Patent GB-378544-A (GB)
Title: Improvements in the manufacture and production of polymerisation products from vinylethers
IPC: C09J123/00
Filed: 1931-05-18
Abstract: As catalysts for the polymerization of vinyl ethers may be employed addition or conversion products of boron halides or boron hydrogen halides, e.g. boron fluoride, chloride or bromide or boron hydrogen fluoride, with oxygenated organic compounds, e.g. ethers, such as diethyl or dibutyl ethers, ketones or alcohols. The compounds are advantageously employed in the form of very dilute, e.g. about 2 per cent, solutions, e.g. in the alcohols or ethers employed for the preparation of the addition products. Examples describe the use of solutions, in the ethers employed for their preparation, of the addition products of boron fluoride with diethyl and di-n-butyl ethers.  The latter compound is prepared by passing boron fluoride into an equimolecular proportion of di-n-butyl ether.ALSO:Vinyl ethers, of the general formula <FORM:0378544/IV/1> where R is an aliphatic, aromatic or hydroaromatic radicle and R1, R2 and R3 are hydrogen atoms or aliphatic radicles, are polymerized by bringing them singly or in admixture with one another into contact with practically anhydrous inorganic acid reacting condensing agents, such as tin tetrachloride, stannous chloride, aluminium chloride or sulphate, iron chloride, zinc chloride, boron fluoride, boron hydrogen fluoride, silicon tetrachloride, mercury chloride, sodium bisulphate, potassium bisulphate, alum, or practically anhydrous sulphuric, phosphoric, hydrochloric or hydrofluoric acids.  The quantities of the condensing agents are usually from ,001 to 5 per cent of the weight of the vinyl ether.  The vinyl ethers which may be employed include the alkyl, cycloalkyl or aryl ethers of vinyl alcohols, such as methyl-, ethyl-, propyl-, butyl-, hexyl- or cyclohexyl-vinyl, -propenyl or -isopropenyl ethers, the vinyl or alkyl-vinyl ethers of long-chain alcohols corresponding to the acids containing 8-35 carbon atoms, especially of animal and vegetable fats and waxes, e.g. octyl, decyl, dodecyl, tetradecyl, docosanyl or octodecyl alcohols, vinyl ethers or montanol, phenyl-, a - or b -naphthyl- or cresyl-vinyl ethers, also mono- and di-vinyl ethers of glycols and polyalkylene glycols, e.g. of di-, tri- or tetra-ethylene or -propylene glycols and of higher glycols, e.g. octodecandiol, also vinyl ethers of mono-alkyl or -aryl ethers of glycols, e.g. of ethylene or propylene glycol mono-methyl, -ethyl, -butyl, -phenyl or -cresyl ethers and the corresponding mono-alkyl or -aryl ethers of di- or tri-ethylene or propylene glycols, e.g. di- or tri-ethylene glycol and 1 : 2-di- or tri-propylene glycol mono- and di-vinyl ethers, and also divinyl ether.  The polymerization may be carried out in the liquid or, with solid condensing agents, in the gaseous phase, in the latter case if desired with the employment of inert gaseous diluents such as carbon dioxide, nitrogen, methane or carbon monoxide.  When working in the liquid phase it is preferable to add the condensing agents to the vinyl ethers in small portions with cooling.  Inert organic diluents, e.g. liquid or liquefied aromatic hydrocarbons such as benzene, toluene, xylene, decahydronaphthalene, saturated ethers, such as diethyl ether, ethyl n-butyl ether, di-n-butyl ether or ethyl propyl ether, aliphatic liquid hydrocarbons, such as benzine or like mineral oil fractions, or acetone or esters such as butyl or ethyl acetates may be employed. Advantageously a part of the vinyl ether is first diluted with the solvent, the condensing agent is added and the remainder of the vinyl ether added gradually with cooling, and the solution is then refluxed to complete the polymerization.  The reaction is generally carried out at 10-120 DEG  C. preferably at 20-100 DEG  C.  Particularly advantageous condensing agents are boron halides and boron hydrogen halides, e.g. boron fluoride, chloride or bromide or boron hydrogen fluoride, in the form of their addition or conversion products with organic oxygenated compounds, e.g. ethers, such as diethyl or dibutyl ether, ketones or alcohols.  The compounds are advantageously employed in the form of very dilute, e.g. about 2 per cent, solutions, e.g. in the alcohols or ethers employed for the preparation of the addition products, the quantity of condensing agent required frequently amounting to only about ,001 per cent of the vinyl ether. Traces of these condensing agents in the polymerization product can be removed by steam distillation.  When employing these condensing agents the preferred temperature for the reaction is 40-60 DEG  C.  The products may be employed for coating and adhesive purposes, as substitutes for oils in oil-filled subsoil or submarine cables, as resins in the production of artificial masses, as substitutes for polishing and like waxes, as intermediate layers for compound glass, and as softening and plastifying agents for indiarubber and rubber-like polymerization products of diolefines or for masses from polymerized styrene, whilst the lower members, e.g. polymerized vinyl methyl ether, vinyl ether of diethyleneglycol monoethyl ether or ethylene glycol monoethyl ether, which are soluble in water with or without the help of a dissolution assistant such as methyl or ethyl alcohols or ethylene glycol mono-methyl or -ethyl ethers, may be employed in sizing or dressing.  Examples describe the polymerization of: (1) vinyl-n-butyl ether (obtainable by heating anhydrous n-butanol with vinyl chloride in an autoclave in the presence of metallic sodium) by refluxing with stannous chloride, tin tetrachloride or aluminium chloride; (2) vinyl ethyl ether by adding it gradually to a suspension of aluminium chloride in benzene; (3) ethyl-n-propenyl ether, similarly, but using tin tetrachloride as condensing agent; (4) ethyl-isopropenyl ether, by the method of (2); (5) vinyl-o-cresyl ether (obtainable by heating sodium o-cresolate with vinyl chloride in the presence of ethyl alcohol in an autoclave) or vinyl phenyl ether by the same method; (6) vinyl-m-cresyl ether, by standing for 2 days with zinc chloride, or by heating therewith to 80-95 DEG  C. for 1-2 hours; (7) vinyl ethyl ether, by refluxing with a 2 per cent di-n-butyl ether solution of the addition product of boron fluoride and di-n-butyl ether (obtainable by passing boron fluoride into an equimolecular proportion of di-n-butyl ether), further quantities of vinyl p  ethyl ether and condensing agent being added in the course of 2 hours; (8) vinyl-n-butyl ether or vinyl-cyclohexyl ether, similarly, but using a solution of the addition product of boron fluoride and diethyl ether in diethyl ether; (9) vinyl methyl ether, by the method of (7), or by heating with the same condensing agent to 60 DEG  C. in an autoclave for 4-6 hours; (10) vinyl octodecyl ether (obtainable from octodecyl alcohol and acetylene in the presence of caustic potash), vinyl-octyl, -decyl, -dodecyl or tetradecyl ethers or the vinyl ethers of oleyl alcohol or the alcohols corresponding to the acids of montan wax, by the method of (7), or by means of a solution of boron fluoride in acetic acid; (11) octodecandiol divinyl ether (obtainable from acetylene and octodecandiol, which is prepared by catalytic hydrogenation of castor oil) in admixture with vinyl ethyl ether, by the method of (7); (12) octodecandiol divinyl ether or triethylene glycol divinyl ether, by dissolving in benzene or benzine and adding a 1 per cent solution of boron fluoride in di-n-butyl ether; (13) the vinyl ether of diethylene glycol monoethyl ether (obtainable from acetylene and the said ether) by the method of (7); (14) divinyl ether, by adding the condensing agent employed in (7). Specifications 332,605, [Class 2 (iii), Dyes &c.], 341,074, 345,253, and 369,297 are referred to.ALSO:Polymerized vinyl ethers may be employed as softening or plastifying agents for indiarubber or rubber-like polymerization products of diolefines, and for adhesive purposes.  The lower members, which are soluble in water with or without the help of a dissolution assistant such as methyl or ethyl alcohols or ethylene glycol mono-ethyl or methyl ethers, may be employed in sizing.