US4452914A
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Titanium complexes and catalysts prepared therefrom
Assignee: Dow Chemical Co
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Filing: 1982-08-13
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Granted: 1984-06-05
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Expires: 2002-08-13
Abstract
Abstract Novel titanium compounds or complexes are prepared by reacting a titanium compound such as titanium tetraisopropoxide with a compound containing at least one aromatic hydroxyl group. These compounds and/or complexes are useful as the transition metal component in Ziegler-Natta catalysts.
Inventors
- 👤 William M. Coleman, III
- 👤 Morris S. Edmondson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 04:33
CPC Classifications
C; C08; C08F; C08F10/00; C07; C07F; C07F7/00; C07F7/28
Claims Analysis
Total Claims: 79
Claim 1
Independent Claim
267 words
A titanium complex or compound resulting 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 aromatic hydroxyl group represented by the formulas ##STR20## wherein each A is independently, ##STR21## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR22## or a hydroxyl substituted hydrocarbyl or hydroxyl substituted hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; n has a value of 1; each x independently has a value of zero to 2; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and wherein components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 0.1:1 to about 10:1.
Claim 2
Dependent Claim
267 words
A titanium complex or compound resulting 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 aromatic hydroxyl group represented by the formulas ##STR20## wherein each A is independently, ##STR21## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR22## or a hydroxyl substituted hydrocarbyl or hydroxyl substituted hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; n has a value of 1; each x independently has a value of zero to 2; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and wherein components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 0.1:1 to about 10:1.
Claim 3
Dependent Claim
170 words
A titanium compound or complex of claim 1 wherein (1) in component (A) (a) R has from about 1 to about 10 carbon atoms; and (b) X is chlorine; (2) in component (B) (a) when A' is a divalent hydrocarbyl group it has from about 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; (c) when R' is a hydrocarbyl group, it has from about 1 to about 6 carbon atoms; (d) when X is hydrocarbyl or hydrocarbyloxy, it has from about 1 to about 12 carbon atoms; (e) m has a value of from about 1 to about 3; (f) y has a value of from zero to 2; (g) z has a value from 1 to 2; (h) x has a value of zero; and (3) components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 1:1 to about 4:1.
Claim 4
Dependent Claim
58 words
A titanium compound or complex of claim 2 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms, (b) component (B) is represented by the formula ##STR23## and (c) wherein 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
Dependent Claim
32 words
A titanium compound or complex of claim 3 wherein in component (B) n has a value of 1 and A is ##STR24## and the hydroxyl groups are in the ortho (2) position.
Claim 6
Dependent Claim
32 words
A titanium compound or complex of claim 4 wherein in component (B) each X is independently a hydrocarbyl group or a halogen and each y has a value of 1 or 2.
Claim 7
Dependent Claim
26 words
A titanium compound or complex of claim 5 wherein in component (B) each X is independently methyl or t-butyl and y has a value of 2.
Claim 8
Dependent Claim
22 words
A titanium compound or complex of claim 6 wherein in component (B) each X is t-butyl located at positions 3 and 5.
Claim 9
Dependent Claim
31 words
A titanium compound or complex of claim 5 wherein in component (B) A is ##STR25## each X is independently chlorine, methyl or t-butyl and each y has a value of 2.
Claim 10
Dependent Claim
42 words
A titanium compound or complex of claim 8 wherein (a) one X is t-butyl at position 3 and the other X is methyl at position 5; and (b) each X is t-butyl, one at position 3 and the other at position 5.
Claim 11
Dependent Claim
27 words
A titanium compound or complex of claim 5 wherein in component (B) each X is chlorine in position 5 and each y has a value of 1.
Claim 12
Dependent Claim
12 words
A titanium compound or complex of claim 4 wherein y is zero.
Claim 13
Dependent Claim
22 words
A titanium compound or complex of claim 3 wherein in component (B) and the hydroxyl groups are in the ortho (2) position.
Claim 14
Dependent Claim
57 words
A titanium compound or complex of claim 2 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms, (b) component (B) is represented by the formula ##STR26## and (c) 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 15
Dependent Claim
40 words
A titanium compound or complex of claim 2 wherein (1) in component (A), each R independently has from about 2 to about 4 carbon atoms; and (2) component (B) is two different components each independently represented by the formulas ##STR27##
Claim 16
Dependent Claim
172 words
A titanium compound or complex of claim 14 wherein in component (B) (a) one component is represented by formula I wherein R is OH, y has a value of zero and the other component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y has a value of 1; (b) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position; or (c) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other is represented by formula II wherein A is ##STR28## each X is independently a hydrocarbyl group, each y is 2, and n is 1; and wherein 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 17
Dependent Claim
294 words
A titanium compound or complex of claim 14 wherein in component (B) (a) one component is represented by formula I wherein R is a hydroxyl group at position 2 and y has a value of zero and the other component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; (b) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is a t-butyl group at position 4, and y has a value of 1 and the other component is represented by the formula I wherein R is a hydroxyl group at position 2, each X is a t-butyl group, one at position 3 and the other at position 5 and y has a value of 2; (c) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position and y has a value of zero; and (d) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein A is ##STR29## n is 1, one X is methyl at position 5, the other X is t-butyl at position 3 and y has a value of 2; and wherein 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 18
Dependent Claim
38 words
A titanium compound or complex of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 wherein component (A) is tetraisopropoxy titaium; tetra-n-butoxy titanium; titanium tetrachloride or a mixture thereof.
Claim 19
Dependent Claim
297 words
In a Zeigler-Natta catalyst containing a titanium component; the improvenent which comprises employing as the titanium component 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 aromatic hydroxyl group represented by the formulas ##STR30## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms, ##STR31## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR32## or a hydroxyl substituted hydrocarbyl or hydroxyl substituted hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; each n independently has a value of zero or 1; each X independently has a value of zero to 2; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and wherein components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 0.1:1 to about 10:1.
Claim 20
Dependent Claim
297 words
In a Zeigler-Natta catalyst containing a titanium component; the improvenent which comprises employing as the titanium component 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 aromatic hydroxyl group represented by the formulas ##STR30## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms, ##STR31## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR32## or a hydroxyl substituted hydrocarbyl or hydroxyl substituted hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; each n independently has a value of zero or 1; each X independently has a value of zero to 2; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and wherein components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 0.1:1 to about 10:1.
Claim 21
Dependent Claim
188 words
A Ziegler-Natta catalyst of claim 18 wherein (1) in component (A) (a) each R independently has from about 1 to about 10 carbon atoms; and (b) X is chlorine; (2) in component (B) (a) when A is a divalent hydrocarbyl group, it has from about 1 to about 4 carbon atoms; (b) when A' is a divalent hydrocarbyl group it has from about 1 to about 4 carbon atoms; (c) when R is a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group, it has from 1 to about 10 carbon atoms; (d) when R' is a hydrocarbyl group, it has from about 1 to about 6 carbon atoms; (e) when X is hydrocarbyl or hydrocarbyloxy, it has from about 1 to about 12 carbon atoms; (f) m has a value of from about 1 to about 3; (g) y has a value from zero to 2; (h) z has a value from 1 to 2; and (i) x has a value of zero; and (3) components (A) and (B) are employed in quantities which provides a molar ratio of B:A of from about 1:1 to about 4:1.
Claim 22
Dependent Claim
56 words
A Ziegler-Natta catalyst of claim 19 wherein (A) in component (A), each R independently has from about 2 to about 4 carbon atoms; (B) component (B) is represented by the formula ##STR33## and (C) 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 23
Dependent Claim
28 words
A Ziegler-Natta catalyst of claim 20 wherein in component (B) (A) R is --OH and (B) each X is independently hydrocarbyl, hydrocarbyloxy, halogen, nitrile, nitro, formyl or carboxyl.
Claim 24
Dependent Claim
21 words
A Ziegler-Natta catalyst of claim 21 wherein in component (B) each X is independently chlorine, methyl, isopropyl, t-butyl, t-octyl or methoxy.
Claim 25
Dependent Claim
24 words
A Ziegler-Natta catalyst of claim 22 wherein in component (B) y has a value of 1 and X is t-butyl, t-octyl, methoxy or chlorine.
Claim 26
Dependent Claim
12 words
A Ziegler-Natta catalyst of claim 23 wherein component (B) is 4-t-butyl catechol.
Claim 27
Dependent Claim
27 words
A Ziegler-Natta catalyst of claim 21 wherein in component (B) y has a value of 2 and each X is the same and is t-butyl or t-octyl.
Claim 28
Dependent Claim
50 words
A Ziegler-Natta catalyst of claim 22 wherein in component (B) y has a value of 2 and (a) one X is isopropyl in position 3 and the other is methyl in position 6, or (b) each X is t-butyl, one being at position 3 and the other at position 5.
Claim 29
Dependent Claim
55 words
A Ziegler-Natta catalyst of claim 19 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms; (b) component (B) is represented by the formula ##STR34## and (c) 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 30
Dependent Claim
30 words
A Ziegler-Natta catalyst of claim 27 wherein in component (B) n has a value of 1 and A is ##STR35## and the hydroxyl groups are in the ortho (2) position.
Claim 31
Dependent Claim
30 words
A Ziegler-Natta catalyst of claim 28 wherein in component (B) each X is independently a hydrocarbyl group or a halogen and each y has a value of 1 or 2.
Claim 32
Dependent Claim
27 words
A Ziegler-Natta catalyst of claim 29 wherein in component (B) A is ##STR36## each X is independently methyl or t-butyl and y has a value of 2.
Claim 33
Dependent Claim
20 words
A Ziegler-Natta catalyst of claim 30 wherein in component (B) each X is t-butyl located at positions 3 and 5.
Claim 34
Dependent Claim
29 words
A Ziegler-Natta catalyst of claim 28 wherein in component (B) A is ##STR37## each X is independently chlorine, methyl or t-butyl and each y has a value of 2.
Claim 35
Dependent Claim
40 words
A Ziegler-Natta catalyst of claim 32 wherein (a) one X is t-butyl at position 3 and the other X is methyl at position 5; and (b) each X is t-butyl, one at position 3 and the other at position 5.
Claim 36
Dependent Claim
31 words
A Ziegler-Natta catalyst of claim 29 wherein in component (B) A is --CH 2 -- and each X is chlorine in position 5 and each y has a value of 1.
Claim 37
Dependent Claim
16 words
A Ziegler-Natta catalyst of claim 28 wherein A is --CH 2 -- and y is zero.
Claim 38
Dependent Claim
26 words
A Ziegler-Natta catalyst of claim 27 wherein in component (B) n has a value of zero and the hydroxyl groups are in the ortho (2) position.
Claim 39
Dependent Claim
38 words
A Ziegler-Natta catalyst of claim 19 wherein (1) in component (A), each R independently has from about 2 to about 4 carbon atoms, and (2) component (B) is two different components each independently represented by the formulas ##STR38##
Claim 40
Dependent Claim
170 words
A Ziegler-Natta catalyst of claim 37 wherein in component B (a) one component is represented by formula I wherein R is OH, y has a value of zero and the other component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y has a value of 1; (b) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position; or (c) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other is represented by formula II wherein A is ##STR39## each X is independently a hydrocarbyl group, each y is 2, and n is 1; and wherein 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 41
Dependent Claim
292 words
A Ziegler-Natta catalyst of claim 37 wherein in component (B) (a) one component is represented by formula I wherein R is a hydroxyl group at position 2 and y has a value of zero and the other component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; (b) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is a t-butyl group at position 4, and y has a value of 1 and the other component is represented by the formula I wherein R is a hydroxyl group at position 2, each X is a t-butyl group, one at position 3 and the other at position 5 and y has a value of 2; (c) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position and y has a value of zero; and (d) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein A is ##STR40## n is 1, one X is methyl at position 5, the other X is t-butyl at position 3 and y has a value of 2; and wherein 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 42
Dependent Claim
42 words
A Ziegler-Natta catalyst of claims 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38 or 39 wherein component (A) is tetraiisopropoxy titanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.
Claim 43
Dependent Claim
627 words
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 sufficient quantity of at least one halide source so as to convert all of the organic groups attached to a magnesium atom in component (A) to a halide group; said halide source being 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; (C) 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 (D) at least one compound containing at least one aromatic hydroxyl group represented by the formulas ##STR41## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms, ##STR42## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR43## or a hydroxyl substituted hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; each n independently has a value of zero or 1; each x independently has a value of zero or 1; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and when components (A) and/or (C) do not contain or contain an insufficient quantity of aluminum, then (E) 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) and (D) are employed in quantities which provide a molar ratio of D:C of from about 0.1:1 to about 10:1; (3) an excess X to 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 44
Dependent Claim
627 words
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 sufficient quantity of at least one halide source so as to convert all of the organic groups attached to a magnesium atom in component (A) to a halide group; said halide source being 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; (C) 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 (D) at least one compound containing at least one aromatic hydroxyl group represented by the formulas ##STR41## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms, ##STR42## each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is independently ##STR43## or a hydroxyl substituted hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, hydroxyl or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; each X is independently a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; m has an average value of from about 0.01 to about 6; each n independently has a value of zero or 1; each x independently has a value of zero or 1; each y independently has a value of from zero to 4, and z has a value of from zero to 3; and when components (A) and/or (C) do not contain or contain an insufficient quantity of aluminum, then (E) 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) and (D) are employed in quantities which provide a molar ratio of D:C of from about 0.1:1 to about 10:1; (3) an excess X to 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 45
Dependent Claim
326 words
A catalyst composition of claim 41 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), (a) R has from about 1 to about 10 carbon atoms; and (b) X is chlorine; (4) in component (D) (a) when A is a divalent hydrocarbyl group, it has from about 1 to about 4 carbon atoms; (b) when A' is a divalent hydrocarbyl group it has from about 1 to about 4 carbon atoms; (c) when R is a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group, it has from 1 to about 10 carbon atoms; (d) when R' is a hydrocarbyl group, it has from about 1 to about 6 carbon atoms; (e) when X is hydrocarbyl or hydrocarbyloxy, it has from about 1 to about 12 carbon atoms; (f) m has a value of from about 1 to about 3; (g) y has a value from zero to 2; (h) z has a value from 1 to 2; and (i) x has a value of zero; (5) in component (E), (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) and (D) are employed in quantities which provide a molar ratio of D:C of from about 1:1 to about 4:1; (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 46
Dependent Claim
33 words
A catalyst composition of claim 42 wherein (a) in component (C), each R independently has from about 2 to about 4 carbon atoms; and (b) component (D) is represented by the formula ##STR44##
Claim 47
Dependent Claim
82 words
A catalyst composition of claim 43 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) components (C) and (D) are employed in quantities which provide a molar ratio of D:C of from about 1:1 to about 2:1; (c) an excess X to Al ratio of from about 0.01:1 to about 1.4:1; and (d) an Al:Ti atomic ratio of from about 1:1 to about 75:1.
Claim 48
Dependent Claim
21 words
A catalyst composition of claim 44 wherein in component (D) each X is independently chlorine, methyl, isopropyl, t-butyl, t-octyl or methoxy.
Claim 49
Dependent Claim
24 words
A catalyst composition of claim 45 wherein in component (D) y has a value of 1 and X is t-butyl, t-octyl, methoxy or chlorine.
Claim 50
Dependent Claim
12 words
A catalyst composition of claim 46 wherein component (D) is 4-t-butyl catechol.
Claim 51
Dependent Claim
27 words
A catalyst composition of claim 45 wherein in component (D) y has a value of 2 and each X is the same and is t-butyl or t-octyl.
Claim 52
Dependent Claim
50 words
A catalyst composition of claim 45 wherein in component (D) y has a value of 2 and (a) one X is isopropyl in position 3 and the other is methyl in position 6, or (b) each X is t-butyl, one being at position 3 and the other at position 5.
Claim 53
Dependent Claim
33 words
A catalyst composition of claim 42 wherein (A) in component (C), each R independently has from about 2 to about 4 carbon atoms; and (B) component (D) is represented by the formula ##STR45##
Claim 54
Dependent Claim
82 words
A catalyst composition of claim 49 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) components (C) and (D) are employed in quantities which provide a molar ratio of D:C of from about 1:1 to about 2:1; (c) an excess X to Al ratio of from about 0.01:1 to about 1.4:1; and (d) an Al:Ti atomic ratio of from about 1:1 to about 75:1.
Claim 55
Dependent Claim
30 words
A catalyst composition of claim 51 wherein in component (D) n has a value of 1 and A is ##STR46## and the hydroxyl groups are in the ortho (2) position.
Claim 56
Dependent Claim
30 words
A catalyst composition of claim 52 wherein in component (D) each X is independently a hydrocarbyl group or a halogen and each y has a value of 1 or 2.
Claim 57
Dependent Claim
27 words
A catalyst composition of claim 53 wherein in component (D) A is ##STR47## each X is independently methyl or t-butyl and y has a value of 2.
Claim 58
Dependent Claim
20 words
A catalyst composition of claim 54 wherein in component (D) each X is t-butyl located at positions 3 and 5.
Claim 59
Dependent Claim
29 words
A catalyst composition of claim 53 wherein in component (D) A is ##STR48## each X is independently chlorine, methyl or t-butyl and each y has a value of 2.
Claim 60
Dependent Claim
43 words
A catalyst composition of claim 56 wherein in component (D) (A) one X is t-butyl at position 3 and the other X is methyl at position 5; or (B) each X is t-butyl, one at position 3 and the other at position 5.
Claim 61
Dependent Claim
31 words
A catalyst composition of claim 53 wherein in component (D) A is --CH 2 -- and each X is chlorine in position 5 and each y has a value of 1.
Claim 62
Dependent Claim
16 words
A catalyst composition of claim 52 wherein A is --CH 2 -- and y is zero.
Claim 63
Dependent Claim
26 words
A catalyst composition of claim 51 wherein in component (D) n has a value of zero and the hydroxyl groups are in the ortho (2) positions.
Claim 64
Dependent Claim
55 words
A catalyst composition of claim 42 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms, (b) component (B) is represented by the formula ##STR49## and (c) 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 65
Dependent Claim
55 words
A catalyst composition of claim 42 wherein (a) in component (A), each R has from about 2 to about 4 carbon atoms, (b) component (B) is represented by the formula ##STR50## and (c) 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 66
Dependent Claim
38 words
A catalyst composition of claim 42 wherein (A) in component (C), each R independently has from about 2 to about 4 carbon atoms; and (B) component (D) is two different components each independently represented by the formulas ##STR51##
Claim 67
Dependent Claim
170 words
A catalyst composition of claim 63 wherein in component D (a) one component is represented by formula I wherein R is OH, y has a value of zero and the other component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y has a value of 1; (b) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position; or (c) one component is represented by formula I wherein R is OH, X is a hydrocarbyl group and y is 1 and the other is represented by formula II wherein A is ##STR52## each X is independently a hydrocarbyl group, each y is 2, and n is 1; and wherein 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 68
Dependent Claim
292 words
A catalyst composition of claim 63 wherein in component (D) (A) one component is represented by formula I wherein R is a hydroxyl group at position 2 and y has a value of zero and the other component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; (B) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is a t-butyl group at position 4, and y has a value of 1 and the other component is represented by the formula I wherein R is a hydroxyl group at position 2, each X is a t-butyl group, one at position 3 and the other at position 5 and y has a value of 2; (C) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein n is zero and the hydroxyl groups are in the ortho (2) position and y has a value of zero; and (D) one component is represented by formula I wherein R is a hydroxyl group at position 2, X is t-butyl at position 4 and y has a value of 1; and the other component is represented by formula II wherein A is ##STR53## n is 1, one X is methyl at position 5, the other X is t-butyl at position 3 and y has a value of 2; and wherein 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 69
Dependent Claim
98 words
A catalyst composition of claims 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64 or 65 wherein the components are added in the order selected from (A) A, B, (C and D, prereacted), E (if required); (B) A, B, E (if required), (C and D, prereacted); (C) (A and B, prereacted), (C and D, prereacted), E (if required); (D) (A and B, prereacted), E (if required), (C and D, prereacted); or (E) (A, B, and E (if required), prereacted), (C and D, prereacted).
Claim 70
Dependent Claim
45 words
A catalyst composition of claims 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64 or 65 wherein component (C) is tetraiisopropoxy titanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.
Claim 71
Dependent Claim
20 words
A catalyst composition of claim 66 wherein component (C) is tetraiisopropoxy titanium, tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof.
Claim 72
Dependent Claim
171 words
A bidentate ligand-containing titanium compound or complex represented by the formulas ##STR54## wherein each A is independently ##STR55## each X is independently a hydroxyl group, a nitro group a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; each Z is independently a halogen or an R 2 O--group, each R 2 is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value of 1; m' has a value of 1 or 2; n' has a value of zero when m' has a value of 2 and a value of 2 when m' has a value of 1; and y has a value from zero to 4; ##STR56## wherein each R 2 , X, Z, m', n', y and x are as defined above; or ##STR57## wherein each R 2 , X, Z, m', n', x and y are as defined above.
Claim 73
Dependent Claim
171 words
A bidentate ligand-containing titanium compound or complex represented by the formulas ##STR54## wherein each A is independently ##STR55## each X is independently a hydroxyl group, a nitro group a nitrile group, a hydrocarbyl group, a hydrocarbyloxy group, a hydroxyl substituted hydrocarbyl or a hydroxyl substituted hydrocarbyloxy group each such groups having from 1 to about 20 carbon atoms or a halogen; each Z is independently a halogen or an R 2 O--group, each R 2 is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value of 1; m' has a value of 1 or 2; n' has a value of zero when m' has a value of 2 and a value of 2 when m' has a value of 1; and y has a value from zero to 4; ##STR56## wherein each R 2 , X, Z, m', n', y and x are as defined above; or ##STR57## wherein each R 2 , X, Z, m', n', x and y are as defined above.
Claim 74
Dependent Claim
47 words
A bidentate ligand-containing titanium compound or complex of claim 69 wherein each R 2 has from 1 to about 10 carbon atoms; and when X is a hydrocarbyl, hydrocarbyloxy, hydroxyl substituted hydrocarbyl or hydroxyl substituted hydrocarbyloxy, each such group has from 1 to about 10 carbon atoms.
Claim 75
Dependent Claim
35 words
A bidentate ligand-containing compound or complex of claim 70 represented by Formula XI wherein A is --CH 2 --; n=1, X is 3,3'-di-t-butyl and 5,5'-dimethyl; bridging is in the o,o' positions, m'=2, n'=0 and y=2.
Claim 76
Dependent Claim
29 words
A bidentate ligand-containing compound or complex of claim 70 represented by Formula XIII wherein x=0, y=0, m'=2, n'=0 and the oxygen atoms are in the 1 and 2 positions.
Claim 77
Dependent Claim
17 words
A bidentate ligand-containing compound or complex of claim 72 which is in the form of a monohydrate.
Claim 78
Dependent Claim
36 words
A bidentate ligand-containing compound or complex of claim 70 represented by Formula XIV wherein y=0, x=0, the bridging is in the 1,1' positions, m'=2 and n'=0 and the oxygen atoms are in positions 2 and 2'.
Claim 79
Dependent Claim
17 words
A bidentate ligand-containing compound or complex of claim 74 which is in the form of a monohydrate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-06-05 | 1987-12-05 | 1988-06-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-06-05 | 1991-12-05 | 1992-06-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-06-05 | 1995-12-05 | 1996-06-05 | $7700.00 | Window Closed / Lapsed |