Патент USA US2121695код для вставки
Patented‘ June 21,':1-938 1 2,121,595 UNITED STATES PAT-ENT- orrics ' . 2,121,695 v ' POLYMEBIZATION PROCESS Rowland Hill, Biackley, Manchester, England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. bpplicationoctober 13, 1938, Se rial No. 105,444. In Great Britain October 23, 1985 ‘ 3 GlaimsThis invention relates to a process for the‘ manufacture of valuable polymerization prod ucts from. cyclohexene oxide. (Cl. 280-2) with a small amount (2 parts) of active carbon and ?ltered to remove kieselguhr. _- The benzene . is then evaporated from the ?ltrate by heating ' at 80°- C. under ‘reduced pressure (20-30 mm.). The residue so obtained is a pale straw-colored, 5 It is known to obtain resinous polymers by sub 5 jecting cyclohexene oxide to very high pressures hard, somewhat brittle transparent resin. It dis- , for several days in presence of a small amount of benzoyl peroxide. ‘solves readily in cold benzene, toluene or tur - pentine but is insoluble inv cold methylated spirits According to the present invention I ,obtain resinous polymers by treating cyclohexene oxide or ethylene glycol monoethyl ether. It is freely soluble in linseed oil, tung oil or a linseed “stand” 10 10 in the presence of an active earth or clay as poly-> merization catalyst. By an active earth or clay I mean a ?nely-divided, highly-absorbent clay or earth such as, for example, bentonite, fuiler’s o . The resin produced in accordance with the foregoing example is in addition to being com patible with drying oils also compatible with rosin modi?ed glyceryl phthalate resins and other rosin 15 earth or talc or a diatomaceous earth such as 15 kieselguhr. In carrying the invention into e?ect it is not modi?ed polyhydric alcohol-polycarboxylic acid resins. The resin of the foregoing example is necessary to use very high pressures. Thus, in also compatible in equal proportions with nitro presence of active earth catalysts polymerization cellulose and ethyl cellulose, and with cellulose acetate in the ratio of 60 partsjof the polymer to 20 may conveniently be e?ected at atmospheric 2o pressures by the application of moderate heat. Polymerization may be carried out in presence or absence of a solvent or diluent. The reaction ‘after it is initiated is highly exothermic and may be controlled by cooling. After the initial violent as reaction subsides the reaction mixture is heated 100 parts of the acetate. - .. It is to ‘be observed that although the alkylene oxides can be polymerized by a large number of agents such as calcium chloride, metallic sodium, ultra violetlight. etc., these agents are ineilec- 25 to maintain reaction temperature until a product. tive for polymerizing cyclohexene'oxide, and the oxides mentioned herein. ‘ of the desired degree of condensation is obtained. other The present invention is applicable to all car The polymerization products obtained accord bocyclic epoxy compounds in which the; oxygen ing to the invention-are usually in the form of a is linked to adjacent carbon atoms‘,v which are 30 30 hard, somewhat brittle, transparent mass. The ' ‘both members of a carbocyelie group. I may for products are readily soluble in organic solvents instance use alkyl substituted cyclohexene oxides, ' such as benzene, toluene or turpentine and in dry—, e. g.,_ methyl, dimethyl, isopropyl, butyl, etc., ing oils such as linseed oil. Becauseof their solu bility in organic media and their other physical cyclohexene oxides as well as dlhydronaphtha lene. oxides. vPartially or completely hydrogen- '35 35 properties, the polymerization products are valu ated substituted or v unsubstituted dihydro able ingredients for varnish compositions, nitro naphthalene oxides may also be used. Carbo cellulose lacquers and the like. The following example, in which the parts are , cyclic epoxy compounds containing less than six atoms may also be used. Compounds of by weight, illustratesbut does not-limit the in carbon the kind mentioned herein may be- interpoly- 40 40 vention: ' merized, as for instance by using any combination Example ' of these compounds. One (1) partv kieselguhr is suspended in 50 parts cyclohexene oxide (“Organic Syntheses", 45 vol. 5, page 35, London,,1925), the mixture is heated to 100° ‘C. to initiate the reaction in a vessel ?tted with are?ux condenser. After they initial violent reaction subsides the temperature is adjusted to 110 to 115° C. Polymerization, ‘ae 50 companied by an increase in viscosity. is rapid at ?rst. After 4-6 hours, the reaction mixture. changes from a mobile into a moderately viscous ?uid at reactionv temperature. After 40 hours, the reaction mixture is very viscous and the 55 viscous mass is then dissolved in benzene, boiled v The preferred materials, ' however, are the carbocyclic epoxy compoimds of thehydroaromatic seriessuch as cyclohexene oxide. ' " ' ' . - v 45 As vmany apparently widely different embodi ' ments of this invention may be made without de parting from the spirit and scope thereof, it is to be understood that I do not limit myself to the speci?c embodiments thereof except‘ as de?ned 5o in the appended claims. _ 1. A process for vproducing polymers which comprises heating in the presence-of a catalyst an epoxy compound in which the oxygen is linked 55 I 8,121,6Q5 to eiiec-ent carbon atoms in e cerbccyclic ring, and ccntin the heating until said epoxy ' S. A process which comprises heating cyc1o~ hexene omde with an active earth and after the eompcund is polymerized, said ceteiyst being‘ reaction has been initiated maintaining the tem selected from the class of active earths and cieys. pereture from 110 to 115° C. until a. resinous 2. In a. process for making resins from cyclo product soluble in drying oil is obtained. hexene oxide the step which comprises heating cyciohexene oxide with an active earth. R0 EIIL.