US4409126A
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Ultra high efficiency catalyst for polymerizing olefins
Assignee: Dow Chemical Co
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Filing: 1981-10-22
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Granted: 1983-10-11
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Expires: 2001-10-22
Abstract
Abstract Compositions consisting of the reaction product or complex resulting from the mixing of a transition metal compound such as a tetraalkoxy titanium compound and an organo compound of magnesium, aluminum, boron or lithium such as a dialkyl magnesium compound are useful in the preparation of catalysts for polymerizing α-olefins at ultra-high efficiencies at high polymerization temperatures.
Inventors
- 👤 Randall S. Shipley
- 👤 Donald F. Birkelbach
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 19:10
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 12
Claim 1
Independent Claim
222 words
A hydrocarbon soluble reaction product or complex formed from the admixture at a temperature and time sufficient to provide a color change of (a) at least one transition metal compound represented by the empirical 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 (b) at least one organometal compound represented by the empirical formula MR x X y ; wherein M is a metal selected from magnesium, aluminum, boron, lithium or mixtures thereof; R is an alkyl group having from 1 to about 20 carbon atoms; X is a halogen, x has a value of from 1 to the valence of metal M; the value of x+y is equal to the valence of M; the quantities of (a) and (b) employed being that which provides a ratio of Q:Tm of from about 0.1:1 to about 2:1; and wherein Q has a value corresponding to the value of x divided by the valence of M times the number of moles of MR x X y .
Claim 2
Dependent Claim
222 words
A hydrocarbon soluble reaction product or complex formed from the admixture at a temperature and time sufficient to provide a color change of (a) at least one transition metal compound represented by the empirical 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 (b) at least one organometal compound represented by the empirical formula MR x X y ; wherein M is a metal selected from magnesium, aluminum, boron, lithium or mixtures thereof; R is an alkyl group having from 1 to about 20 carbon atoms; X is a halogen, x has a value of from 1 to the valence of metal M; the value of x+y is equal to the valence of M; the quantities of (a) and (b) employed being that which provides a ratio of Q:Tm of from about 0.1:1 to about 2:1; and wherein Q has a value corresponding to the value of x divided by the valence of M times the number of moles of MR x X y .
Claim 3
Dependent Claim
64 words
A reaction product or complex of claim 1 wherein in component (a) Tm is titanium, each R is independently a hydrocarbyl group having from 2 to about 10 carbon atoms and X is chlorine or bromine; and in component (b) R is an alkyl group having from 1 to about 10 carbon atoms; and the Q:Ti ratio is from about 0.2:1 to about 1.5:1.
Claim 4
Dependent Claim
30 words
A reaction product or complex of claim 2 wherein in component (a) R is a saturated aliphatic hydrocarbyl group and the Q:Ti ratio is from about 0.5:1 to about 1:1.
Claim 5
Dependent Claim
46 words
A reaction product or complex of claims 1, 2, or 3 wherein component (a) is titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide or titanium tetra-(2-ethylhexoxide) or mixture thereof and component (b) is n-butyl, sec-butyl magnesium, triethyl aluminum, sec-butyl lithium, ethyl aluminum dichloride or mixture thereof.
Claim 6
Dependent Claim
500 words
A catalytic reaction product of (A) a hydrocarbon soluble reaction product or complex formed from the admixture at a temperature and time sufficient to provide a color change 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 compound represented by the empirical formula MR x X y ; wherein M is a metal selected from magnesium, aluminum, boron, lithium or mixtures thereof; R is an alkyl group having from 1 to about 20 carbon atoms; X is a halogen, x has a value of from 1 to the valence of metal M; the value of x+y is equal to the valence of M; the quantities of (a) and (b) employed being that which provides a ratio of Q:Tm of from about 0.1:1 to about 2:1 and wherein Q has a value corresponding to the value of x divided by the valence of M times the number of moles of MR x X y ; (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR' 2 .xM'R" 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 enpirical formula M"R y-a X a wherein M" is a metal of Group IIV, 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 empirical 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 200:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 5:1.
Claim 7
Dependent Claim
500 words
A catalytic reaction product of (A) a hydrocarbon soluble reaction product or complex formed from the admixture at a temperature and time sufficient to provide a color change 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 compound represented by the empirical formula MR x X y ; wherein M is a metal selected from magnesium, aluminum, boron, lithium or mixtures thereof; R is an alkyl group having from 1 to about 20 carbon atoms; X is a halogen, x has a value of from 1 to the valence of metal M; the value of x+y is equal to the valence of M; the quantities of (a) and (b) employed being that which provides a ratio of Q:Tm of from about 0.1:1 to about 2:1 and wherein Q has a value corresponding to the value of x divided by the valence of M times the number of moles of MR x X y ; (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR' 2 .xM'R" 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 enpirical formula M"R y-a X a wherein M" is a metal of Group IIV, 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 empirical 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 200:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 5:1.
Claim 8
Dependent Claim
197 words
A catalytic reaction product of claim 5 wherein (i) 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; (ii) in component (A-2), R is an alkyl group having from 1 to about 10 carbon atoms; (iii) 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; (iv) in component (B-2-a), R' is hydrogen or a tertiary butyl group and X is chlorine; (v) in component (B-2-b), M" is a metal from Groups IIIA or IVA, y-a is zero or 1 and X is chlorine; (vi) 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 (vii) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 2:1 to about 100:1; Q:Ti from about 0.2:1 to about 1.5:1; Al:Ti of from about 0.5:1 to about 100:1 and excess X:Al of from about 0.002:1 to about 2:1.
Claim 9
Dependent Claim
75 words
A catalytic reaction product of claim 6 wherein (i) in component (A-1), R is a saturated aliphatic hydrocarbyl group; (ii) in component (B-1), x has a value of from about 0.15 to about 2.5; and (iii) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 5:1 to about 75:1; Q:Ti of from about 0.5:1 to about 1:1 and excess X:Al of from about 0.01:1 to about 1.4:1.
Claim 10
Dependent Claim
77 words
A catalytic reaction product of claim 7 wherein (i) component (A-1) is titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, or titanium tetra-(2-ethylhexoxide); (ii) component (A-2) is is n-butyl, sec-butyl magnesium, triethyl aluminum, sec-butyl lithium, ethyl aluminum dichloride or mixture thereof; (iii) component (B-1) is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (iv) component (B-2) is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride.
Claim 11
Dependent Claim
26 words
A catalyst reaction product of claims 5, 6, 7 or 8 wherein the components are added in the order (B-1), (B-2), (C) if employed and (A).
Claim 12
Dependent Claim
38 words
A catalytic reaction product of claims 5, 6, 7 or 8 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.
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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) | 1986-10-10 | 1987-04-11 | 1987-10-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-10-10 | 1991-04-11 | 1991-10-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-10-10 | 1995-04-11 | 1995-10-11 | $7700.00 | Window Closed / Lapsed |