US4269733A — Ultra high efficiency catalyst for polymerizing o…

Claim 1

Independent Claim 406 words

The catalytic reaction product of (A) the reaction product or complex formed from the admixture of (1) at least one transition metal compound represented by the formulae Tm(OR) y X x-y or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; each X is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (2) at least one zinc compound represented by the formulae R 2 Zn and RZnX wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms and X is a halogen; and (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the formula MgR" 2 .xMR" y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (a) an active non-metallic halide, said non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group 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 (b) a metallic halide corresponding to the formula MR y-a X a wherein M is a metal of Group IIB, and IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound represented by the formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from about 1:1 to about 2000:1; Zn:Tm at least about 0.03:1; Al:Tm of from about 0.1:1 to about 2000:1 and an excess X:Al of from about 0.0005:1 to about 10:1.

Claim 2

Dependent Claim 406 words

The catalytic reaction product of (A) the reaction product or complex formed from the admixture of (1) at least one transition metal compound represented by the formulae Tm(OR) y X x-y or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; each X is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (2) at least one zinc compound represented by the formulae R 2 Zn and RZnX wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms and X is a halogen; and (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the formula MgR" 2 .xMR" y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (a) an active non-metallic halide, said non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group 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 (b) a metallic halide corresponding to the formula MR y-a X a wherein M is a metal of Group IIB, and IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound represented by the formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from about 1:1 to about 2000:1; Zn:Tm at least about 0.03:1; Al:Tm of from about 0.1:1 to about 2000:1 and an excess X:Al of from about 0.0005:1 to about 10:1.

Claim 3

Dependent Claim 208 words

The catalytic reaction product of claim 1 wherein (a) in component (A-1), Tm is titanium, each R is independently a hydrocarbyl group having from 1 to about 10 carbon atoms and X is chlorine or bromine; (b) in component (A-2), the zinc compound is represented by the formula ZnR 2 wherein R is a hydrocarbyl group having from 1 to about 10 carbon atoms; (c) in component (B-1), M is aluminum and R" is a hydrocarbyl group having from 1 to about 10 carbon atoms and x has a value of from about 0.001 to about 5; (d) in component (B-2-a), R' is hydrogen or a tertiary butyl group and X is chlorine; (e) in component (B-2-b), M is a metal from Groups IIIA or IVA, y-a is zero or 1 and X is chlorine; (f) in component (C), the aluminum compound is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (g) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 2:1 to about 200:1; Zn:Ti from about 0.12:1 to about 5:1; Al:Ti of from about 0.5:1 to about 200:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 4

Dependent Claim 72 words

The catalytic reaction product of claim 2 wherein (a) in component (A-1), R is a saturated aliphatic hydrocarbyl group; (b) in component (B-1), x has a value of from about 0.15 to about 2.5; and (c) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 5:1 to about 75:1; Zn:Ti of from about 2:1 and excess X:Al of from about 0.01:1 to about 1.4:1.

Claim 5

Dependent Claim 70 words

The catalytic reaction product of claim 3, wherein (a) component (A-1) is titanium tetraethoxide, titaniumm tetra-n-propoxide, titanium tetra-isopropoxide, titanium tetra-n-butoxide, or titanium tetra-(2-ethyl-hexoxide); (b) component (A-2) is dimethyl zinc, diethyl zinc or diphenyl zinc; (c) component (B-1) is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (d) component (B-2) is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride.

Claim 6

Dependent Claim 26 words

The catalytic reaction product of claims 1, 2, 3 or 4 wherein the components are added in the order (B-1), (B-2), (C) if employed and (A).

Claim 7

Dependent Claim 38 words

The catalytic reaction product of claims 1, 2, 3 or 4 wherein the components are added in the order (B-1), (B-2), (A) and (C) if employed, and provided that the halide source, (B-2), is not a tin compound.

Claim 8

Dependent Claim 83 words

In a catalyst composition comprising a magnesium halide, a transition metal compound and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 2000:1; Zn:Tm at least about 0.03:1 Al:Tm of from about 0.1:1 to about 2000:1 and an excess X:Al of from about 0.0005:1 to about 10:1; the improvement which comprises forming a reaction product or complex of the transition metal compound and the zinc compound prior to preparation of the catalyst therefrom.

Claim 9

Dependent Claim 83 words

In a catalyst composition comprising a magnesium halide, a transition metal compound and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 2000:1; Zn:Tm at least about 0.03:1 Al:Tm of from about 0.1:1 to about 2000:1 and an excess X:Al of from about 0.0005:1 to about 10:1; the improvement which comprises forming a reaction product or complex of the transition metal compound and the zinc compound prior to preparation of the catalyst therefrom.

Claim 10

Dependent Claim 48 words

The catalyst composition of claim 7 wherein the atomic ratios of the elements are Mg:Tm of from about 2:1 to about 200:1; Zn:Tm of from about 0.12:1 to about 5:1; Al:Tm of from about 0.5:1 to about 200:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 11

Dependent Claim 48 words

The catalyst composition of claim 7 wherein the atomic ratios of the elements are Mg:Tm of from about 5:1 to about 75:1; Zn:Tm of from about 0.25:1 to about 2:1; Al:Tm of from about 1:1 to about 75:1 and excess X:Al of from about 0.01:1 to about 1.4:1.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1984-05-25	1984-11-24	1985-05-26	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1988-05-25	1988-11-24	1989-05-26	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1992-05-25	1992-11-24	1993-05-26	$7700.00	Window Closed / Lapsed

Ultra high efficiency catalyst for polymerizing olefins

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