Patent GB-978875-A (GB)
Inventor: PEARS G E A
IPC: F02B47/00
Abstract: 978,875. Polymerizing vinyl chloride. IMPERIAL CHEMICAL INDUSTRIES Ltd. Nov. 18, 1963 [Dec. 7, 1962; March29, 1963(2); May 10, 1963], Nos. 46247/62, 12617/63, 12618/63 and 18621/63 Heading C3P. Vinyl chloride and 0 to 20 weight per cent of at least one other ethylenically unsaturated copolymerizable compound are dispersed in water together with an emulsifier or dispersing agent and at least 0À005% by weight of the monomer of a catalyst comprising one or more organic peroxydicarbonates in which the organic groups attached to each carbonate group each contain at least 5 carbon atoms, homogenizing the resulting dispersion, and polymerizing the homogenized dispersion at elevated temperature in the presence of at least one compound selected from:- (a) peroxides of structure P.CO.OO.CO.P<SP>1</SP> in which P and P<SP>1</SP> are each alkyl or substituted alkyl radicals containing at least 7 carbon atoms; (b) compounds of structure ROR<SP>1</SP> where R is a monovalent hydrocarbon radical containing an aliphatic chain of at least eight carbon atoms and R<SP>1</SP> is hydrogen or a monovalent hydrocarbon radical; (c) hydrocarbons and halogenated hydrocarbons having an aliphatic group containing a chain of at least eight carbon atoms; (d) carbonyl compounds of structure ZA.CO.BZ<SP>1</SP> where Z is hydrogen, an alkyl or substituted alkyl group, Z<SP>1</SP> is an alkyl or substituted alkyl group, A and B are direct linkages or oxygen atoms and B is an oxygen atom when A is an oxygen atom and the sum of the oxygen and aliphatic carbon atoms in a single chain in the compound is at least 12; and (e) compounds of the structure M.O.CO.L.CO.O.N where M and N are each monovalent hydrocarbon radicals and L is a direct link or divalent organic radical and in which the sum of atom in L forming the chain between the ester groups plus the sum of carbon atoms in M in the longest straight chain connected to the carboxyl oxygen atom plus the sum of carbon atoms in N in the longest straight chain connected to the carboxyl oxygen atom is at least 20. Specified comonomers are ethylene, propylene, n-butene, isobutene, vinyl acetate, acrylic and methacrylic acids, esters and nitriles, vinyl ethers, vinylidene chloride, maleic and fumaric acids and esters, and maleic anhydride. Specified peroxydicarbonates are di-n-amyl, diisoamyl, dihexyl, dioctyl, di-2-ethylhexyl, di- 3, 5, 5-trimethylhexyl, dinonyl, diisodecyl, dilauryl and distearyl peroxydicarbonates, and peroxydicarbonates derived from mixtures of alcohols having 7 to 9 carbon atoms. Specified emulsifiers are sodium salts of sulphated and sulphonated hydrocarbons and esters, e.g. sodium lauryl sulphate, sulphonated diesel oil, sodium dioctyl sulphosuccinate and sodium dodecyl benzene sulphonate; quaternary ammonium compounds, e.g. stearamidopropyl dimethyl-#-hydroxyethyl ammonium nitrate, cetyl pyridinium chloride and cetyl trimethyl ammonium bromide; and block copolymers of ethylene oxide and propylene oxide. Specified dispersing agents are gelatin, methyl cellulose, polyethylene oxides, gum tragacanth and hydrolyzed polyvinyl acetates. Transfer agents, e.g. methylene chloride, chloroform and dichloroethane, may be present. The polymers may be recovered by tray, drum or spray drying and may be compounded with stabilizers, pigments lubricants, mould release agents, fillers and plasticizers. They may be mixed with plasticizers to form pastes for casting, moulding, coating and foaming. Long lists of suitable compounds of the specified classes are given and examples describe the polymerization of vinyl chloride in the presence of (1 and 3 to 6) lauroyl peroxide, (2) di-3, 5, 5-trimethyl-hexanoyl peroxide, (7) capryloyl peroxide; (8) lauryl alcohol, (9) a mixture of cetyl alcohol and stearyl alcohol, (10) isodecyl alcohol, (12) a mixture of n-decanol, lauryl alcohol and myristyl alcohol, (13) di-nnonyl ether, (14) dicetyl ether; (15) n-heptadecane, (16) n-octadecane, (17) paraffin wax (s.p. 61‹C.), (18) microcrystalline wax (s.p. 76‹C.), (19) nparaffins containing 10 to 20 (average 15) carbon atoms, (20) n-paraffins containing 8 to 10 carbon atoms, (22) dodecyl benzene, (23, 24, 28 and 31) eicosane, (25) chlorinated paraffins (average 24 carbons, 42% chlorine), (26) chlorinated paraffins (10 to 13 carbons, 70% chlorine), (27) chlorinated paraffins (12 to 16 carbons, 50% chlorine), (29) n-paraffins containing 15 to 17 carbon atoms, (32) a condensation product of a propylene polymer containing 9 to 18 carbon atoms and benzene, (33) a mixture of cyclic and non-cyclic paraffins; (34) methyl laurate, (35) ethyl palmitate, (36 and 37) undecyl laurate, (38) cetyl formate, (41) methyl heptadecylketone; and (42) di-noctyl maleate and (43) diisodecyl phthalate.