Synthesis of magnesium dichloride support for the AST off-line ZN catalyst with a plug flow reactor (PFR)

Patent metadata

Field	Value
Publication number	US-10647588-B2
Application number	US-201615776810-A
Country	US
Kind code	B2
Filing date	Dec 5, 2016
Priority date	Dec 9, 2015
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

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

First claim

The invention claimed is:

1. A method of making a disordered form of MgCl 2 comprising
combining MgR 2 and reactive organic chloride or HCl and a solvent chosen from C 5-12 alkanes in a plug flow reactor (PFR), wherein each R is independently chosen from C 2-8 alkyl radicals; and
operating the PFR at conditions sufficient to create the disordered form of MgCl 2 .

2. The method of claim 1 wherein the disordered form of MgCl 2 is characterized by having a peak in the GADDS spectrum at 15 2 theta with a FWHM that is at least 10% greater than the FWHM of the peak at 15 2 theta for MgCl 2 prepared in a stirred reactor (STR).

3. The method of claim 1 wherein the disordered form of MgCl 2 is characterized by having a peak in the GADDS spectrum at 15 2 theta with a full width of half maximum (FWHM) that is at least 20% greater than the FWHM of the peak at 15 2 theta for MgCl 2 prepared in a STR.

4. The method of claim 1 wherein the mole ratio of added Cl from the organic chloride or HCl to Mg from the MgR 2 is from about 2.0 to about 3.0.

5. The method of claim 1 wherein the reactive organic chloride is tertiary-butylchloride ( t BuCl).

6. The method of claim 1 wherein MgR 2 is chosen from butylethyl magnesium (BEM), dibutyl magnesium, and butyloctyl magnesium (BOM).

7. The method of claim 1 wherein the solvent is isohexane, cyclohexane, or decane.

8. The method of claim 1 wherein the mole ratio of added Cl from the organic chloride or HCl to Mg from the MgR 2 is from about 2.15 to about 2.5.

9. The method of claim 1 wherein a STR is used in combination with the PFR.

10. The method of claim 9 wherein the PFR feeds into the STR.

11. A method for making a Ziegler Natta (pro) catalyst comprising
combining MgR 2 and reactive organic chloride or HCl and a solvent chosen from C 5-12 alkanes in a PFR reactor, wherein each R is independently chosen from C 2-8 alkyl radicals;
operating the PFR reactor to create a disordered form of MgCl 2 ;
contacting the disordered form of MgCl 2 with i BuAlCl 2 , TiCl 4 and Et 2 AlOEt to form the (pro)catalyst.

12. The method of claim 11 wherein the plug flow reactor is combined with at least one other reactor.

13. The method of claim 11 wherein the plug flow reactor is combined with at least one STR.

14. The method of claim 13 wherein the i BuAlCl 2 , TiCl 4 and Et 2 AlOEt contact the disordered form of MgCl 2 in the STR reactor.

15. The method of claim 11 wherein the solvent is isohexane, cyclohexane or decane.

16. A method for making polyethylene polymers and copolymers comprising
combining MgR 2 and reactive organic chloride or HCl and a solvent selected from C 5-12 alkanes in a PFR reactor, wherein each R is independently selected from C 2-8 alkyl radicals;
operating a PFR reactor to create a disordered form of MgCl 2 ;
contacting the disordered form of MgCl 2 with i BuAlCl 2 , TiCl 4 and Et 2 AlOEt to form the (pro)catalyst;
contacting the procatalyst of the previous step with ethylene, and optionally an alpha-olefin and operating the reactor to create the desired polyethylene polymers and copolymers.

17. The method of claim 16 wherein the plug flow reactor is combined with at least one STR.

18. The method of claim 17 wherein the i BuAlCl 2 , TiCl 4 and Et 2 AlOEt are added to the STR reactor and the solvent is isohexane, cyclohexane or decane.

Assignees

• Nova Chem Int Sa

Inventors

• Zoricak Peter
• Wang Qinyan
• Severin Holly Ann
• Aiffa Mohamed Elamine
• Dickinson Kevin

Classifications

• B01J2219/00481

  by the use of moving stirrers within the reaction vessels · CPC title

• B01J19/18

  Stationary reactors having moving elements inside (B01J19/08, B01J19/26 take precedence) · CPC title

• C01F5/30 Primary

  Chlorides · CPC title

• B01J21/063

  Titanium; Oxides or hydroxides thereof · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title