Ziegler-Natta catalyst for high temperature polymerization

Patent metadata

Field	Value
Publication number	US-9481748-B2
Application number	US-201414457565-A
Country	US
Kind code	B2
Filing date	Aug 12, 2014
Priority date	Aug 12, 2014
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

The various embodiments of the invention provide, a magnesium titanium polymerization procatalyst, methods for making and using the same.

First claim

What is claimed is:

1. A procatalyst for polymerization of ethylene and α-olefins on a delta form MgCl 2 support comprising a Ti 3+ complex of the formula TiCl 3 *[[R 4 ] a [R 5 O] b AlX 3-c ] d
wherein
a is 0 to 1;
b is 0 to 1;
c=a+b;
d is from about 0.33 to about 1.0;
each R 4 and R 5 is independently selected from C 1-8 alkyl radicals;
each X is independently selected from the halogen radicals;
the Mg/Ti molar ratio is from about 5 to about 10;
and further wherein at least 60% of the total Ti present is in the Ti 3+ oxidation state.

2. The procatalyst of claim 1 , wherein X is Cl.

3. The procatalyst of claim 1 , wherein a is 0 and b is 0.

4. The procatalyst of claim 1 , wherein a is 0 and b is 1.

5. The procatalyst of claim 1 , wherein a is 1 and b is 0.

6. The procatalyst of claim 1 , wherein each R 5 is ethyl.

7. The procatalyst of claim 1 , wherein the Mg/Ti ratio is from about 5 to about 8.

8. The procatalyst of claim 1 , wherein the Ti 3+ complex is TiCl 3 *[OEtAlCl 2 ] d , and the Mg/Ti molar ratio is from about 5 to about 8.

9. The procatalyst of claim 1 , wherein the Ti 3+ complex is TiCl 3 *[ClAlCl 2 ] d , and the Mg/Ti molar ratio is from about 5 to about 8.

10. The procatalyst of claim 1 , wherein the EPR spectrum and its simulation of the procatalyst has a characteristic g value of 1.950.

11. The procatalyst of claim 1 , wherein electron paramagnetic resonance (EPR) indicates the presence of a species C, wherein the species C is associated with a tetrahedral Ti 3+ species and wherein species C is about 0.2% or more of the Ti 3+ species detected in the EPR spectra.

12. The procatalyst of claim 1 , wherein electron paramagnetic resonance (EPR) indicates the presence of a species C, wherein the species C is associated with a tetrahedral Ti 3+ species and wherein species C is about 0.3% to about 1% of the Ti 3+ species detected in the EPR spectra.

13. A process to prepare an olefin polymerization procatalyst comprising a Ti 3+ complex, said process comprising:
a) forming a delta form MgCl 2 species by combining
i) R 2 Mg in a solvent selected from C 5-12 alkanes, and
ii) reactive organic chloride or HCl;

wherein each R is independently selected from C 2-8 alkyl radicals,
and wherein the mole ratio of added Cl and Mg is from about 2.0 to about 3.0;
b) adding to said delta form MgCl 2 species prepared in step a) either
i) R 1 x AlX 3-x and a tetravalent titanium compound in any order or at the same time,

wherein the AIM molar ratio is from about 3 to about 10;
or
ii) an aluminum alkyl halide of the formula R 1 x AlX 3-x first, a tetravalent titanium compound second, followed by an alkyl aluminum alkoxide of the formula R 4 y AlOR 5 3-y , wherein the Al/Ti molar ratio when measuring Al supplied from R 1 x AlX 3-x only is from about 0.7 to about 2 and the Al/Ti molar ratio when measuring Al supplied from R 4 y AlOR 5 3-y is from about 1 to about 2;

and further wherein
the Mg/Ti molar ratio is from about 5 to about 10;
x is 1 or 2;
y is 1 or 2;
each R 1 is independently selected from C 1-8 alkyl radicals;
the tetravalent titanium compound is selected from TiR 2 X 3 , Ti(OR 3 )X 3 , TiX 4 , and mixtures thereof;
each X is independently selected from the halogen radicals;
each R 2 is independently selected from C 1-8 alkyl radicals and benzyl; and
each R 3 , R 4 and R 5 are independently selected from C 1-8 alkyl radicals.

14. The process of claim 13 , wherein the reactive organic chloride is tertiary-butylchloride (tBuCl).

15. The process of claim 13 , wherein step a) is performed at a temperature between about 20° C. and about 160° C.

16. The process of claim 13 , wherein step b) or c) is performed at a temperature between about 40° C. and 90° C.

17. The process of claim 13 , wherein R 2 Mg is selected from butylethyl magnesium (BEM), dibutyl magnesium, and butyloctyl magnesium (BOM).

18. The process of claim 13 , wherein the solvent is decane.

19. The process of claim 13 , wherein the Cl/Mg mole ratio is from about 2.15 to about 2.5.

20. The process of claim 13 , wherein R 1 x AlX 3-x is selected from isobutylaluminum dichloride (IBADC), ethylaluminumdichloride.

21. The process of claim 13 , wherein the tetravalent titanium compound is TiCl 4 .

22. The process of claim 13 , wherein R 4 y AlOR 5 3-y is diethylaluminumethoxide.

23. A procatalyst product comprising a Ti 3+ complex prepared by the process of claim 13 .

24. A solution olefin polymerization process comprising
i) adding to one or more continuous stirred tank reactor (CSTR), optionally followed by a tubular reactor, either in series or parallel, a solvent selected from C 5-12 alkanes, or mixtures thereof, and a procatalyst for polymerization on a delta form MgCl 2 support comprising a Ti 3+ complex of the formula TiCl 3 *[[R 4 ] a [R 5 O] b AlX 3-c ] d
wherein
a is 0 to 1;
b is 0 to 1;
c=a+b;
d is from 0.33 to 1.0;
each R 4 and R 5 is independently selected from C 1-8 alkyl radicals;
each X is independently selected from the halogen radicals;
wherein at least 60% of the total Ti present is in the Ti 3+ oxidation state;
ii) adding ethylene, hydrogen and optionally one or more comonomers selected from C 3-8 comonomers to the reactor; and
iii) adding an aluminum alkyl activator to the reactor in a molar ratio of about 1 to about 10 relative to the amount of procatalyst.

25. The polymerization process of claim 24 , wherein the activator is an aluminum alkyl activator selected from diethylaluminumethoxide and trialkyl aluminum compounds, and MAO.

26. The polymerization process of claim 24 , wherein the solvent is isohexane or decane.

27. The polymerization process of claim 24 , wherein the polymerization temperature is at least about 240° C.

28. The polymerization process of claim 24 , wherein the polymerization results in a polymer having the same density but where the process uses at least about 10% less comonomer feed compared to a polymerization process using a procatalyst for polymerization that contains substantially no tetrahedral Ti 3+ species.

29. The polymerization process of claim 24 , wherein the polymerization results in a polymer with the same density but with a higher Mw at any polymerization temperature than the Mw obtained for a polymer prepared using a procatalyst for polymerization that contains substantially no tetrahedral Ti 3+ species.

30. The polymerization process of claim 24 , wherein the reactor hold-up time is from about 30 seconds to about 5 minutes.

Assignees

• Nova Chemicals International Sa

Inventors

• Wang Qinyan
• Ouskine Helena
• Aiffa Mohamed
• Baltimore Amy
• Severin Holly
• Dewit Perry
• Clemens Steven
• Van Asseldonk Lawrence Martin Josef
• Jaber Isam

Classifications

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C08J5/00

  Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00) · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title