GB618249A - Improvements in or relating to low-temperature olefinic polymers - Google Patents

Abstract

A mixture containing at least 45 per cent of C4 to C14 polyolefins and the remainder C3 to C20 aliphatic or cyclo-aliphatic mono-olefins other than isobutylene alone is polymerized in the presence of a Friedel-Crafts catalyst at a temperature between -40 DEG C. and +10 DEG C. to produce a resinous copolymer in a yield not exceeding 80 per cent. Specified polyolefins are butadiene, isoprene, piperylene, 2 - methylpentadiene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, dimethylbutadiene, myrcene, dimethallyl, vinylcyclohexene, hexadiene-1,5. The mono-olefin may be disiobutylene, 2-methyl-pentene-1, 2,5-dimethyl-hexene-2, n-butene, n-pentene, n-hexene, 2-methylhexene-1, propylene, their dimers, trimers and tetramers, isobutylene trimer and tetramer, undecylene, decylene, dodecylene, tetradecylene, octadecylene, trimethyl- and tetramethyl-ethylene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene. Specified catalysts are aluminium chloride, chlorobromide and alkoxy-halides, boron trifluoride, titanium tetrachloride, preferably dissolved in methyl or ethyl chloride, carbon disulphide, liquid propane, butane, pentane or hexane. Polymerization is arrested at the desired yield by stopping addition of catalyst or by discharging the reaction mixture into warm water. The copolymers may be added to greases, rubber, guayule, polyolefin sulphides, rosin, ester gum, dammar, manila and copal resins, phenol-formaldehyde resins, which may be modified by rosin, ester gum, natural resins or drying oils, urea-formaldehyde resins, melamine resins, asphalt, cellulose, cellulose esters and ethers, coumarone-indene resins, alkyd and modified alkyd resins, polystyrene, polyisobutylene, polyvinyl chloride, acetate and chloroacetate, acrylic and methacrylic resins. The products may be heat-bodied alone or dissolved in a drying oil, e.g. linseed, tung or dehydrated castor oils and pigments and fillers, e.g. carbon black, graphite, clay, mica, aluminium powder, ferric oxide, silicon carbide, marble, lithopone, talc, ground cork, wood flour, sisal, corn fibres, cotton linters, glass wool and asbestos; solvents, e.g. turpentine and naphtha; dyes; driers, e.g. manganese, lead or cobalt naphthenate; lubricants, stabilizers and plasticisers may be added. The copolymers may be vulcanized, nitrated, sulphated, alkylated, halogenated, hydrohalogenated or hydrogenated, condensed with chloroform, sulphuryl chloride, sulphonyl chlorides, phosphorus trichloride, pentoxide or pentasulphide, phosgene, hydrogen sulphide, mercaptans, ammonia, amines, alkyl and aryl hypochlorites, hypochlorous acid, maleic and succinic anhydrides, carbazoles, furfuraldehyde, nitrogen peroxide or pentoxide, nitrosyl chloride, nitro-mono- and di-halo-amides, diazocompounds, a -halo-ethers, or reacted with ketones, olefine oxides, sulphur dioxide, aryl isocyanates, with alcohols to yield ethers, with carbon monoxide and water in the presence of boron trifluoride to yield acids, with formaldehyde to yield dioxanes and glycols, with organic acids, acid chlorides, anhydrides or esters in the presence of sulphuric acid or zinc chloride to yield unsaturated ketones. They may be condensed with phenols, naphthols, aromatic amines, e.g. aniline and dimethyl aniline and further treated with formaldehyde, or condensed with phenol-formaldehyde or aniline-formaldehyde resins or polystyrene. The copolymers may also be oxidized with selenium dioxide, peroxides, permanganates, dichromates, ozone, nitric acid or mixtures of hydrogen peroxide and acetic acid to yield acids, ketones, glycols, hydroxy- and ketoacids and acetylated polyalcohols, which may be further reacted to yield halides, acetals, ketals, amines, esters, ethers, amides, oxiones, nitrites. Polymerization processes resulting in the production of a solution of the copolymer in naphtha or lubricating oil or of solid copolymer are described. The copolymer itself and its reaction product with phosphorus pentasulphide may be used as viscosity index improvers for lubricating oils to which also pour point depressors, anti-oxidants, metal soaps, polysilicones or dyes may be added. The copolymers may also be used as adhesives, for coating or impregnating paper, metal, wood, ceramics, cloth, glass, leather, rubber and plastics, for electric insulation, and for making inlaid linoleum. In examples a butadienediisobutylene copolymer is (6) modified by heating it with a pentaerithritol - modified rosin, then dissolved in dehydrated castor oil and thinned with naphtha; (9) compounded with a butadiene-styrene copolymer, natural rubber, polychloroprene or a butadiene-acrylonitrile copolymer, zinc oxide, carbon black, tetra-methyl thiuram monosulphide and sulphur and vulcanized; (15) stirred with molten paraffin wax and coated on to paper.