Patent GB-896844-A (GB)
Title: Polymerization of unsaturated ethers
IPC: C08F16/12
Filed: 1960-09-07
Abstract: The Specification describes, as a polymerization catalyst, a mixture of sulphuric acid and a metal compound of the formula:-MOx Ry (OR1)z in which M is a metal of Group IIIb, IVa, IVb, Va, VIa or VIII of the Periodic Table, R is hydrogen, alkyl, cycloalkyl, aralkyl or aryl, R1 is alkyl, cycloalkyl, aralkyl or aryl, x is 0-2 and, when x is 0, y+2 is equal to n, the valence of the metal, when x is 1, y+2 equals n-2, and when x is 2, y+2 equals n-4.  Specified metal compounds include aluminium methoxide, ethoxide, propoxide, isopropoxide, butoxide, phenoxide, benzyl oxide, acetyl acetonate, 2-methoxy ethoxide, or 2-ethoxy ethoxide, titanium alkoxides or acetoacetonate, ferric alkoxides and acetoacetonate, stannate esters and zirconium alkoxides.  The catalyst is usually made by mixing the metal compound with sulphuric acid in an inert diluent such as hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, ethylene dichloride, chlorobenzene, ethyl acetate or diethyl ether.  The activity of the catalyst may be enhanced by the use of an activator. This may be a metal alkyl, alkoxide or alkyl alkoxide; the metal being either the same or different from that of the catalyst.  If a metal alkyl is used it can be reacted with a complexing agent such as diethyl ether, tetrahydrofuran or ethyl acetate.ALSO:A process is described for polymerization of unsaturated ethers of the type:-CH=CH-O-using as a catalyst a mixture of sulphuric acid and a metal compound of formula MOxRy(OR1)z in which M is a metal of Group IIIb, IVa or IVb, Va, VIa or VIII of the Periodic Table (Mendel<\>eeff), R is hydrogen, or alkyl, cycloalkyl, aralkyl, or aryl, R1 is alkyl, cycloalkyl, aralkyl or aryl, x is 0 to 2 and when x is 0, the sum of y and z is equal to n the valence of the metal; when x is 1, the sum of y and z is equal to (n-2); and when x is 2, the sum of y and z is equal to (n-4).  Ethers specified are vinyl methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, trifluoroethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, neopentyl, n-hexyl, 2-ethylhexyl, stearyl, allyl, cyclohexyl, a -terpinyl, isobornyl, benzyl, p-chlorobenzyl, a ,a -dimethylbenzyl, phenyl, p-methylphenyl, p-chlorophenyl, and a -naphthyl ether, and 1-methoxybutadiene.  Metal compounds specified are aluminium, gallium, and indium trimethyl, triethyl, diethyl hydride, tripropyl, triisopropyl, triisobutyl, diisobutyl hydride, tri-n-hexyl, trioctyl, tricyclohexyl and triphenyl, and tin tetralkyls.  Also specified are aluminium methoxide, ethoxide, propoxide, isopropoxide, butoxide, phenoxide, benzyloxide, acetylacetonate, 2-methoxyethoxide, 2-ethoxyethoxide, mixed aluminium alkyl alkoxides, titanium alkoxides and acetylacetonates, vanadium alkoxides, acetylacetonate and ethyl vanadate, ferric alkoxides and acetylacetonate, tert.-butyl chromate, chromium acetylacetonate, stannate esters, and zirconium alkoxides. The catalyst is usually made by mixing the metal compound with sulphuric acid in an inert diluent such as hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, ethylene dichloride, chlorobenzene, ethylacetate or diethyl ether.  These liquids may be used as diluents during polymerization as also may ethyl chloride, methyl chloride, chloroform and ethers such as dioxane and tetrahydrofuran.  The activity of the catalyst may be enhanced by the use of an activator.  This may be a metal alkyl, alkoxide or alkyl alkoxide; the metal being either the same or different from that of the catalyst.  If a metal alkyl is used, it can be reacted with a complexing agent such as diethyl ether, tetrahydrofuran or ethyl acetate to cut down side reactions. Examples are given illustrating the invention.