CATALYST SYSTEM FOR POLYMERIZATION OF AN OLEFIN

• US 20160311947A1
• Filed: 12/19/2014
• Published: 10/27/2016
• Est. Priority Date: 12/20/2013
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia), Saudi Basic Industries Corporation (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia), Saudi Basic Industries Corporation (Government of Saudi Arabia)
• Inventors: Batinas-Geurts, Aurora Alexandra, Zuideveld, Martin Alexander, Bukatov, Gennadii Dimitrievich, Sergeev, Sergei Andreevich, Zakharov, Vladimir Aleksandrovich
• Granted Patent: US 9,944,731 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 110/06 Propene
• 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 2500/15 Isotactic
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6557 and metals of C08F4/64 or compounds thereof
• CPC Class Codes: C08F 4/6565 and magnesium or compounds thereof
• CPC Class Codes: C08F 4/6567 and aluminium or compounds thereof

Abstract

A process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the procatalyst obtained or obtainable by the process; and a catalyst composition for olefin polymerization comprising the procatalyst. In particular a benzamide can be used as an activator in the preparation of a supported Ziegler-Natta type procatalyst useful for a process for the preparation of polyolefins. The Polyolefins and polypropylene homopolymers are also disclosed.

Claims

1. A process for the preparation of a procatalyst for preparing a catalyst composition for olefin polymerization, said process comprising:

providing a magnesium-based support, contacting said magnesium-based support with a Ziegler-Natta type catalytic species, an internal donor, and an activator, to yield a procatalyst, wherein the activator is a benzamide according to formula X;

2. The process according to claim 1, comprising:

A) providing said procatalyst obtained via a process comprising;

i) contacting a compound R⁴_zMgX⁴_2-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR¹)_xX¹_2-x, wherein;

R⁴ is the same as R¹ being a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups, and one or more combinations thereof;

wherein said hydrocarbyl group is substituted or unsubstituted, optionally comprises one or more heteroatoms and has from 1 to 20 carbon atoms;

X⁴ and X¹ are each independently selected from fluoride (F⁻

), chloride (Cl⁻

), bromide (Br⁻

) or iodide (I⁻

);

z is in a range of larger than 0 and smaller than 2, being 0<

z<

2;

ii) contacting the solid Mg(OR¹)_xX¹_2-x obtained in step i) with at least one activating compound of formula M¹(OR²)_v-w(OR³)w or M₂(OR²)_w, to obtain a second intermediate product;

wherein;

M¹ is a metal selected from Ti, Zr, Hf, Al or Si;

M² is a metal being Si;

v is the valency of M¹ or M²;

R² and R³ are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups, and one or more combinations thereof;

wherein said hydrocarbyl group is substituted or unsubstituted, optionally comprises one or more heteroatoms, and has from 1 to 20 carbon atoms; and

iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound, an activator according to Formula X and an internal electron donor according to Formula VII to obtain said procatalyst.

3. The process according to claim 1, wherein the hydrocarbyl groups R⁵³ and R⁵⁴ each have from 1 to 10 carbon atoms.

4. The process according to claim 1, wherein the internal donor is selected from the group consisting of 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, 1-methoxy-3-cyclohexoxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diiso-butyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-diethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-n-butyl-1,3 -dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenyllethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-di-npropyl-1,3-dimethoxypropane, 2-methyl-2-n-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(pchlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxy propane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl) 1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicylopentyl-1,3-dimethoxypropane, 2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, or any combination of the foregoing, for example wherein the internal donor is selected from the group of 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, 2,2-dicyclopentyl-1,3-dimethoxypropane and any combinations thereof.

5. The process according to claim 1, wherein the internal donor is 9,9-bis(methoxymethyl)fluorene.

6. The process according to claim 1, wherein in the activator according to Formula X, at least one of R⁷⁰ and R⁷¹ is an alkyl group, wherein the alkyl has from 1 to 6 carbon atoms.

7. The process according to claim 1, wherein the activator is N,N-dimethylbenzamide.

8. The process according to claim 1, wherein the benzamide is present in the procatalyst, in an amount of from 0.1 to 4 wt. % as measured using HPLC.

9. A procatalyst obtained or obtainable by the process according to claim 1.

12. A process for the preparation of polyolefins, polypropylene, comprising contacting a procatalyst of claim 9 with at least one olefin, and optionally an external donor and/or optionally a co-catalyst.

13. A polyolefin, preferably a polypropylene, obtained by the process according to claim 12.

14. The polyolefin according to claim 13, wherein the polyolefin has a molecular weight distribution (M_w/M_n) below 5.0, wherein M_w and M_n are determined according to ASTM D6474-12.

16. The process of claim 1, wherein the hydrocarbyl groups R⁵³ and R⁵⁴ each have from 1 to 6 carbon atoms;

and at least one of R⁷⁰ and R⁷¹ is an alkyl group, wherein the alkyl has from 1 to 6 carbon atoms.

17. The process according to claim 4, wherein the activator is N,N-dimethylbenzamide.

18. The process according to claim 5, wherein the activator is N,N-dimethylbenzamide.

19. A procatalyst obtained by the process according to claim 18.

10. A catalyst composition for olefin polymerization comprising a procatalyst comprising

a benzamide according to formula X,

11. The catalyst composition of claim wherein the catalyst is a supported Ziegler-Natta catalyst.

15. A polypropylene homopolymer prepared by a slurry polymerization using a solvent, having:

a molecular weight distribution (M_w/M_n) below 5.0, wherein M_w and M_n are determined according to ASTM D6474-12;

a melt flow rate of above 14, wherein the melt flow rate is as measured according to ISO 1133;

2005, at 230°

C. under a load of 2.16 kg;

a weight percentage of atactic polypropylene (APP) of less than 1.5, wherein the APP is measured according to the following procedure;

a quantity A of the product stream from said slurry polymerization process is collected;

this quantity A is filtered using a filter having pores between 10 and 16 μ

m in diameter, to obtain a filtrate Y and a polymer quantity of weight x, said polymer quantity of weight x being the quantity of material that remained on the filter;

said filtrate Y is dried over a steam bath and then under vacuum at 60°

C. to obtain a dry mass of APP of weight z;

the weight percentage of APP is calculated by;

20. The polypropylene homopolymer prepared by the slurry polymerization of claim 15 using heptane as a solvent and having:

a molecular weight distribution (M_w/M_n) from 2 to 4.5, wherein M_w and M_n are determined according to ASTM D6474-12;

a melt flow rate from 14 to 1000; and

a weight percentage of atactic polypropylene (APP) of less than 1.0.