Ziegler-Natta catalyst for high temperature polymerization

• US 10,590,214 B2
• Filed: 06/06/2018
• Issued: 03/17/2020
• Est. Priority Date: 08/12/2014
• Status: Active Grant

• Current Assignee: NOVA Chemicals (International) S.A. (NOVA Chemicals Holding GmbH)
• Original Assignee: NOVA Chemicals (International) S.A. (NOVA Chemicals Holding GmbH)
• Inventors: Wang, Qinyan, Ouskine, Helena, Aiffa, Mohamed, Baltimore, Amy, Severin, Holly, Dewit, Perry, Clemens, Steven, Van Asseldonk, Lawrence Martin Josef, Jaber, Isam
• Primary Examiner(s): Branch, Catherine S
• Application Number:
  US16/001,268
• Publication Number:
  US 20180282453A1
• Time in Patent Office: 650 Days
• Field of Search: None
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/26 Use as polymer for film forming
• CPC Class Codes: C08F 4/6543 halides of magnesium
• CPC Class Codes: C08F 4/6546 organo-magnesium compounds
• CPC Class Codes: C08F 4/6555 and magnesium or compounds thereof
• CPC Class Codes: C08J 2323/08 Copolymers of ethene C08J2323/16 takes precedence
• CPC Class Codes: C08J 5/00 Manufacture of articles or shaped materials containing macromolecular substances manufacture of semi-permeable membranes B01D67/00 - B01D71/00

Abstract

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

Claims

1. A process to prepare an olefin polymerization procatalyst comprising a Ti³⁺ complex, said process comprising:

a) forming a delta form MgCl₂ species by combining

i) a Mg compound chosen from butylethyl magnesium (BEM), dibutyl magnesium, and butyloctyl magnesium (BOM), in cyclohexane,

and

ii) reactive organic chloride or HCl;

wherein the mole ratio of added Cl and Mg is from 2.15 to 2.5;

b) adding to said delta form MgCl₂ species prepared in step a), an aluminum alkyl halide of the formula R¹_xAlX_3-x first, a tetravalent titanium compound second, followed by an alkyl aluminum alkoxide of the formula R⁴_yAlOR⁵_3-y, wherein the Al/Ti molar ratio when measuring Al supplied from R¹_xAlX_3-x only is from about 0.7 to about 2 and the Al/Ti molar ratio when measuring Al supplied from R⁴_yALOR⁵_3-y is from about 1 to about 1.7;

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 R¹ is independently chosen from C_1-8 alkyl radicals;

the tetravalent titanium compound is chosen from TiR²X₃, Ti(OR³)X₃, TiX₄, and mixtures thereof;

each X is independently chosen from the halogen radicals; and

each R² is independently chosen from C_1-8 alkyl radicals and benzyl;

each R³, R⁴ and R⁵ are independently chosen from C_1-8 alkyl radicals

wherein the process used to prepare the delta form MgCl₂ species allows for the next steps of the procatalyst formation to follow without the need for intervening washing steps.

2. The process of claim 1, wherein the reactive organic chloride is tertiary-butylchloride (tBuCl).

3. The process of claim 1, wherein step a) is performed at a temperature between about 20°

C. and about 160°

C.

4. The process of claim 1, wherein step b) is performed at a temperature between about 40°

C. and 90°

C.

5. The process of claim 1, wherein the Mg compound is butylethyl magnesium (BEM).

6. The process of claim 1, wherein the Cl/Mg mole ratio is about 2.3.

7. The process of claim 1, wherein R¹_xAlX_3-x is chosen from isobutylaluminum dichloride (IBADC) and ethylaluminumdichloride.

8. The process of claim 1, wherein the tetravalent titanium compound is TiCl₄.

9. The process of claim 1, wherein R⁴_yAlOR⁵_3-y is diethylaluminumethoxide.

10. 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 chosen from C_5-12 alkanes, or mixtures thereof, and a procatalyst for polymerization on a delta form MgCl₂ support comprising a Ti³⁺ complex of the formula TiCl₃*[[R⁴]_a[R⁵O]_bAlX_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 R⁴ and R⁵ is independently chosen from C_1-8 alkyl radicals;

each X is independently chosen from the halogen radicals;

wherein at least 60% of the total Ti present is in the Ti³⁺oxidation state;

and further wherein the next steps of the procatalyst formation follow without the need for intervening washing steps;

ii) adding ethylene, hydrogen and optionally one or more comonomers chosen 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.

11. The polymerization process of claim 10, wherein the activator is an aluminum alkyl activator chosen from diethylaluminumethoxide and trialkyl aluminum compounds, and MAO.

12. The polymerization process of claim 10, wherein the solvent is cyclohexane.

13. The polymerization process of claim 10, wherein the polymerization temperature is at least about 240°

C.

14. The polymerization process of claim 10, 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 Ti³⁺species.

15. The polymerization process of claim 10, 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 Ti³⁺species.

16. The polymerization process of claim 10, wherein the reactor hold-up time is from about 30 seconds to about 5 minutes.