JPS63199251A - Elastomer composition containing silane-containing compound - Google Patents

Abstract

PURPOSE:To obtain the titled composition having sharply improved heat resistance and suitable for electrical components and automobile components, by blending a reaction product of a specific silane compound and polysiloxane with an elastomer. CONSTITUTION:1-20pts.wt. reaction product of (A) silane compound containing at least one C=C double bonds and at least one Si-X group (X is Cl or Br) in a molecule and (B) polysiloxane containing at least one hydroxyl group and/or amino group in a molecule is blended with 100pts.wt. elastomer. (2- propenyl) dimethylchlorosilane, 5-trichlorosilyl-2-norbornene, etc., and poly dimethylsiloxane-ended silanol, etc., are used as components (A) and (B), respec tively and a condensation reaction is carried out in a ratio of (A)/(B) of 1/3-2.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an elastomer composition containing a silane-containing compound, and more particularly to an elastomer composition containing a silane-containing compound that can impart excellent heat resistance to various elastomers. The present invention relates to elastomer compositions.

[Conventional technology]

The heat resistance limit temperature of all conventionally known polyolefins is less than 150°C, and therefore, when used regularly at temperatures higher than that, silicone rubber or fluororubber had to be used. These silicone rubbers and fluoro rubbers are 2
It can withstand temperatures of 00°C or higher and has excellent heat resistance, but it has the disadvantage of being expensive. Therefore, silicone rubber and fluororubber do not require heat resistance, but in application fields where the heat resistance of conventional ethylene-α-olefin copolymers is insufficient, it is possible to use one at a relatively low cost.
It has been desired to develop a compound capable of imparting heat resistance of 50 to 200°C.

[Problem that the invention seeks to solve]

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

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that a reaction condensate obtained by condensing a specific silane compound and a specific silicone oil imparts excellent heat resistance to elastomers such as polyolefins. Heading,
We have arrived at the present invention.

That is, the present invention provides (a) at least one C=C double bond and at least one Si-X group (X
is a silane compound having a chlorine atom or a bromine atom),
(b) A silane-containing compound comprising 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, based on 100 parts by weight of the elastomer. An elastomer composition comprising:

(a) At least one C in the molecule used in the present invention
The silane compound having a =C double bond and at least one Si-X group (X is a chlorine atom or a bromine atom) has the general formula l CH2=CH(CH2)n-3i R1m X3-m
(I) (where n is an integer of 1 to 20, preferably 4 to 12, m is an integer of 0 to 2, X is a chlorine atom or a bromine atom, and R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) ) and/or a silane compound represented by the general formula ■ (where β is an integer of 0 to 2, k is an integer of 0 to 6, X is a chlorine atom or a bromine atom, R2, R3 and R4 are , meaning a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which are the same or different from each other.

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

Examples of the silane compound represented by the general formula (1) used in the present invention include 5-trichlorosilyl-2-norbornene, 5-methyldichlorosilyl-2-norbornene, 5-dimethylchlorosilyl-2-norbornene, 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)
Examples include n-butyltrichlorosilane, 2-(5-norbornenyl)n-butylmethyldichlorosilane, and 2-(5-norbornenyl)n-butyldimethylchlorosilane.

Among the compounds represented by the general formulas (1) and/or (2), (5-hexenyl)dimethylchlorosilane, (7-octenyl)dimethylchlorosilane, 5-methyldichlorosilyl-2-norbornene, 5-dimethylchlorosilyl −
Particularly preferred are 2-norbornene, 2-(5-norbornenyl)ethyldimethylchlorosilane, and the like.

The polysiloxane (b) having at least one hydroxyl group and/or amino group in the molecule used in the present invention has the general formula (1) (where p and q are integers of 1 to 10.000, r and 3 is O or 1, Y is a hydroxyl group and/or an amino group, R11, R6, R7, R8, R9 and R10 are the same or different from each other and are an alkyl group having 1 to 6 carbon atoms,
A compound represented by a phenyl group or a vinyl group, R11, R12, R13 and R1i, which are the same or different and mean a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, is preferable.

As the compound represented by the general formula (2), commercially available silicone oils modified with hydroxyl groups at both ends, carbinol-modified silicone oils at both ends, amino-modified silicone oils at both ends, etc. can be used. Specifically, for example, polydiphenylsiloxane-terminated silicone oils can be used. Examples include silanol, polydimethylsiloxane-terminated silanol, polydimethyldiphenylpolysiloxane-terminated diphenylsilanol, polydimethylmethylvinylsiloxane-terminated silanol, polydimethylsiloxane-terminated carbinol, among which polydimethylsiloxane-terminated silanol, polydimethyldiphenyl poly 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. The reaction temperature is not particularly limited, but usually (a) and (b)
The temperature range above the melting point and below the boiling point of any of the compounds (
In particular, a temperature of 10 to 100°C is preferably used. Generally speaking, a higher reaction temperature is preferable in order to shorten the reaction time. Further, (a) and (b) are reacted directly or diluted in a solvent, and the solvent used at this time is preferably toluene or benzene. Further, the dilution ratio is preferably 5 to 20 (weight ratio) to (a) and (b). Furthermore, it is preferable to remove HCl and the like generated during the reaction by a method such as nitrogen bubbling.

Moreover, the silane-containing compound obtained in the present invention can impart excellent heat resistance to the composition by mixing with an elastomer such as a polyolefin. The mixing ratio thereof is preferably 1 to 20 parts by weight per 100 parts by weight of the elastomer from the viewpoint of heat resistance and hardness of the composition after crosslinking.

As the elastomer, commercially available elastomers can be used, 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 distyrene butadiene rubber, hydrogenated acrylonitrile butadiene rubber, hydrogenated natural rubber, hydrogenated styrene butadiene styrene block copolymer, and the like. Among these, EPM, EBM, PE, polybutene, polyhexene, etc., which are polyolefin (co)polymers containing no unsaturated bonds in the main chain, are preferred. In EPM,
Particularly preferred are EPMs with an ethylene content of 50% by weight or more.

In addition, when manufacturing elastomer compositions, general rubber kneading machines (e.g., Banbury mixer, kneader blender, intermixer, roll, continuous mixer, etc.) or resin extruders are used depending on the type of elastomer. can do.

Furthermore, the composition contains general rubber compounding agents, such as reinforcing agents, fillers, softeners, plasticizers, activators, heat stabilizers, antioxidants, crosslinking agents, crosslinking aids, vulcanization accelerators, etc. Can be blended. Specifically, the reinforcing agents include carbon black, white carbon, basic magnesium carbonate,
Examples include activated calcium carbonate. Examples of the filler include calcium carbonate, clay, talc, silica, etc., and examples of the softener include paraffin oil, naphthenic oil, aroma oil, silicone oil, etc. Examples of the heat stabilizer and antioxidant include phenol-based, imidazole-based, and amino-based heat stabilizers and antioxidants. Examples of crosslinking agents include organic peroxides.

Note that it is preferable to use a crosslinking aid in the elastomer composition, and examples of the crosslinking aid include sulfur, p-benzoquinone dioxime, p,p'-dibenzoylquinone dioxime, dinitrosobenzene, and ethylene glycol dioxime. Methacrylate, triallylisocyanurate, liquid polybutadiene, polybutene, polybutadiene resin, etc. can be used.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Note that the physical property tests in the examples were conducted according to JIS K6301.

A) Synthesis of silane-containing compounds 5-methyldichlorosilyl-2-norbornene (reagent:
After stirring 1 mol of double-terminated silanol variable silicone oil (XF40-518, manufactured by Toshiba Silicone Co., Ltd.) at 20°C for 5 hours, bubbling with nitrogen gas for 4 hours to form a condensate. Hereinafter, the obtained product will be referred to as reaction product-1.

B) Evaluation of physical properties An elastomer composition was obtained according to the formulation shown in Table 1 using 100 parts by weight of ethylene fibrobylene rubber (JSREPII, manufactured by Japan Synthetic Rubber Co., Ltd.) and 12 parts by weight of the reaction condensate. This elastomer composition was first prepared by removing the cross-linking agent from the mixture in a 250 cc laboratory plastomill at 70°C for 4 hours.
The mixture was kneaded for a minute, and then a crosslinking agent was added using a 4-inch roll mill. The obtained elastomer composition was pressed in a press at 160° C. for 35 minutes to crosslink the elastomer composition, and a sheet with a thickness of about 211 mm was formed, and the physical properties were evaluated. The physical property test results are shown in Table 2. The composition containing the silane-containing compound of the present invention has excellent heat resistance (
200°C).

Table 1 (Note) *1... White carbon manufactured by Nippon Silica *2...
Paraffin oil manufactured by Idemitsu Kosan Co., Ltd.*3...Tetrakis-[methylene-3-(3',5'-di-t-butyl-4°-hydroxyphenyl)propionate comethane*4...Ciba Geigy Co., Ltd.] Dicumyl peroxide manufactured by NOF Corporation Table 2 Hs JIS-A: 65! Anti-Comparative Example In Example 1, 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, and the heat resistance was poor.

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

Example 3 A) Synthesis of silane-containing compound A silicone oil modified with amino at both ends (S
Using 0.5 mol of F-8417 (manufactured by Toshi Silicone Co., Ltd.), a condensation reaction was carried out in the same manner as in Example IA) to obtain a reaction condensate (hereinafter referred to as reaction condensate-2).

B) Physical property evaluation ethylene-propylene-diene rubber (JSREP43:
Physical properties were evaluated in the same manner as in Example-IB) using 100 parts by weight of Nippon Synthetic Rubber Co., Ltd.) and 10 parts by weight of reaction condensate-2. The results are shown in Table 2, and the resulting composition showed excellent heat resistance.

〔Effect of the invention〕

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

Claims (2)

[Claims] (1) (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; and (b) at least one C=C double bond in the molecule. Elastomer 100 is a reaction product with a polysiloxane having one hydroxyl group and/or amino group.
An elastomer composition containing a silane-containing compound, characterized in that the silane-containing compound is blended in an amount of 1 to 20 parts by weight. (2) The silane compound in (a) has the general formula I CH_2=CH-(CH_2)_n-SiR^1_mX
_3_-_m(I) (where 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, and R^1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) and/or general formula II ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(II) (In the formula, l is an integer from 0 to 2, k is an integer from 0 to 6, and X is Chlorine atom or bromine atom, R^2, R^3 and R^4 are the same or different, hydrogen atom or carbon number 1
~5), and the polysiloxane (b) has the general formula III ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) (where p and q are integers from 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^
1^0 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a vinyl group, which are the same or different from each other, R
^1^1, R^1^2, R^1^3 and R^1^4 are each the same or different and have a hydrogen atom or a carbon number of 1
5. An elastomer composition comprising a silane-containing compound according to claim 1.