JPS6023412A - Oil-resistant rubber composition - Google Patents

Abstract

PURPOSE:The titled composition having improved freeze resistance, and improved resistance to an addition agent, etc., obtained by adding an agent for vulcanization to a copolymer comprising a specific glycidyl carboxylate, an ethylenic unsaturated group-containing epoxide, etc. as comonomer components. CONSTITUTION:(A) Glycidyl carboxylate (e.g., glycidyl acetate, etc.) containing 1-4C alkyl group is copolymerized with (B) an ethylenic unsaturated group- containing epoxide (e.g., allylglycidyl ether, etc.) and/or a halogen-containing epoxide (e.g., epichlorohydrin, etc.), and, if necessary, (C) another epoxide (e.g., ethylene oxide, etc.) in the presence of an organotin compound and phosphoric acid, etc. as a catalyst, to give a copolymer having >=0.8 reduced viscosity (in 0.1wt% monochlorobenzene solution at 40 deg.C). The copolymer is blended with (D) an agent for ulcanization, to give the desired rubber composition.

Description

[Detailed description of the invention] The present invention relates to a novel oil-resistant rubber composition.

Typical oil-resistant rubbers include acrylonitrile-butadiene copolymer rubber, epichlorohydrin rubber, and acrylic rubber, which are used depending on the usage environment. However, in recent years, as the components of fuel oil and lubricating oil have changed, various problems have arisen.

For example, the content of aromatic hydrocarbons is increasing in fuel parts, and the types and amounts of various additives in lubricating oils are increasing, so rubbers that come into contact with or are immersed in these substances may experience a decline in physical properties or be contaminated with additives. There is a need to improve resistance to prevent deterioration due to the effects of

- Mechanical deterioration caused by oil degraded by oxidation, so-called rancid oil, is also a major problem for oil-resistant rubber products.

As a countermeasure to this type of problem, fluororubber is often used as a substitute due to its excellent performance, but this rubber has the drawbacks of being very expensive and having significantly poor cold resistance. Generally, as oil resistance improves, cold resistance of rubber decreases, and shrimp chlorohydrin-ethylene oxide typical composite rubbers are known as rubbers that have both high oil resistance and cold resistance. However, on the other hand, this rubber is susceptible to deterioration due to various additives in the oil or rancid oil. In this way, epichlorohydrin rubber has the oxidizing power WI (
It is susceptible to lubricating oil additives due to oxidative deterioration (oxidative deterioration) and the presence of chlorine, and the possibility of corrosion to metals is a problem.

In addition, 21-lyl rubber has poor ozone resistance due to the presence of unsaturated bonds and tends to become brittle during aging.

Furthermore, the balance between oil resistance and cold resistance is poor.

Furthermore, although acrylic rubber has excellent lubricating oil resistance, it has extremely poor resistance to fuel oil and very poor cold resistance.

Under these circumstances, there is a desire for an inexpensive rubber that has both high oil resistance and cold resistance, and has improved resistance to the above-mentioned additives, rancid oil, and the like.

The present inventors have arrived at the present invention as a result of intensive research to satisfy these conditions. That is, the present invention has been developed to meet these conditions.
- A copolymer consisting of a glycidyl carboxylate having a C4 alkyl group, an ethylenically unsaturated group-containing epoxide and/or a halogen-containing epoxide, and a vulcanizing agent for the copolymer. It is an oil-resistant rubber composition.

- Carboxylic acid glycidyl ester, which is a comonomer component in the present invention, is represented by the general formula (C1-04 represents an alkyl group), and is one type of glycidyl acetate, glycidyl propione-1 to glycidyl butylene-1, etc. or two or more kinds, and glycidyl acetate-1- and glycidyl probionate are particularly preferred. Ethylenically unsaturated group-containing epoxides with other monomer components include allyl glycidyl ether and glycidyl acrylate.

Examples include glycidyl methacrylate, glycidyl sorbate, glycidyl quinamate, butadiene monoxide, and vinylcyclohexene oxide. Examples of halogen-containing epoxides include epichlorohydrin,
■ Examples include pibromhydrin and glycidyl monochloroacetate. Examples of epoxides other than those mentioned above that can be used as the =1 monomer component include ethylene oxide, propylene oxide, and styrene oxide.

Specific examples of various copolymers used in the present invention are as follows.

Glycidyl acetate-allyl glycidyl ether copolymer Glycidyl probionate-allyl glycidyl ether copolymer Glycidyl butyrate-allyl glycidyl ether copolymer Glycidyl acetate-glycidyl acrylate copolymer Glycidyl acetate-glycidyl methacrylate copolymer Glycidyl Acetate-monochloroglycidyl acetate copolymer Glycidyl acetate-ethylene oxide-allyl glycidyl ether copolymer Glycidyl acetate-ethylene oxide-glycidyl acrylate copolymer Glycidyl amide-ethylene oxide-Glycidyl methacrylate copolymer Glycidyl acetate-Ethylene oxide-Glycidyl methacrylate copolymer Glycidyl acetate-Ethylene oxide-Glycidyl acrylate copolymer Glycidyl sorbate copolymer Glycidyl areate-ethylene oxide monochloroacetate copolymer Glycidyl acetate-1-monoethylene A oxide Ebihalohydrin copolymer Glycidyl arechie 1--Epihalohydrin copolymer Glycidyl propionate- Epihalohydrin copolymer glycidyl zodiley 1--epihalohydrin typical polymer glycidyl aredate-epihalohydrin-allyl glycidyl ether copolymer glycidyl acetate-shrimp helohydrin-glycidyl acrylate copolymer glycidyl arechie 1-mono-shrimp halohydrin- Glycidyl methacrylate copolymer glycidyl acetate-1-mono-shrimp halohydrin-glycidyl sorbate copolymer glycidyl acetate-shrimp halohydrin-ethylene oxide-allyl glycidyl ether copolymer glycidyl acetate-shrimp halohydrin-ethylene oxide-allyl glycidyl ether copolymer glycidyl Acetate - Shrimp halohydrin - Ethylene oxide - Glycidyl acrylate copolymer Glycidyl allotate - Shrimp halohydrin - Ethylene oxide - Glycidyl methacrylate copolymer Glycidyl acetate - Shrimp halohydrin - Ethylene oxide - Glycidyl sorbate copolymer Glycidyl aretate - Shrimp halohydrin - Ethylene oxide - Glycidyl monochloroacetate Copolymer glycidyl aredate-glycidyl propione-1-monoallyl glycidyl ether copolymer integral glycidyl arede 1--glycidyl propione-1--glycidyl acrylate copolymer glycidyl acetate-1--glycidyl propionate- Typical combination of glycidyl methacrylate Glycidyl acetate-glycidyl norobione-1-1 Typical combination of glycidyl sorbate -Epiha] cohydrin copolymer glycidyl ahidate-glycidyl brobioneto-epiha 1 hydrin-ethylene oxide copolymer glycidyl acetate-1 - glycidyl brobione A-1-
- Ethylene A gycido allyl glycidyl ether co-containing glycidyl acetate-1 - glycidyl brobionate epiha 1 cohydrin - ethylene oxide glycidyl acrylate typical combination glycidyl acetate glycidyl brobionate shrimp halohydrin - ethylene oxide - Glycidyl methacrylate copolymer glycidyl aretate - Glycidyl propionate - Shrimp halohydrin - Ethylene oxide - Glycidyl monochloroacetate copolymer.

(In the above 'epihalohydrin' stands for epichlorohydrin and/or epibromohydrin).

As the copolymer component of these copolymers, those containing at least 10 mol % of glycidyl nisdale carboxylate are used. If the content of the above components is less than 10 mol %, the oil resistance of the vulcanized rubber decreases, which is not preferable. Further, it is necessary that at least 1 mol % or more of an epoxide having an ethylenically unsaturated group or a halogen-containing epoxide serving as a vulcanizing functional group is contained.

For example, in the carboxylic acid glycidyl nisder-allyl glycidyl ether copolymer, the former is preferably 8 (1 = 997 mol%), and the latter is preferably in the range of 20-1 mol%; in the carboxylic acid glycidyl ester-epihalohydrin copolymer, The former is preferably in a range of 20 to 95 mol%, and the latter is preferably in a range of 5 to 80 mol%.

These copolymers are disclosed in the United States filed by the applicant.
It can be obtained by ring-opening copolymerization of each heptamer component using as a catalyst a thermal condensation product of a) an organotin compound and b) an alkyl ester of orthophosphoric acid or polyphosphoric acids disclosed in Q3773694@. The polymerization reaction is usually carried out at a temperature range of 10 to 80°C in the presence or absence of a solvent, and the catalyst is
~1. It is desirable that the Og range is appropriate and that the water content in the reaction system is as low as possible. The thus obtained copolymer is a rubbery random Jt having a reduced viscosity of 0.5 or more when measured in a 0.1% benzene solution at 40°C.
It is a polymer.

The composition of the present invention can contain polymers other than the above copolymers as polymer components.

These polymers are not particularly limited, but are preferably those that can be vulcanized using the same vulcanization system as the above-mentioned copolymers.

For example, preferred polymers for the copolymer with hepatomer having an ethylenically unsaturated group such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate include natural rubber and isoprene rubber.

Butadiene rubber, styrene-butadiene rubber.

Ethylene-propylene-butadiene rubber, butyl rubber,
Examples include halogenated butyl rubber, Robrene rubber, acrylonitrile-butadiene rubber, epichlorohydrin-allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer rubber, and unsaturated group-containing acrylic rubber.

Examples of preferable polymers for copolymers with halogen-containing polymers such as epihalohydrin and glycidyl monochloroacetate include epichlorohydrin homopolymer rubber, epichlorohydrin-allyl glycidyl ether copolymer rubber, and epichlorohydrin-ethylene oxide copolymer rubber. , shrimp chlorohydrin-ethylene oxide allyl glycidyl ether copolymer rubber, chloroprene rubber, chlorine-containing acrylic rubber, chlorinated polyethylene rubber.

Examples include chlorosulfonated polyethylene rubber, fluorine rubber, and brominated butyl rubber.

As the vulcanizing agent used in the composition of the present invention having these polymer compositions, when the comonomer component of the copolymer is an ethylenically unsaturated epoxide, a known vulcanizing agent for unsaturated rubber can be used.

Examples of such vulcanizing agents include organic peroxides, sulfur,
Examples include sulfur-donating compounds, sulfur compound-based promoters, and combinations of these and various promoters. Examples of the organic peroxide include dicumyl peroxide, dicumyl peroxide, menhydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, and benzoyl peroxide. Examples of sulfur donor compounds include tetramethylthiuram disulfide and pentamethylene tetrasulfide. Examples of sulfur compound promoters include deazoles such as 2-mercaptobenzothiazole and dibenzothiazole, and 2-cyclohexylbenzodeazilsulfenamide. Examples include mercapto-imidacillins, thiocarbamates such as dimethylthiolylbamic acid, and quinananthate salts such as zinc isoprovirgizan 1 hegenate. Examples of accelerators used in combination with sulfur or sulfur-based compounds include guanidines such as diphenylguanidine and amines such as hexamethylenetetramine. Examples of mercaptotriazines include dibutylamino-3,5-dimercaptotriazine. Examples of resin vulcanizing agents include alcohol phenol formaldehyde resins, and oxime vulcanizing agents include p-quinone dioxime and pp'-dibenzylquinone dioxime.

Further, when the comonomer component of the copolymer in the composition of the present invention is a halogen-containing epoxide, examples of the vulcanizing agent include polyamines, thioureas, mercapto-1-lyazines, polyphenols, and the like. Specific examples of polyamine vulcanizing agents include hexamethylene diamine carbame 1 to 2. Specific examples of thioureas include ethylenethiourea and dibutylthiourea.

Further, specific examples of mercaptotriazines include 1-limerbutytriazine, dibutylamino-3,5-triazine, and the like.

When mixing rubbers that do not have the above-mentioned functional groups, such as ethylene-propylene rubber, silicone rubber, etc., a vulcanization method using an organic peroxide can be employed for appropriate blending.

These vulcanizing agents are used in combination with vulcanization aids as appropriate according to known techniques in the art.

The amount of these vulcanizing agents and vulcanization aids blended into the composition of the present invention is 0.01 to 20% by weight, usually 0.1% by weight, based on the polymer component.
It is used in a range of 15% by weight. These amounts are arbitrarily determined depending on the composition of the polymer, the type of drug, the purpose of the molded product, etc.

Furthermore, the composition of the present invention may optionally contain various reinforcing agents, fillers, plasticizers, processing aids, stabilizers, anti-aging agents, pigments, flame retardants, etc. necessary for processing or for adjusting various physical properties in practical use. Can be combined with Furthermore, various processing methods used in the technical field can be used in the production and processing of the composition of the present invention.

As described above, the composition of the present invention can be easily vulcanized using a common vulcanizing agent, and the resulting vulcanizate has the following characteristics.

1) It has extremely good oil resistance against various oils, as well as cold resistance and heat resistance, giving it an excellent balance of performance as a rubber.

ti) It has excellent resistance to rancid oil.

111) Corrosion to metals is improved compared to conventional halogen-containing rubbers.

111) Compared to fluororubber, it has comparable lubricating oil resistance and engine oil resistance, has significantly improved cold resistance, and has the advantage of being economically inexpensive.

The effects of the composition of the present invention will be explained below using Examples and Comparative Examples. The formulations in the table are parts by weight.

Examples 1 to 11, Comparative Examples 1 to 6 Each compound shown in Table 1 was kneaded with a 6-inch roll at a roll temperature of 60°C, and then pressure-molded at 160°C for 20 minutes. Physical property tests were conducted. The results are shown in Table 2.

Rice I NBR, JSR, N230s (product name: manufactured by Japan Synthetic Rubber (2)) *2 Epichromer-CG (product name, manufactured by Osaka Soda (2)) *3 Ebichroma-〇 (product name, manufactured by Osaka Soda ■) *4-door Acron AR740 (product name, Toa Paint (2)
) *5 Daiel G701 (contains vulcanizing agent) (trade name, manufactured by Daikin Industries ■) *6 Nickel dibutyl carbamate (Examples 1 to 3,
5.7. Comparative Example 1, 3.4) 2.2.41-dimethyl-
1,2-dihydroquinoline polymer (Example 4.7. Comparative example 2) 7 Dibenzodeazyl disulfide (Examples 1 to 3.
5.6. Comparative Example 1) Tetramethyldiuram sulfide (Examples 1 to 3.5.6) Iron lead dimethyldithiocarbamate (Comparative example 5) Iron dimethyldithiocarbamate (Comparative example 5) 2-Mercaptoimidacillin (Example 8. 10.11. Comparative Examples 2 to 4) From the above test results, the vulcanized composition of the present invention has the following properties: ), epichlorohydrin-ethylene oxide copolymer rubber (Comparative Example 3), epichlorohydrin rubber (Comparative Example 4), two!
- Excellent oil resistance compared to Lil Rubber (Comparative Example 5),
It can be seen that it has a good balance between cold resistance and heat resistance. Fluororubber (Comparative Example 6) is excellent in other properties, but poor in cold resistance. Further, by comparing Examples 6 and 7 with Comparative Example 1.2, it can be seen that when the product of the present invention is mixed with 21-ril rubber or Ebiku[1-ruhydrin rubber, the oil resistance of these rubbers is improved.

Corrosion test examples 1, 8 to 11. Each of the vulcanizates of Comparative Examples 3 and 4 was sandwiched between two metal plates and heated in an atmosphere of 100% relative humidity and 50°C.
After standing still for 20 hours, it was taken out and the degree of corrosion of the metal plate where the rubber pieces remained was evaluated using a lath as shown below. The results are shown in Table 3.

However, the steel plate used was JIS G 314 (SPCC), and the aluminum plate used was JIS H4000 (A 505 2p).

The vulcanized composition of the present invention has significantly improved metal corrosion resistance compared to epichlorohydrin rubber.

Applicant: Osaka Soda Co., Ltd. Agent: Patent Attorney: Written amendment to the procedure 1. Display of the case 1982 Patent Application No. 1:1671 No. 2
, Title of the invention: Oil-resistant rubber composition 3, Amendment 1: 4, Agent address: 1-10-8-6, Edobori, Nishi-ku, Osaka 550 Contents of the amendment: (1) The scope of the claims of the specification should be submitted in attached sheet (3). ).

(2) [Glycidyl acetate-1 to . . . copolymer] on page 8, lines 6 to 8 of the specification is deleted.

(3) In the same book, page 10, line 11, "comolymer" is corrected to "comonomer."

(4) “4” from the 4th line to the 3rd line from the bottom of page 11 of the same book.
"0°C...0.5 or more" is corrected to "Reduced viscosity measured in a 10.1% monochlorobenzene solution at 80°C is 0.8 or more."

(5) Change the line after the first line of page 18 of the same book and add the following sentence.

"Examples 12-20 Each compound shown in Table 3 was mixed and pressure molded in the same manner as Examples 1-11, and the results of the physical property test of the obtained vulcanizate were
Shown in the table. j (6) Physical property test in the left column of Table 2, page 22 of the same book, "Heat resistance test j [150℃ x 138hJ [1
50℃ x 168hJ, "Elongation (%)" is changed to "Elongation change rate (
%)” and “Hardness change” as [Hardness change point)”
Correct each.

(7) Note column at the bottom of Table 2 on page 22 of the same book: “*32% by weight
[Lauroyl peroxide-containing twisted wheel doo oil] [32% by weight of rice lauroyl peroxide-containing twisted wheel 1lll
Correct B J.

8) Attachment following the same No. 22 (1) No. 22-(,a)
Page ``Table 3'' and attached sheet <2) No. 22-(1)) Page ``Table 4''
Add "table".

(Huh) Same book No. 23 @ bottom line 1 and page 24, page 24, line 10, "Table 3" are corrected by δ1 as "Table 5" respectively.

Attachment (3) Claims (1) Glycidyl carboxylate having an alkyl group of 01 to C4 and an ethylenically unsaturated group-containing epoxide and/or halogen, which may contain other types of epoxides as comonomer components An oil-resistant rubber composition comprising a copolymer 1 comprising an epoxide containing epoxide, and a vulcanizing agent for the copolymer.

(2) The composition according to claim 1, wherein the ethylenically unsaturated group-containing epoxide is one or more selected from allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and glycidyl sorbate.

(3) The halogen-containing epoxide is epichlorohydrin,
Epib D Muhydrin 1. Claim 1 which is one or more selected from monochloroglycidyl acetate
Compositions as described in Section.

(4) The composition according to claim 1, wherein the other epoxide is one or more selected from ethylene oxide, propylene oxide, and styrene oxide.

(5) The reduced viscosity of the copolymer is equal to or greater than 100 ml in a 0.1% 1 L chlorobenzene solution.
Compositions as described in Section.

Procedural amendment t1 (spontaneous) August 21, 1980 1, Indication of case 1981 Patent Application No. 131671 2
, Title of the invention Oil-resistant rubber composition 3, Relationship with the amended case Patent applicant 4, Agent 1-10-8 Edobori, Nishi-ku, Osaka 550 Osaka Soda 0 In-house patent attorney (7665) 5. Subject of amendment Column 6 of ``Detailed Description of the Invention'' of Book 1, Contents of amendment (1) Change the line after the first line of page 18 of the specification and add the following sentence.

[Examples 12 to 24 Each compound shown in Table 3 was mixed and pressure molded in the same manner as in Examples 1 to 11, and the results of the physical property test of the obtained vulcanizate were
Shown in the table. ” (2) Next to page 22 of the same book, there is an attached sheet (1) “Table 3” on page 22-(a) and an attached sheet (2) No. 22-
(b) Add page ``Table 4.''

Claims (5)

[Claims] (1) Even if other types of epoxides are included as a comonomer component, J: is composed of a glycidyl carboxylate having an alkyl group of 01 to C4, an ethylenically unsaturated base-containing epoxide, and/or a halogen-containing epoxide. An oil-resistant rubber composition comprising a copolymer and a vulcanizing agent for the copolymer. (2) The ethylenically unsaturated group-containing epoxide is one or more selected from allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and glycidyl sorbate. Composition. (3) The halogen-containing epoxide is epichlorohydrin,
The composition according to claim 1, which is one or more selected from shrimp bromohydrin and glycidyl monochloroacetate. (4) The composition according to claim 1, wherein the other epoxide is one or more of ethylene oxide, propylene oxide, and styrene oxide. (5) The composition according to claim 1, wherein the copolymer has a reduced viscosity of 0.5 or more in a 0.1% benzene solution at 40°C.