Patent GB-574034-A (GB)
Title: Polymers and copolymers of esters of vinyl oxyacetic acid
IPC: C08F18/08
Filed: 1943-12-10
Abstract: Polymerising a vinyloxyacetic acid ester in a continuous phase, or polymerising the ester in admixture with one or more polymerisable materials containing the group <FORM:0574034/IV/1> , in the presence of a polymerisation catalyst.  Esters specified are the esters of monohydric alcohols of up to seven carbon atoms including the ethyl, propyl, butyl, cyclohexyl, benzyl, tetrahydrofurfuryl, ethoxyethyl, allyl and methallyl esters. Copolymers may contain propylene, butylene-1, butylene-2, isobutylene, amylene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether isobutyl vinyl ether and amyl vinyl ether styrene, vinylnaphthalene, vinyl acetate, vinyl isobutyrate, vinyl chloride, methyl vinyl ketone, methyl isopropenyl ketone, vinylidene chloride and aceylic, methacrylic, a -phenylacrylic and a -chloracrylic acids, esters and nitriles, e.g., benzyl phenylacrylate, methyl a -chloracrylate and the methyl, ethyl, propyl, butyl, isobutyl, dodecyl, cyclohexyl, allyl, benzyl and 2-acetoxyethylacrylates and methacrylates.  Polymerisation may take place in solution or by bulk methods while copolymerisation may take place in solution, by bulk, granulation or by emulsion technique. The copolymerisation with compounds such as propylene and vinyl isobutyl ether is carried out by treating a solution of the monomers under a nitrogen atmosphere with a metal halide catalyst at a temperature below 0 DEG  C., preferably below -44 DEG  C. Specified catalysts are boron trifluoride, stannic, aluminium, zinc or ferric chloride, aluminium bromide, antimony trichloride or pentachloride, titanium tri- or tetrachloride, zirconium tetrachloride or mercuric chloride and aluminium metal.  Solvents specified are diethyl, dipropyl or diisobutyl ether, methyl or ethyl formate, ethyl acetate, methyl, butyl or methylene chloride, ethyl or n-propyl bromide, trichloroethylene, chloroform or propane.  Copolymerisation with the remaining above specified monomers is carried out using peroxide catalysts such as benzoyl, lauroyl, succinoyl, and hydrogen peroxide, or ascaridole.  In granulation polymerisation a buffering agent such as sodium hydrogen phosphate, citrate, acetates, or other phosphates and a granulating agent such as the sodium salt of polymethylacrylic acid, partially hydrolysed polyvinyl acetate, methyl starch, pectin and agar agar are present in an aqueous system.  In emulsion polymerisation a dispersing agent such as salts of fatty acids, long chain sulphonates and sulphates, e.g. sodium oleyl sulphates, sodium cetyl sulphate, sodium acetoxyoctadecyl sulphate, sodium - penta - decane-8-sulphate, sodium triisopropylnaphthalenesulphonide, and the sodium salt of sulphonated paraffin oil may be added.  Apart from the above-mentioned peroxide catalysts, ammonium persulphate (preferred), sodium and potassium persulphates, and perforates may be used. Coagulants such as aqueous aluminium sulphate are mentioned.  The polyvinyloxyacetic acid esters are useful as bonding agents, pressure adhesives, electric cable insulations and fabric coatings.  When hydrolysed by aqueous or alcoholic alkali they give tanning agents and textile sizes.  When treated with ammonia or primary mono or diamines they give amides useful as wax substitutes or for waterproofing fabrics, these can be reacted with aldehydes, e.g. formaldehyde, acetaldehyde, butyraldehyde, furfuraldehyde and benzaldehyde.  Copolymers of isobutylene and vinyloxyacetic acid esters are useful in cable insulations, as lubricating oil adjuvants and self-sealing fused cell inner-liners.  Copolymers with methacrylic acid esters and other vinyl derivatives are used in the production of moulded products, such as combs, dentures, lenses, jewellery, electrical equipment, automobile accessories and drafting instruments.  Examples are given of the preparation of the polymer and of some of the above copolymers and include an example of a copolymer of methylvinyloxyacetate and isobutylene compounded with carbon black, stearic acid, mercaptobenzothiazole, zinc dimethyldithiocarbonate, zinc oxide, sulphur, and bis(p-aminophenyl) methane and then cured.  Vinyloxyacetic acid esters may be prepared by pyrolysing over a silver on asbestos catalyst 250 DEG -350 DEG C., the corresponding bis-(hydroxyacetic acid ester) acetals which are conveniently prepared by reacting hydroxyacetic acid ester with acetylene under atmospheric pressure and at 25-50 DEG  C. in the presence of mercuric oxide and a boron fluoride-methanol complex as catalyst.  After pyrolysis, fractional distillation and aqueous extraction give the pure product.  The pyrolysis may be carried out by the method of U.S.A.  Specification 1,931,858.  These give monohydric alcohol esters which by ester interchange using, for example, a litharge catalyst, give polyhydric alcohol esters.  An example (1) of the preparation is given.  Specification 568,102 and U.S.A.  Specification 1,931,858 are referred to.