JPH04353546A - Cross-linked chlorine-containing rubber composition - Google Patents

Abstract

PURPOSE:To obtain a cross-linked chlorine-containing rubber composition capable of cross-linking chlorinated polyethylene and/or chlorosulfonated polyethylene and sufficiently receiving practical application. CONSTITUTION:A cross-linked chlorine-containing rubber composition is obtained by blending 100 pts.wt. chlorinated polyethylene and/or chlorosulfonated polyethylene with 1-30 pts.wt., preferably 5-15 pts.wt. epoxy resin and 0.1-20 pts.wt., preferably 2-10 pts.wt. metallic salt of an organic acid. The chlorinated polyethylene and chlorosulfonated polyethylene with a chlorine content within the range of 15-50wt.% assume a rubber-like state.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to chlorine-containing rubber crosslinking compositions. Specifically, the present invention provides a novel crosslinking composition for crosslinking chlorinated polyethylene and/or chlorosulfonated polyethylene.

0002

BACKGROUND OF THE INVENTION Conventionally, chlorinated polyethylene and/or chlorosulfonated polyethylene has been crosslinked and used as rubber products. In the case of chlorinated polyethylene, which is a chlorine-containing rubber, the crosslinking methods include: ■Crosslinking with thioureas, ■Crosslinking with amines/amine salts, ■Crosslinking with organic peroxides, ■Crosslinking with thiol derivatives, and ■Crosslinking with thiol derivatives. Crosslinking using sulfur derivatives, ■crosslinking using silanes, and ■crosslinking using electron beams are known (Polymer Digest, October issue, 1988, p. 23 and November issue, p. 33).
. The crosslinking methods that have been put into practical use are: (1) crosslinking using organic peroxides and (2) crosslinking using thiol derivatives (Japanese Patent Publication No. 54-15458, Japanese Patent Publication No. 55-39250).
and JP-A-58-222129, etc.), crosslinking of chlorinated polyethylene is extremely limited. Furthermore, crosslinking of chlorosulfonated polyethylene, which is a chlorine-containing rubber, is extremely limited. For this reason, there is a strong demand for the provision of a chlorine-containing rubber crosslinking composition that is a novel crosslinking composition that can crosslink chlorinated polyethylene and/or chlorosulfonated polyethylene and that can be put to practical use.

0003

[Problems to be Solved by the Invention] As a result of intensive research, the present inventors have provided a new crosslinking composition capable of crosslinking chlorine-containing rubber, and a chlorine-containing rubber crosslinking composition that can be put to practical use. It is.

0004

SUMMARY OF THE INVENTION The present invention is a novel crosslinking composition capable of crosslinking chlorine-containing rubbers consisting of chlorosulfonated polyethylene and/or chlorinated polyethylene, epoxy resins, and metal salts of organic acids.

The present invention will be explained in detail below.

The chlorinated polyethylene used in the present invention includes polyethylene, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-ethyl acrylate copolymer, Powder or particles of ethylene-methyl acrylate copolymer, etc. are suspended in water or dissolved in an inert organic solvent such as carbon tetrachloride, and chlorine gas is introduced into the product to form a rubber-like product. be. The amount of chlorine is not particularly limited as long as the chlorinated polyethylene is in the form of a rubber, but 15 to 55% by weight of the chlorinated polyethylene is in the form of a rubber.

The chlorosulfonated polyethylene used in the present invention is obtained by dissolving the above polymer in an inert organic solvent such as carbon tetrachloride, chlorinating it by blowing chlorine gas, and then adding chlorosulfonyl. It is made into a rubber by introducing a chlorosulfonyl group through an addition reaction, or by introducing chlorine and a chlorosulfonyl group using chlorosulfonyl. As long as the chlorosulfonated polyethylene is rubbery like chlorinated polyethylene, the amount of chlorine is not particularly limited, but 15 to 55% by weight of the chlorosulfonated polyethylene is in the rubbery state. Although the production methods of chlorinated polyethylene and chlorosulfonated polyethylene have been described above, the production of chlorinated polyethylene and/or chlorosulfonated polyethylene used in the present invention is not limited to these production methods.

The epoxy resin used in the present invention is a resin made by reacting a compound having an active group such as a hydroxyl group, a carboxyl group, or an amino group with epichlorohydrin, and is a resin made by reacting a compound having an active group such as a hydroxyl group, a carboxyl group, or an amino group with epichlorohydrin. Epoxy compounds made by reaction,
Epoxidized novolac compounds made by the reaction of novolac with epichlorohydrin, epoxidized creso-
Representative examples include alcohol compounds, epoxidized alcohol compounds, epoxidized methacrylic acid compounds, and epoxidized phenyldiamine compounds. For example, commercially available epoxy resins include:
Naigai Chemical Materials B Functional polymers: There is an epoxy resin published in CMC Co., Ltd. (1990). These may be used alone or in combination. The amount used is 1 to 30 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of chlorinated polyethylene and/or chlorosulfonated polyethylene. If it is less than 1 part by weight, the amount of crosslinking by the epoxy resin will be small, resulting in poor mechanical properties. If it exceeds 30 parts by weight, the rubber elasticity will be lost due to the effect of the epoxy resin, which is not preferable.

The metal salt of an organic acid of the present invention is a metal salt of a carboxylic acid type organic acid. There are fatty acids, unsaturated fatty acids, chain organic acids having less than 6 carbon atoms, aromatic organic acids, and cyclic organic acids.

[0010] Examples of saturated fatty acids having 6 or more carbon atoms include:
caproic acid, enanthic acid, caprylic acid, pelargonic acid,
Examples of unsaturated fatty acids having 6 or more carbon atoms include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, pargaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid, etc. , hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decylenic acid, undecylenic acid, dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petroselic acid, vaccenic acid, linoleic acid, linoleic acid, eleostearic acid, Examples include monobasic acid type fatty acids such as ricanic acid, parinaric acid, tarylic acid, cadreic acid, arachidonic acid, cetoleic acid, erucic acid, and ceracoleic acid, as well as dibasic acid and tribasic acid types of these fatty acids.

Examples of chain organic acids having less than 6 carbon atoms include:
Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, trimethylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, maleic acid, glycolic acid, lactic acid, methoxyacetic acid , monobasic acid type chain organic acids such as acrylic acid, and these dibasic acid and tribasic acid type fatty acids.

Examples of aromatic organic acids include benzoic acid, phenyl acetic acid, hydrocinnamic acid, phenyl butyric acid, phenyl valeric acid, phenyl caproic acid, phenyl enanthic acid, phenyl caprylic acid, phenyl pelargonic acid, phenyl capric acid, and benzoyl. Cyclic organic acids such as acrylic acid, phenylcyclohexylic acid, phenylbenzoic acid, phenylundecanoic acid, naphthoic acid, phthalic acid, mehalitic acid, toluic acid, salicylic acid, acetylsalicylic acid, etc., cyclopropanecarboxylic acid, Cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, heptylcyclopentyl acetate, octylcyclopentyl acetate, nonylcyclopentyl acetate, undecylcyclopentyl acetate, pentylcyclohexyl acetate, heptylcyclohexyl acetate, nonylcyclohexyl acetate, undecylcyclohexyl Acetic acid, octylcyclopentylbutyric acid, undecylcyclopentylbutyric acid, pentacyclopentylbutyric acid, hexacyclopentylbutyric acid, decylcyclohexylpropionic acid, dodecylcyclohexylpropionic acid, tetradecylcyclohexylpropionic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, cyclohexylcaproic acid, cyclohexylcapric acid, Examples include aromatic organic acids and cyclic organic acids such as cyclohexyllauric acid, naphthenic acid, camphonanic acid, maleprolic acid, maleprestic acid, hydronocarpic acid, methylene octadecenoic acid, dimer acid, and resin acid.

[0013] The metals constituting the metal salt of an organic acid include copper in group I and subgroup b of the fourth period of the periodic table, germanium and titanium in group IV, among metals of transition elements exhibiting a plurality of valences. , V to VII refers to vanadium, chromium, manganese of group a subgroup, iron, cobalt, nickel of group VIII, tin of group IV group b of the fifth period, and lead of group IV group b of the sixth period.

[0014] The metal salt of an organic acid as used in the present invention refers to a compound composed of the above organic acid and a metal. These metal salts of organic acids may be used alone or in combination. These metal salts of organic acids exhibit their effects when used in combination with the above-mentioned epoxy resin. The amount used is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 2 to 10 parts by weight per 100 parts by weight of chlorinated polyethylene and/or chlorosulfonated polyethylene. If it is less than 0.1 part by weight, the amount of crosslinking will be small and the mechanical properties will be poor. If it exceeds 20 parts by weight, the amount of crosslinking increases and rubber elasticity is lost, which is not preferable.

[0015] The chlorinated polyethylene and/or chlorosulfonated polyethylene crosslinked composition of the present invention may optionally contain other rubber compounding agents, such as a dehydrochloric acid scavenger, an anti-aging agent, a tackifier, and a plasticizer. , softeners, reinforcing agents, fillers, etc. The method for producing the crosslinked composition of the present invention is not particularly limited, and may be kneaded and compounded using a kneading machine such as a kneading roll machine, an internal mixer, or a double-arm kneader. In addition, the crosslinking temperature is the crosslinking temperature of ordinary rubber.
It is carried out at a temperature of 00°C or higher.

[0016]

EXAMPLES The present invention is illustrated by the following examples.
The present invention is not limited only to these examples.

Chlorinated polyethylene, which is a chlorine-containing rubber used in Examples, Comparative Examples, and Reference Examples, was produced by the following method.

Carbon tetrachloride 17 was added to a 30 liter reactor.
．． 5 liter and the melt index measured according to JIS K-6760 at a temperature of 190°C and a load of 2160g is 5. 2.8 kg of high-density polyethylene from No. 2 was added, and the temperature was raised to 100° C. while stirring to dissolve the high-density polyethylene in carbon tetrachloride. Next, add 2. chlorine gas. 8
Blow was carried out from the bottom of the reactor at a rate of liter/min to obtain a carbon tetrachloride solution of chlorinated polyethylene with a chlorine content of 35% by weight. Carbon tetrachloride was removed from this solution using a drum dryer to obtain solid chlorinated polyethylene.

Examples 1 to 5, Comparative Examples 1 to 4, and Reference Examples 1 and 2 Tables
1 shows the formulations used in Examples, Comparative Examples, and Comparative Examples. First, the formulations of Examples, Comparative Examples, and Reference Examples were kneaded using an 8-inch roll manufactured by Toyo Seiki Seisakusho Co., Ltd., and this kneaded product was molded using a compression molding machine with a mold temperature of 180°C. 20
Crosslinking was carried out for a minute to obtain a crosslinked rubber sheet with a thickness of 2 mm. Next, using the obtained rubber sheet, JIS K
Hardness test according to 6301, tensile test, 72 at 120 °C
Rate of change and NO. by time air heating aging test. The volume change was measured by a 72-hour immersion test at 120° C. using 3 oils. The results of these tests are shown in Table-1.

From Table 1, it can be seen that the Examples have a higher tensile strength, a smaller change rate in the air heating aging test, and a smaller volume change in the immersion test, which indicates that they are sufficiently crosslinked. Ru. Furthermore, the examples showed test results that were comparable to those of crosslinked rubber sheets obtained by crosslinking with trithiocyanuric acid, a thiol derivative in Reference Example 1, and dicumyl peroxide in Reference Example 2. It shows.

[0021]

[Table 1]

[0022]

Effects of the Invention As is clear from the above explanation, the chlorine-containing rubber crosslinked composition of the present invention, which is composed of chlorinated polyethylene and/or chlorosulfonated polyethylene, an epoxy resin, and a metal salt of an organic acid, This is a novel composition for crosslinking/or chlorosulfonated polyethylene, and it is found that it can be satisfactorily put to practical use.

Claims (1)

[Claims] 1. A chlorine-containing rubber crosslinking composition comprising 1 to 30 parts by weight of an epoxy resin and 0.1 to 20 parts by weight of a metal salt of an organic acid per 100 parts by weight of chlorinated polyethylene and/or chlorosulfonated polyethylene.