US4370449A — Transition metal composition and production there…

Claim 1

Independent Claim 425 words

A process for the production of a polymer or copolymer of an olefine monomer wherein at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, is polymerised by contacting the at least one olefine, or mixture thereof with ethylene, under polymerisation conditions with an olefine polymerisation catalyst comprising (1) a titanium trichloride-containing material; and (2) at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound, wherein the titanium trichloride-containing material which is component (1) of the catalyst is obtained by a process which consists essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atoms, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; and (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid where E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR2## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3.

Claim 2

Dependent Claim 425 words

A process for the production of a polymer or copolymer of an olefine monomer wherein at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, is polymerised by contacting the at least one olefine, or mixture thereof with ethylene, under polymerisation conditions with an olefine polymerisation catalyst comprising (1) a titanium trichloride-containing material; and (2) at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound, wherein the titanium trichloride-containing material which is component (1) of the catalyst is obtained by a process which consists essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atoms, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; and (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid where E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR2## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3.

Claim 3

Dependent Claim 64 words

The process of claim 1 wherein the titanium trichloride-containing material which is component (1) of said catalyst has the formula TiCl.sub.3 (AlR.sub.x X.sub.3-x).sub.n E.sub.a L.sub.b ; where R is a hydrocarbyl group; X is a halogen atom other than fluorine; x is such that 0≦x≦3.0; n is from 0 up to 0.5; and a and b are each, independently, from 0.001 up to 0.50.

Claim 4

Dependent Claim 39 words

The process of claim 2 wherein, in component (1) of the catalyst, the group R is an alkyl group containing from 2 up to 10 carbon atoms, X is chlorine and the value of x is such that 0≦x≦2.0.

Claim 5

Dependent Claim 19 words

The process of claim 1 wherein, in component (1) of the catalyst, E is di-n-butyl ether or di-isoamyl ether.

Claim 6

Dependent Claim 34 words

The process of claim 1 wherein, in component (1) of the catalyst, the compound L is the ethyl ester of phenylacetic acid, glycerol monoacetate, glycerol monostearate, glycerol tripalmitate, glycerol trimethacrylate, pentaerythritol tetra-acrylate or N,N,N',N'-tetramethylethylenediamine.

Claim 7

Dependent Claim 16 words

The process of claim 1 wherein component (2) of the catalyst is a dihydrocarbyl aluminium halide.

Claim 8

Dependent Claim 38 words

The process of claim 1 wherein polymerisation is effected at a temperature in the range from 20° C. up to 100° C. in the presence of from 0.01 up to 5.0% molar, relative to the monomer, of hydrogen.

Claim 9

Dependent Claim 19 words

The process of claim 1 wherein propylene is polymerised and thereafter a mixture of propylene and ethylene is polymerised.

Claim 10

Dependent Claim 49 words

The process of claim 1 wherein the titanium trichloride-containing material which is component (1) of the catalyst is obtained by a process in which the solid, beta titanium trichloride formed in step (1) is separated from the reaction medium of step (1) and washed prior to contacting step (2).

Claim 11

Dependent Claim 77 words

The process of claim 1 wherein the titanium trichloride-containing material which is component (1) of the catalyst is obtained by a process in which said contacting step (2) comprises contacting said suspension of said solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, said contacting being effected only after said solid reduction product of step (1) has been heated to a temperature of at least 60° C.

Claim 12

Dependent Claim 419 words

A process for the production of a polymer or copolymer of an olefine monomer by the steps comprising forming a titanium trichloride-containing material by a process which consists essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atomns, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; and (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid where E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR3## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3; and thereafter contacting at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, under polymerisation conditions with an olefine polymerisation catalyst obtained from (A) the titanium trichloride-containing material which is the product of steps (1), (2) and (3), and (B) at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound.

Claim 13

Dependent Claim 419 words

A process for the production of a polymer or copolymer of an olefine monomer by the steps comprising forming a titanium trichloride-containing material by a process which consists essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atomns, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; and (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid where E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR3## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3; and thereafter contacting at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, under polymerisation conditions with an olefine polymerisation catalyst obtained from (A) the titanium trichloride-containing material which is the product of steps (1), (2) and (3), and (B) at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound.

Claim 14

Dependent Claim 400 words

A process for the production of a polymer or copolymer of an olefine monomer by the steps consisting essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atoms, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid; (4) mixing the solid product of steps (1), (2) and (3) with an organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound; and (5) contacting at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, under polymerisation conditions with the product of step (4), wherein E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR4## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3.

Claim 15

Dependent Claim 400 words

A process for the production of a polymer or copolymer of an olefine monomer by the steps consisting essentially of (1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a solid titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atoms, wherein the titanium trichloride is formed predominantly in the solid beta-form; (2) contacting a suspension of the solid reduction product of step (1) with reagents consisting of compound E and compound L either simultaneously or sequentially, at least part of the contacting being effected while maintaining the suspension at a temperature of at least 60° C. in the presence of at least compound E or compound L; (3) subsequent to the contacting with the compound E washing the solid product obtained with an inert hydrocarbon or inert halohydrocarbon liquid; (4) mixing the solid product of steps (1), (2) and (3) with an organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound; and (5) contacting at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, under polymerisation conditions with the product of step (4), wherein E is an ether or a thioether; and L is an organic Lewis Base compound selected from esters of the formula R.sup.1 R.sup.2 R.sup.3 CCOOR.sup.1 ; esters and partial esters of aliphatic diols and polyols; amines of the formula R.sup.4 R.sup.5 R.sup.6 N; and ketones of the formula ##STR4## where R 1 is a hydrocarbyl group; R 2 and R 3 are each, independently, a hydrogen atom or a hydrocarbyl group; or the group R 1 R 2 R 3 C-- is a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed hydrocarbyl ring system; R 4 and R 5 are hydrocarbyl groups; R 6 is a hydrogen atom, a hydrocarbyl group or a group --C.sub.m H.sub.2m NR.sup.4 R.sup.5 ; or R 4 and R 5 , optionally together with R 6 , together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system; R 7 is a hydrocarbyl group; R 8 is a hydrocarbyl group, which may optionally be substituted with one hydrocarbonoxy group; and m is 1, 2 or 3.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-01-24	1986-07-26	1987-01-25	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-01-24	1990-07-26	1991-01-25	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-01-24	1994-07-26	1995-01-25	$7700.00	Window Closed / Lapsed

Transition metal composition and production thereof

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag