Patent GB-999557-A (GB)
Title: Polymerisation process
IPC: C08F14/18
Filed: 1962-05-16
Abstract: The following compounds are used as polymerization catalyst components: (1) Ti(Oi-C3H7)2 (acetylacetonate residue), prepared by reacting at 70 DEG  C. Ti(Oi-C3H7)4 with CH3-COCH2COCH3, (2) Al(i-C4H9)(OC4H3F6)Cl by reacting Al(i-C4H9)2Cl with CF3.CFH.CF2CH2-OH in benzene, and (3) Ti(Oi-C3H7) (OCH2-CF2-CFH-CF3)3 by reacting in benzene CF3-CFH-CF2-CH2OH with Ti(O-i-C3-H7)4.ALSO:Polymers of fluorine-containing-olefins are made by polymerizing one or more of said olefins with each other and/or with other halogen-containing-olefins, in the presence of a catalyst dissolved and/or dispersed in an organic liquid, and consisting of the reaction product of an organometallic compound of an element of Group III, and a transition metal compound containing an organic radical.  The fluorinated olefin may be completely or partially fluorinated. The catalyst is preferably preformed, but may be formed in situ.  The polymerization may be effected in bulk, or in a solvent or diluent. Completely fluorinated olefins may be C2F4, C3F6, perfluorobutene, perfluoropentene, perfluoro-4-hexene, perfluoroisobutene, perfluorocyclobutene, and perfluorocyclohexene. Partially fluorinated olefins are vinyl and vinylidene fluoride, 1,2-difluoroethylene, trifluoroethylene, 2-fluoropropylene, 3,3,3-trifluoropropylene, 2,3,3,3 - tetrafluoropropylene - 1, 1,1,3,3,3 - pentafluoropropylene - 1, 1,1,2-trifluoropropylene - 1, 1,1,2 - trifluorohexene-1, and, alpha,beta,beta-trifluorostyrene. Other comonomers may be trifluorochloroethylene, trifluorobromoethylene, vinyl and vinylidene chloride, 1,1 - difluoro - 2,2 - dichloroethylene, 3,3,3 - trichloropropylene - 1, 2 - chloropropylene, and halogen-containing compounds of butene, isobutene, butadiene, isoprene, and styrene.  Exemplified catalysts are titanium tetra-isopropylate and triisobutyl aluminium, titanium tetraisopropylate and diisobutyl alumiinium chloride, titanium tetraisopropylate and isobutyl aluminium dichloride, titanium tetrasopropylate and diisobutyl aluminium monohydride, vanadyl acetylacetonate and monoethylmonoethoxy aluminium monochloride, titanium tetramethylate and diisobutyl aluminium monochloride (C5H7O2)2Ti(Oi-C3H7)2 and Al(iC4H9) . (OCH2 - CF2 - CFH - CF3)Cl, Ti(Oi - C3H7) . (OCH2 - CF2 - CFH - CF3)3 and Al(iC4H9)3, vanadyl acetylacetonate and Al(iC4H9)2F, vanadyl acetylacetonate and Al(iC4H9).(Oi-C4H9)Cl, vanadyl acetylacetonate and Al(iC4H9)(Oi-C4H9)F, and vanadyl acetylacetonate and Al(iC4H9)(OCH2 -CF2-CHF-CF3)F. The polymers are recovered by known techniques.  The following polymers are claimed per se (1) crystalline polyhexafluoropropylene soluble in hot carbon tetrachloride, tetrahydrofuran, acetyl methyl ethyl ketone and ethyl acetate, (2) solid poly-3,3,3-trifluoropropylene partially soluble in tetrahydrofuran, acetone, and hot methanol and ethanol, (3) solid poly-2-fluoropropylene soluble in hot n-heptane and tetrahydrofuran, (4) copolymers of tetrafluoroethylene and hexafluoro-propylene, (5) copolymers of hexafluoropropylene and vinyl chloride, (6) copolymers of trifluoropropylene and trichloropropylene, (7) copolymers of trifluoropropylene and vinyl chloride, (8) copolymers of vinylidene fluoride and vinyl chloride, and (9) copolymers of vinyl fluoride and vinylidene fluoride containing more than 50% by mols of combined vinyl fluoride.