Patent GB-466898-A (GB)
Title: Improvements in the manufacture and production of interpolymerisation products
IPC: D01F6/08
Filed: 1935-12-18
Abstract: Interpolymerization products are prepared by polymerizing in aqueous emulsion vinyl chloride together with maleic esters, with or without the addition of other polymerizable substances containing an olefinic linkage.  The polymers may be after-halogenated, e.g. with chlorine. Suitable maleic esters are the di-methyl, di-ethyl, di-n-butyl, di-iso-butyl, mono-n- or iso-hexyl, dicyclohexyl, dibenzyl, di-(b -chlor-ethyl) esters, or those with ethyleneglycol monomethyl, -ethyl, or -butyl ethers, or with ethyleneglycol monoacetate.  As emulsifying agents there may be used substances containing both lipoid and hydrophillic radicals, e.g. soaps, fatty alcohol sulphonates, alkylated naphthalenesulphonic acids, with or without water-soluble organic solvents, e.g. methyl or ethyl alcohol, ethylene glycol, acetone. As polymerization accelerators may be used organic or inorganic peroxide derivatives, e.g. hydrogen peroxide, ammonium persulphate, acetyl or benzoyl peroxide, peracetic acid. The emulsified polymers may be coagulated, e.g. by electrolytes, and are preferably treated with dilute aqueous solutions of alkaline substances, e.g. caustic alkalies, lime, washing soda, ammonia, amines.  The products may be used alone or with plasticizers, e.g. phosphoric or phthalic esters, aralkylated naphthalenes, such as benzylnaphthalene, or chlorinated naphthalenes or diphenyls, fillers, dyestuffs, or solvents e.g. halogenated hydrocarbons such as methylene chloride, chloroform, and tetrachlorethane, aromatic hydrocarbons such as benzene, toluene and benzyl tetrahydronaphthalene, ketones such as acetone and cyclohexanone, esters such as ethyl and butyl acetates, and glycol esters and ethers.  They are compatible with cellulose derivatives and with other polyvinyl resins.  By pressing, extrusion or injection casting there may be produced shaped articles e.g. combs, toothbrush handles, spectacle frames, sound records accumulator cases, dentures, pipes, hoses, rods, armatures, printing-forms. By rolling on heated rollers films may be prepared down to 10m  in thickness, which may be used for preparation of non-splintering glass, for windows for protective masks, as coatings for cigarette tips and as packing material, for preparing hollow articles e.g. dolls, by blowing or by winding the foils on a mandrel and then welding under pressure.  With plasticizers they form rubber substitutes e.g. for electrical insulation and insulating tape. Solutions of the polymers may be used for coatings, adhesives, cements, impregnating or dressing porous materials, e.g. fibrous materials such as threads, yarns, paper to obtain artificial leather, oil-cloth, linoleum, raincoats, tent material, automobile coverings and materials for making membranes for collapsable boats.  Foils or powdered polymers may be pressed on to fabrics or paper, and by pressing alternate layers of fibrous material and foils of polymer, materials are obtained suitable for driving belts or harness leather.  The solution of the polymers can also be used for the preparation of shaped articles e.g. tubes and medicine-flasks, by the immersion method.  The aqueous emulsions directly obtained may also be used, if desired with solvents, plasticizers, fillers, rubber latex or other synthetic polymerizate dispersions.  In examples: (1), (2) Vinyl chloride is emulsified in an aqueous solution of sodium a -hydroxy-octadecane sulphonate, hydrogen peroxide, and peracetic acid, heated to 50 DEG  C. and maleic dimethyl ester emulsified in the same medium added in portions during 24 hours.  The resulting emulsion is coagulated by aluminium sulphate, the unchanged ester removed by steam, the polymer treated at 50 DEG  C. with (1) \ba1/2\be per cent, (2) 1 per cent caustic soda, filtered off, and dried. By polymerizing at 90--100 DEG  C. products of lower molecular weight and greater solubility are obtained.  Foils 1 mm. thick of the product of example 1 can be used for all purposes for which celluloid has been used e.g. for blowing hollow bodies such as dolls and children's toys, for drawing-boxes, hemispheres, and for sound-record discs.  The foils may be superposed and welded by heat and pressure to obtain thick, transparent plates which may be used to make toothbrush, door, and stick handles.  (3), (6), (7), (10), (11), (12).  An emulsion in an aqueous solution of sodium oleate and potassium persulphate of vinyl chloride and (3) maleic di-iso-butyl ester, (6) maleic mono-ethyl ester, (7) maleic dicyclohexyl, dibenzyl, or diphenylethyl ester, (10) maleic dimethyl ester with styrene, (11) maleic dimethyl ester with acrylic acid, (12) maleic di-iso-butyl ester with acrylic nitrile, or maleic diethyl ester with vinyl n-butyl ether, is polymerized at 50 DEG  C., and the product worked up as in example 2.  (4) Vinyl chloride and maleic di-n-butyl ester are emulsified in a dilute aqueous solution of Turkey red oil and peracetic acid and polymerized at 40 DEG  C. The product may be worked up as in example 2.  (5) Vinyl chloride and maleic diethyl ester are emulsified in a dilute aqueous solution of Turkey red oil, sodium perborate, and caustic soda, and polymerized at 55 DEG  C.  (8) Vinyl chloride and maleic di-b -chlorethyl ester are emulsified in a dilute aqueous solution of oleic methyltaurin sodium salt and polymerized as in example 3.  (9) Vinyl chloride and the neutral maleic esters of ethylene glycol mono-methyl, -ethyl, or -butyl ethers or of ethyleneglycol mono-acetate are emulsified in an aqueous solution of sodium a -hydroxy-octadecane sulphonate in the presence of hydrogen peroxide, peracetic acid, sodium pyrophosphate, and sodium persulphate, and polymerized at about 42 DEG  C.  (13) A map is sprayed with an emulsion of the interpolymer of vinyl chloride and the neutral maleic ester of ethyleneglycol mono-ethyl ester prepared as in example 9 and diluted with water, dried, and pressed between heated highly polished steel plates to obtain a highly polished waterproof coating.  (14) Cotton fabric is waterproofed by impregnating with an emulsion of an interpolymer of vinyl chloride and maleic di-n-butyl ester to which tricresylphosphate has been added, followed by ironing.  (15) An interpolymer of vinyl chloride and maleic di-iso-butyl ester is rolled to a foil at 140 DEG  C., which foil may be drawn to a film of 20m  thickness on a four-roller calender.  (16) An interpolymer of vinyl chloride and maleic di-iso-butyl ester is pressed to form a transparent acid-stable accumulator case.  (17) An interpolymer of vinyl chloride and the neutral maleic ester of ethyleneglycol monobutyl ether is rolled at 140 DEG  C. with dibutyl phthalate and carbon black to form a leather substitute.  By rolling in cork meal also, linoleum - like masses are obtained.  The mixture may be drawn into thin foils and these alternated with cotton fabric and pressed to form a strong plate, stable to oil and benzine, suitable for preparing packing rings. (18) An interpolymer of vinyl chloride and maleic di-iso-butyl ester is rolled with chlorinated diphenyl containing 50 per cent chlorine, and the mixture may be used for preparing insulating sheaths.  (19) A solution of an interpolymer of vinyl chloride and the neutral maleic ester of glycol-mono-ethyl ester in methylene chloride and benzyl tetrahydronaphthalene may be used as a lacquer and for the production of bodies by the immersion process.  Samples have been furnished under Sect. 2 (5) as follows: (1) vinyl chloride and maleic di-n-butyl ester are emulsified in an aqueous solution of ethyl alcohol and ammonium persulphate and polymerized at 50 DEG  C.; (2) vinyl chloride, maleic dimethyl ester, and tung oil are emulsified in an aqueous solution of sodium a -hydroxy-octodecane sulphonate, hydrogen peroxide, and ammonium persulphate, polymerized at 50 DEG C., and coagulated by aluminium sulphate solution; (3), (4) vinyl chloride, maleic dimethyl ester, and (3) butadiene, (4) indene, are emulsified in an aqueous solution of sodium a -hydroxy-octodecane sulphonate, ammonium persulphate, benzoyl peroxide, and hydrogen peroxide, polymerized at 70--75 DEG  C., and precipitated by aluminium sulphate solution. Specification 376,479 is referred to. The first Provisional Specification refers to the use of the interpolymers in the preparation of putty.