Process for the polymerization of olefins

Claim 1

A method for the production of olefin polymers having a high crystallinity which comprises polymerizing an olefin using: a solid catalyst produced by preparing a titanium trichloride composition by reducing titanium tetrachloride with an organo-aluminum compound of the formula: R.sub.n AlX.sub.3-n wherein R is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom or a hydrogen atom, and n satisfies the relationship 1≦n≦3, at a temperature of about -100° to about 60° C. to obtain a solid reduction product, and then treating the resulting solid reduction product by one of the following methods, (a), (b), (c), (d), (e) or (f): (a) heat-treating the solid reduction product at about 100° to about 180° C. in the absence of or presence of an inert solvent, (b) catalytically treating the solid reduction product with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group of an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, and, optionally, further catalytically treating the resulting product with an ether, (c) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, and, optionally, further catalytically treating the resulting product with an ether, (d) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, in the presence of an organo-halogen compound of the formula: R'''X wherein R''' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, and X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (e) catalytically treating the solid reduction product with an ether and then with an aluminum halide of the formula: AlX.sub.3 wherein X is a halogen atom, dissolved in an aromatic hydrocarbon in the presence of a hydrogen halide of the formula: HX wherein X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (f) catalytically treating the solid reduction product with an ether and then with titanium tetrachloride, and treating the thus produced titanium trichloride composition at a temperature of from about 0° to about 150° C. with a mixture of a halogenated hydrocarbon (1) represented by the formula: CH.sub.q X.sub.4-q wherein X is a halogen atom and q is an integer satisfying the relationship 0≦q≦4, and an ether (2) represented by the formula: R.sub.3 --0--R.sub.4 wherein R 3 and R 4 , which may be the same or different, each is an alkyl group, each having up to 10 carbon atoms, wherein the amount of the halogenated hydrocarbon and ether used in the catalytic treating of the titanium trichloride composition are about 0.001 to about 1.0 and about 0.001 to about 5 times on a molar basis to the amount of the titanium trichloride contained in the titanium trichloride composition, respectively; and an organo-aluminum compound of the formula: R'l AlX.sub.3-l wherein R' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms; X is a halogen atom, a hydrogen atom or an alkoxy group; and l satisfies the relationship 1.5≦l≦3, as an activator.

Claim 2

A method for the production of olefin polymers having a high crystallinity which comprises polymerizing an olefin using: a solid catalyst produced by preparing a titanium trichloride composition by reducing titanium tetrachloride with an organo-aluminum compound of the formula: R.sub.n AlX.sub.3-n wherein R is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom or a hydrogen atom, and n satisfies the relationship 1≦n≦3, at a temperature of about -100° to about 60° C. to obtain a solid reduction product, and then treating the resulting solid reduction product by one of the following methods, (a), (b), (c), (d), (e) or (f): (a) heat-treating the solid reduction product at about 100° to about 180° C. in the absence of or presence of an inert solvent, (b) catalytically treating the solid reduction product with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group of an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, and, optionally, further catalytically treating the resulting product with an ether, (c) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, and, optionally, further catalytically treating the resulting product with an ether, (d) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p AlX.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1≦p≦1.5, in the presence of an organo-halogen compound of the formula: R'''X wherein R''' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, and X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (e) catalytically treating the solid reduction product with an ether and then with an aluminum halide of the formula: AlX.sub.3 wherein X is a halogen atom, dissolved in an aromatic hydrocarbon in the presence of a hydrogen halide of the formula: HX wherein X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (f) catalytically treating the solid reduction product with an ether and then with titanium tetrachloride, and treating the thus produced titanium trichloride composition at a temperature of from about 0° to about 150° C. with a mixture of a halogenated hydrocarbon (1) represented by the formula: CH.sub.q X.sub.4-q wherein X is a halogen atom and q is an integer satisfying the relationship 0≦q≦4, and an ether (2) represented by the formula: R.sub.3 --0--R.sub.4 wherein R 3 and R 4 , which may be the same or different, each is an alkyl group, each having up to 10 carbon atoms, wherein the amount of the halogenated hydrocarbon and ether used in the catalytic treating of the titanium trichloride composition are about 0.001 to about 1.0 and about 0.001 to about 5 times on a molar basis to the amount of the titanium trichloride contained in the titanium trichloride composition, respectively; and an organo-aluminum compound of the formula: R'l AlX.sub.3-l wherein R' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms; X is a halogen atom, a hydrogen atom or an alkoxy group; and l satisfies the relationship 1.5≦l≦3, as an activator.