Polymerization of olefins employing catalysts prepared from novel titanium compounds

Claim 2

In a process for polymerizing at least one α-olefin or a mixture of at least one α-olefin and at least one polymerizable ethylenically unsaturated monomer in the presence of a supported Ziegler-Natta catalyst; the improvement which comprises employing as the transition metal component of such catalyst that which results from reacting (A) at least one titanium compound represented by the formula Ti(OR) x X 4-x wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen and x has a value from zero to 4; with (B) at least one compound containing at least one aliphatic hydroxyl group represented by the formula ##STR5## wherein A is a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently hydrogen, a hydrocarbyl group or a halogen, nitro or hydrocarbyloxy substituted hydrocarbyl group, each such hydrocarbyl or hydrocarbyloxy groups having from 1 to about 20 carbon atoms; n is zero or 1; and wherein components (A) and (B) are employed in quantities which provide a molar ratio of (B):(A) of 0.1:1 to about 10:1.

Claim 3

A process of claim 1 wherein (1) in component (A) (a) each R independently has from 1 to about 10 carbon atoms; and (b) X is chlorine; (2) in component (B) (a) A has from 1 to about 4 carbon atoms; (b) when R is a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group, it has from 1 to about 10 carbon atoms; and (c) when R' is a hydrocarbyl group or a hydrocarbyloxy group, it has from about 1 to about 10 carbon atoms; (3) components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 1:1 to about 5:1.

Claim 4

A process of claim 2 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms; and (b) components (A) and (B) are employed in quantities which provide a molar ratio of B:A of from about 1:1 to about 2:1.

Claim 5

A process of claim 3 wherein (a) n has a value of 1; (b) A is a methylene group; and (c) each R is independently hydrogen, a methyl group or phenyl group.

Claim 6

A process of claims 1, 2, 3 or 4 wherein component A is tetraisopropoxytitanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.

Claim 7

A process of claims 1, 2, 3 or 4 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 8

A process of claim 6 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.

Claim 9

A process of claim 5 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 10

A process of claim 8 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.

Claim 11

A process for polymerizing at least one α-olefin or a mixture of at least one α-olefin and at least one polymerizable ethylenically unsaturated monomer under suitable polymerization conditions in the presence of a catalyst composition resulting from reacting in an inert hydrocarbon medium (A) at least one hydrocarbon soluble organomagnesium component represented by the formula MgR" 2 .xMR" y wherein each R" is independently a hydrocarbyl group having from 1 to 20 carbon atoms; M is a metal selected from Al, Zn, Si, Sn, B and P; y has a number corresponding to the valence of M and x has a value from about 0.001 to about 10; (B) a halide source selected from (1) an active non-metallic halide, said non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen; or (2) a metallic halide corresponding to the formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, X is halogen, Y is a number corresponding to the valence of M and a is a number from 1 to y; and (C) a compound or complex resulting from reacting (1) at least one titanium compound represented by the formula Ti(OR) x X 4-x wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen and x has a value from zero to 4; with (2) at least one compound containing at least one aliphatic hydroxyl group represented by the formula ##STR6## wherein each A is a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently hydrogen, a hydrocarbyl group or a halogen, nitro or hydrocarbyloxy substituted hydrocarbyl group, each such hydrocarbyl or hydrocarbyloxy groups having from 1 to about 20 carbon atoms; n is zero or 1; and when components (A) and/or (B) do not contain or contain an insufficient quantity of aluminum, then (D) an aluminum compound represented by the formula AlR y' X y" wherein R is a hydrocarbyl group having from 1 to about 10 carbon atoms; X is halogen and y' and y" each have a value of from zero to three with the sum of y' and y" being three is employed; and wherein the components are employed in quantities so as to provide the following ratios: (1) a Mg:Ti atomic ratio of from about 1:1 to about 200:1; (2) components (C-2) and (C-1) are employed in quantities which provide a molar ratio of (C-2):(C-1) of from about 0.1:1 to about 10:1; (3) excess X:Al ratio of from about 0.0005:1 to about 10:1; and (4) an Al:Ti atomic ratio of from about 0.1:1 to about 2000:1.

Claim 12

A process for polymerizing at least one α-olefin or a mixture of at least one α-olefin and at least one polymerizable ethylenically unsaturated monomer under suitable polymerization conditions in the presence of a catalyst composition resulting from reacting in an inert hydrocarbon medium (A) at least one hydrocarbon soluble organomagnesium component represented by the formula MgR" 2 .xMR" y wherein each R" is independently a hydrocarbyl group having from 1 to 20 carbon atoms; M is a metal selected from Al, Zn, Si, Sn, B and P; y has a number corresponding to the valence of M and x has a value from about 0.001 to about 10; (B) a halide source selected from (1) an active non-metallic halide, said non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen; or (2) a metallic halide corresponding to the formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, X is halogen, Y is a number corresponding to the valence of M and a is a number from 1 to y; and (C) a compound or complex resulting from reacting (1) at least one titanium compound represented by the formula Ti(OR) x X 4-x wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen and x has a value from zero to 4; with (2) at least one compound containing at least one aliphatic hydroxyl group represented by the formula ##STR6## wherein each A is a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently hydrogen, a hydrocarbyl group or a halogen, nitro or hydrocarbyloxy substituted hydrocarbyl group, each such hydrocarbyl or hydrocarbyloxy groups having from 1 to about 20 carbon atoms; n is zero or 1; and when components (A) and/or (B) do not contain or contain an insufficient quantity of aluminum, then (D) an aluminum compound represented by the formula AlR y' X y" wherein R is a hydrocarbyl group having from 1 to about 10 carbon atoms; X is halogen and y' and y" each have a value of from zero to three with the sum of y' and y" being three is employed; and wherein the components are employed in quantities so as to provide the following ratios: (1) a Mg:Ti atomic ratio of from about 1:1 to about 200:1; (2) components (C-2) and (C-1) are employed in quantities which provide a molar ratio of (C-2):(C-1) of from about 0.1:1 to about 10:1; (3) excess X:Al ratio of from about 0.0005:1 to about 10:1; and (4) an Al:Ti atomic ratio of from about 0.1:1 to about 2000:1.

Claim 13

A process of claim 10 wherein (1) in component (A), (a) R" has from 1 to about 10 carbon atoms; (b) M is aluminum; and (c) x has a value from 0.001 to about 5; (2) in component (B), (a) M is aluminum; (b) R' is hydrogen or a tertiary butyl group; (c) X is chlorine; and (d) R and R' independently have from 1 to about 10 carbon atoms; (3) in component (C-1), (a) R has from about 1 to about 10 carbon atoms; and (b) X is chlorine; (4) in component (C-2) (a) A has from 1 to about 4 carbon atoms; (b) when R is a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group, it has from 1 to about 10 carbon atoms; and (c) when R' is a hydrocarbyl group or a hydrocarbyloxy group, it has from about 1 to about 10 carbon atoms; (5) in component (D), (a) M is aluminum; (b) R has from 1 to about 10 carbon atoms; and (c) X is chlorine; and (6) the components are employed in quantities so as to provide the following ratios: (a) a Mg:Ti atomic ratio of from about 2:1 to about 100:1; (b) components (C-1) and (C-2) are employed in quantities which provide a molar ratio of (C-2):(C-1) of from about 1:1 to about 5:1; (c) an excess X to Al ratio of from about 0.002:1 to about 2:1; and (d) an Al:Ti atomic ratio of from about 0.5:1 to about 200:1.

Claim 14

A process of claim 11 wherein in component (C-1), each R has from about 2 to about 4 carbon atoms.

Claim 15

A process of claim 12 wherein the components are employed in quantities so as to provide the following ratios: (a) a Mg:Ti atomic ratio of from about 5:1 to about 50:1; (b) in component (C-2) (i) n has a value of 1; (ii) A is a methylene group; and (iii) each R is independently hydrogen, a methyl group or a phenyl group; (C) components (C-1) and (C-2) are employed in quantities which provide a molar ratio of (C-2):(C-1) of from about 1:1 to about 2:1; (d) an excess X to Al ratio of from about 0.01:1 to about 1.4:1; and (e) an Al:Ti atomic ratio of from about 1:1 to about 75:1.

Claim 16

A process of claims 11, 12 or 13 wherein the components are added in the order selected from (A) A, B, ((C-1) and (C-2), prereacted), D (if required); (B) A, B, D (if required), ((C-1) and (C-2), prereacted); (C) (A and B, prereacted), ((C-1) and (C-2), prereacted), D (if required); (D) (A and B, prereacted), D (if required), ((C-1) and (C-2), prereacted); or (E) (A, B, and D (if required), prereacted), ((C-1) and (C-2), prereacted).

Claim 17

A process of claims 11, 12 or 13 wherein component (C-1) is tetraiisopropoxy titanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.

Claim 18

A process of claim 14 wherein component (C-1) is tetraiisopropoxy titanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.

Claim 19

A process of claims 11, 12 or 13 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 20

A process of claim 17 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.

Claim 21

A process of claim 14 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 22

A process of claim 19 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.

Claim 23

A process of claim 15 wherein wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 24

A process of claim 21 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.

Claim 25

A process of claim 16 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 2 to about 10 carbon atoms is polymerized.

Claim 26

A process of claim 23 wherein ethylene or a mixture of ethylene and at least one of butene-1, hexene-1 or octene-1 is polymerized.