of 0 to 6, X is a chlorine atom or a bromine atom, R ² , R ³ and R ⁴ are the same or different from each other, a hydrogen atom or a carbon number of 1 to 5 means an alkyl group) and the polysiloxane of (b) has the general formula III (In the formula, p and q are integers of 1 to 10,000, r and s are 0 or 1, Y is a hydroxyl group and / or an amino group, R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different from each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a vinyl group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ Are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, which are the same or different from each other), and the elastomer composition containing the silane-containing compound according to claim 1.