Patent GB-373643-A (GB)
Title: Improvements in the manufacture and production of polymerisation products
IPC: C08F16/12
Filed: 1931-02-11
Abstract: Mixed polymerization products, manufactured by polymerizing aqueous, neutral to alkaline emulsions of mixtures of vinyl ethers with other neutral, polymerizable organic compounds containing an aliphatic double linkage, may be employed for the manufacture of coatings, varnishes, lacquers, and priming compositions.  In an example, a lacquer comprises the polymerization product of a mixture of vinyl n-butyl ether and acrylic nitrile, acetone, methyl acetate and toluene; part of the polymerization product may be replaced by nitrocellulose while replacing part of the toluene by cyclohexyl acetate.  According to another example, the polymerization product of a mixture of the vinyl ether of ethylene glycol monoethyl ether and acrylic acid methyl ester may be used, alone or with the addition of nitrocellulose or other binding agents, for the preparation of pale-coloured coverings on elastic or tensile bases (leather, cotton fabrics, paper), e.g. for oilcloth, artificial leather or lacquers for insulated wires or cables.  Emulsions, making.--When the neutral, polymerizable organic compound in the mixed polymerization products described above is acrylic nitrile or chloride, the products may be saponified to produce water-soluble products which may be employed as dispersing or emulsifying agents.  In an example, the polymerization product of vinyl ethyl ether and acrylic nitrile is worked at room temperature with concentrated hydrochloric acid until dissolved; on addition of ethyl alcohol, flakes are obtained which may be dissolved in aqueous caustic alkali to give solutions useful as dispersive or emulsifying agents.  In an example of the manufacture of the polymerization products, a mixture of the vinyl ether of ethylene glycol monoethyl ether and acrylic acid methyl ester is emulsified with the help of the sodium salt of isobutylnaphthalenesulphonic acid and oleylmethyltaurine <FORM:0373643/III/1> Specifications 313,569, [Class 2 (iii), Dyes &c.], 319,588, [Class 1 (i), Chemical processes &c.], 340,474, [Group IV], 343,899; 355,712, [Group IV], 357,173; 369,297 and 374,436, [both in Group IV], are referred to.  Reference has been directed by the Comptroller to Specifications 351,508 and 358,534.ALSO:Mixed polymerization products are manufactured by polymerizing aqueous, neutral to alkaline emulsions of mixtures of vinyl ethers with other neutral, polymerizable organic compounds containing an aliphatic double linkage.  Vinyl ethers specified are those of aliphatic open chain or cycloaliphatic alcohols, e.g. the methyl, ethyl, propyl and butyl ethers of vinyl alcohol, those of polyhydric alcohols, e.g. the vinyl ethers of the alkyl ethers of glycols such as ethylene, propylene or butylene glycols (obtainable by the action of acetylene on monoalkyl ethers of glycols), also those of aromatic alcohols, e.g. the benzyl ether (obtainable by the action of acetylene on benzyl alcohol in the presence of caustic potash) and those of hydroaromatic alcohols, e.g. the cyclohexyl ether.  Neutral polymerizable organic compounds specified are vinyl esters, e.g. vinyl chloride, acetate or chloracetate, styrene and its homologues, e.g. methylstyrene, vinylchlorobenzene, acrylic nitrile, amide, anilide and esters, e.g. the methyl, ethyl, propyl, butyl or benzyl esters.  The quantities of these compounds employed are generally between 100 and 600 per cent, preferably between 100 and 400 per cent by weight of the vinyl ether.  The polymerization may be effected in the presence or absence of diluents such as organic solvents not capable of forming acids during the reaction, e.g. benzene, toluene, xylene, methylene chloride, chlorobenzene, dioxane, aliphatic ketones such as acetone or methylethylketone, or mixtures thereof, and in the presence or absence of oxygen or agents splitting off oxygen, such as inorganic or organic peroxides, e.g. hydrogen peroxide, alkali metal peroxides or perborates, barium peroxide, acetyl or benzoyl peroxides or acetone peroxide, or also of boron fluoride.  It is preferable to exclude acids or even to add an alkaline agent, the polymerization preferably being effected in a medium of from PH = 7 to PH = 8.  Buffer substances may be added to maintain a weak alkaline reaction.  The temperature of the reaction may be from 35 to 150 DEG  C., preferably from 50 to 100 DEG  C. Soaps or other emulsifying agents may be employed provided they have not an acid reaction or are neutralized before use.  The products, alone or mixed with camphor, may be pressed, blown, injection-moulded and cut.  They are also suitable as binding agents for the manufacture of compound glass, or may be worked up into films, threads, coatings, varnishes, lacquers or priming compositions, or electrical insulating materials, or, together with fillers, fabrics or pigments, into substitutes for oilcloth, linoleum or leather.  The additional materials, such as softening agents, fillers and pigments, may be added before the polymerization provided they have not an acid reaction.  By saponifying the polymerization products containing acrylic nitrile or chloride, water-soluble products are obtained which may be employed as dispersing, emulsifying, thickening, dressing, sizing and binding agents.  In examples: (1) vinyl ethyl ether and acrylic nitrile are emulsified with the help of Turkey red oil and the sodium salt of isobutylnaphthalenesulphonic acid (obtainable by the action of crude naphthalenesulphonic acid on isobutyl alcohol in the presence of concentrated sulphuric acid) and polymerized by means of hydrogen peroxide; on coagulation with hydrochloric acid, a transparent product is obtained which can be moulded by pressing, e.g. to combs; (2) vinyl-n-butyl ether and acrylic nitrile are similarly polymerized, yielding a material which is readily pressed and is suitable for insulating cables or wires or as an addition to lacquers for electrically insulating metal conductors; a lacquer may comprise the polymerization product, acetone, methyl acetate and toluene; part of the polymerization product may be replaced by nitrocellulose while replacing part of the toluene by cyclohexyl acetate; (3) vinyl n-butyl ether and acrylic nitrile are emulsified with Turkey red oil and the sodium salt of isobutylnaphthalenesulphonic acid, with the addition of the sodium salt of polymerized acrylic acid, and polymerized by means of hydrogen peroxide and benzoyl peroxide; the product, when coagulated by means of hydrochloric acid, may be pressed and worked up in the same way as celluloid, if desired with the p  addition of softening agents; (4) vinyl ethyl ether and acrylic nitrile are emulsified with Turkey red oil and Marseilles soap and polymerized by means of hydrogen peroxide, yielding, on pouring into dilute sulphuric acid, a white powder which can be moulded; (5) vinyl ethyl ether and acrylic nitrile are polymerized as in (4) and the product is worked at room temperature with concentrated hydrochloric acid until dissolved; on addition of ethyl alcohol, flakes are obtained which may be dissolved in aqueous caustic alkali to give solutions useful as dispersive, emulsifying, thickening, sizing or dressing agents, or as binding media in leather or like varnishes; (6) a mixture of the vinyl ether of ethylene glycol monoethyl ether and acrylic acid methyl ester is emulsified with the help of the sodium salt of isobutylnaphthalenesulphonic acid and oleylmethyltaurine (C17H33CO.N(CH3).  C2H4. SO3H, obtainable by the action of oleic chloride on methyl taurine), and polymerized by means of benzoyl peroxide, hydrogen peroxide and potassium persulphate; the product, alone or with the addition of nitrocellulose or other binding agents, is useful for the preparation of pale-coloured coverings on elastic or tensile bases (leather, cotton fabrics, paper), e.g. for oilcloth, artificial leather or lacquers for insulated wires or cables; (7) a mixture of the vinyl ether of ethylene glycol monoethyl ether and acrylic nitrile is polymerized as in (6); the product is soluble in acetone, cyclohexanone and halogenated aliphatic hydrocarbons such as methylene or ethylene chlorides, from solutions in which it yields elastic films; it is also suitable as a binding agent in the lacquer and varnish industry as a substitute for cellulose derivatives or drying oils.  Specifications 313,569, 319,588, [both in Class 2 (iii), Dyes &c.],340,474, 343,899, 355,712, 357,173, 369,297, and 374,436 are referred to.  Reference has been directed by the Comptroller to Specifications 351,508 and 358,534.ALSO:Sizing agents are manufactured by saponifying the mixed polymerization products obtained by polymerizing aqueous, neutral to alkaline emulsions of mixtures of vinyl ethers with other neutral, polymerizable organic compounds containing an aliphatic double linkage.  In an example, the polymerization product of vinyl ethyl ether and acrylic nitrile is worked at room temperature with concentrated hydrochloric acid until dissolved; on addition of ethyl alcohol, flakes are obtained which may be dissolved in aqueous caustic alkali to give solutions useful as sizing agents.  Specifications 313,569, 319,588, [both in Class 2 (iii), Dyes &c.], 340,474, 343,899, [both in Group IV], 355,712; 357,173, 369,297, and 374,436, [all in Group IV], are referred to. Reference has been directed by the Comptroller to Specifications 351,508 and 358,534.