Patent GB-1015928-A (GB)
Title: Peroxide-curing of polyethylene
IPC: C08L23/04
Filed: 1962-08-16
Abstract: A heat-curable polyethylene composition comprises (1) (a) one or more polyethylenes; (b) a blend of one or more polyethylenes and up to 75% by weight of the blend of at least one of (i) a polymer of at least one alkene having 3 to 8 carbon atoms; (ii) a polymer or copolymer of a conjugated butadiene or an alkyl substituted conjugated butadiene: (iii) a solid organopolysiloxane; (iv) a polymer of a monohydric alcohol ester of acrylic acid; (v) a polystyrene; (v) a chlorosulphonated polyethylene; or (vii) a chlorinated polymer of at least one alkene having 2 to 8 carbon atoms; (c) one or more copolymers of ethylene and up to 75% by weight of the polymerizable mixture of at least one alkene having 3 to 8 carbon atoms; or (d) a blend of one or more of said copolymers (c) and up to 75% by weight of the blend of one or more of a polyethylene or of any of said polymers (i) to (vi) above; and (2) an acetylenic peroxide having the general formula <FORM:1015928/C3/1> or <FORM:1015928/C3/2> where n is 1 or 2 R R1 and R11 are each a monovalent alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkaryl, haloalkaryl, aralkyl, haloaralkyl, aryl or haloaryl radical, but each R1 may also be a divalent alkylene, alkylidene, haloalkylene or haloalkylidine radical, which when taken together with the tertiary carbon atom attached to the peroxide oxygen, form a ring, and R11 may also be hydrogen.  R111 is a divalent alkylene, haloalkylene, cycloalkylene, halocycloalkylene, alkarylene, haloalkarylene, aralkylene, haloarylalkylene, arylene or haloarylene radical.  The polyethylene component may also be compounded with one or more fillers e.g. carbon blacks, silicas, clays, diatomaceous earth, chromic oxide, titanium dioxide, ferric oxide, calcium carbonate, cadmium sulphide, asbestos, wood flour, cellulose fibers, mineral fibers, glass, fibers, alumina, lithopone, talc and calcium silicate.  Dyes and/or pigments may be added.  The curing of the composition is effected by heating at a temperature in the range of 160 DEG  C. to just below the decomposition temperature of the polyethylene components. Generally 0.1 to 20% by weight of the acetylenic peroxide, based on the polyethylene component, is used.  In the examples the peroxides used are 2,5-bis-(t-butylperoxy)-2,5 - dimethyl - hexyne - 3; 2,5 - bis - (a ,a 1- dimethyl - benzyl peroxy) - 2,5 - dimethylhexyne - 3; 3 - (a ,a  - dimethyl - benzylperoxy)-3 - methyl - butyne - 1; 2,5 - bis - (1,1 - dimethy - propyne peroxy) - 2,5 - dimethylhexane; 2,5 - bis - (t - butyl peroxy) - 2,5- diphenyl - hexyne - 3 and 2,5 - bis - (a ,a dimethylbenzylperoxy) - 2,5 - diphenyl - hexyne-3. The cured composition may be used to coat conductors or it may be used in insulating tapes, spark plug insulators and gaskets &c.  Reference has been directed by the Comptroller to Specification 910,204.ALSO:Acetylenic peroxides having the general formula <FORM:1015928/C2/1> or <FORM:1015928/C2/2> where n is 1 or 2; R, R1 and R11 are each a monovalent alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkaryl, haloalkaryl, aralkyl, haloaralkyl, aryl or haloaryl radical with the provisos that each R1 may also be a divalent alkylene, alkylidine, haloalkylene or haloalkylidene radical, which, when taken together with the tertiary carbon atom attached to the peroxide oxygen, form a ring, and that R11 may also be hydrogen; and R111 is a divalent alkylene, haloalkylene, cycloalkylene, halocycloalkylene, alkarylene, haloalkarylene, aralkylene, haloaralkylene, arylene or haloarylene radical, may be prepared by reacting hydrogen peroxide with an alcohol in the presence of sulphuric acid to form the corresponding hydroperoxide which is then reacted with an acetylenic glycol or alcohol. Alternatively the acetylenic glycol or alcohol is reacted with hydrogen peroxide to form the corresponding dihydroperoxide or monoperoxide which is then reacted with the appropriate alcohol.  2,5 - Bis - (t - butylperoxy) - 2,5 - dimethyl - hexyne-3 may be made by reacting t-butyl alcohol with hydrogen peroxide and then reacting the product with 2,5-dihydroxy-2,5-dimethylhexyne-3; however it is preferably made by reacting 2,5-dihydroxy-2,5-dimethylhexyne-3 with hydrogen peroxide to form 2,5-bis - (hydroperoxy) - 2,5 - dimethyl hexyne - 3 which is then reacted with t-butyl alcohol.  Reference has been directed by the Comptroller to Specification 910,204.