Patent GB-848614-A (GB)
Title: Acrylonitrile polymerisation
IPC: C08F20/44
Filed: 1958-11-03
Abstract: Acrylonitrile polymers are prepared by polymerising acrylonitrile or a monomer mixture comprising at least 80% by weight acrylonitrile in a solvent medium comprising a solvent for the polymer and from 0 to 20%, based on the weight of the reaction mixture, of a diluent which is a non-solvent for the polymer, the polymerisation being carried out continuously and in a substantially constant environment, i.e. the ratio of the components is maintained substantially constant. The solvent may be dimethylformamide, dimethylacetamide, dimethylsulphoxide, butyrolactone, ethylene carbonate, methyl ethyl ketone, succinonitrile or tetramethylene sulphone.  The preferred diluent is water.  Acrylonitrile may be copolymerised with any of the monomers disclosed in Specifications 586,881, 597,368 and 670,268 and U.S.A.  Specifications 2,527,300 and 2,601,256, and especially with methyl acrylate and monomers containing sulphonic acid groups or salts thereof with amines of the form <FORM:0848614/IV(a)/1> where R1 is hydrogen or alkyl, R2 alkyl and R is alkyl or aryl, many suitable amines being listed.  Initiators, e.g. hydrogen peroxide, diacyl peroxides such as diacetyl and dibenzoyl peroxides, azo compounds, e.g. a ,a 1-azobisisobutyronitrile and a ,a 1-azobis(a ,g -dimethylvaleronitrile); redox systems such as the above peroxides together with oxidisable sulphur compounds, e.g. sulphur dioxide, oxidisable heavy metal ions, e.g. of iron, manganese, lead, chromium or cobalt, such as ferrous ammonium sulphate, or triethylamine, or mixtures of perdisulphates and sodium bisulphite, may be added, many suitable catalysts and catalyst components being listed.  The polymerisation may be stopped by adding diphenylthiourea, thiourea, hydroxylamine, hydrochloride, tetramethylthiuram disulphide, thioacetamide, thioglycollic acid, thiosorbitol disulphide, 1-thioglycerol, zinc dimethyl dithiocarbamate, the zinc salt of 2-mercaptobenzothiazole or b -mercaptoethanol. Examples describe the polymerisation of (I, II and III) acrylonitrile and methyl acrylate in the presence of benzoyl peroxide, sulphur dioxide and ferrous ammonium sulphate; (IV) acrylonitrile, methyl acrylate with sodium allyl sulphonate, sodium ethylene sulphonate, triethylammonium ethylene sulphonate and zinc ethylene sulphonate; (V) acrylonitrile and methyl acrylate in the presence of hydrogen peroxide and thiourea; (VII) acrylonitrile with vinylidene chloride, N-vinyl pyrrclidone, acrylamide, N-methylol acrylamide and triethylammonium styrene sulphonate, and triethylammonium styrene sulphonate, in the last run poly(N-vinyl pyrrolidene) being added, in the presence of benzoyl peroxide and sulphur dioxide; (VIII) acrylonitrile with sodium allyl sulphonate, triethylammonium allyl sulphonate, methallyl sulphonic acid and and sodium methallyl disulphonate in the presence of a ,a 1-azobisisobutyronitrile; and acrylonitrile, methyl acrylate and triethylammonium ethylene sulphonate in the presence of benzoyl peroxide, sulphur dioxide and ferrous ammonium sulphate; (IX) acrylonitrile, methylacrylate with triethylammonium ethylene sulphonate, sodium ethylene sulphonate and zinc ethylene sulphonate in the presence of benzoyl peroxide, sulphur dioxide and ferrous ammonium sulphate; p  acrylonitrile and methyl acrylate with (X) dimethylammonium, trimethylammonium, triethylammonium and sodium ethylene sulphonates and (XI) dimethylammonium, trimethylammonium and sodium allyl sulphonates; and (XII) acrylonitrile, methyl acrylate with triethylammonium, sodium and zinc ethylene sulphonates and ethylene sulphonic acid.  The products may be converted directly into spinning or casting solutions by distilling off unreacted monomer and diluent, or by replacing the unreacted monomer and diluent with polymer solvent in a stripping column.  The polymers are particularly suitable for the preparation of textile fibres. U.S.A. Specifications 2,425,192, 2,471,959, 2,528,710 and 2,768,148 also are referred to.