CATALYST SYSTEM FOR POLYMERIZATION OF AN OLEFIN

• US 20160311950A1
• 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: Steenbakkers-Menting, Henrica Norberta Alberta Maria, Batinas-Geurts, Aurora Alexandra, Zuideveld, Martin Alexander, Gerlofsma, Raymond, Degenhart, Peter
• Granted Patent: US 10,000,591 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 110/06 Propene
• 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 210/02 Ethene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/6465 containing silicium
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6565 and magnesium or compounds thereof
• CPC Class Codes: C08L 2207/02 Heterophasic composition
• CPC Class Codes: C08L 23/12 Polypropene
• CPC Class Codes: C08L 23/16 Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Abstract

A process for the preparation of a catalyst system for olefin polymerization, including: A) providing said procatalyst obtainable 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, ii) optionally contacting the solid product obtained in step i) with at least one activating compound selected from an activating electron donor or metal alkoxide compound; iii) contacting the first or second intermediate reaction product, with a halogen-containing Ti-compound and optionally an internal electron donor to obtain the procatalyst; and B) contacting the procatalyst with a co-catalyst and at least diethylaminotriethoxysilane as the external donor. Further disclosed is a catalyst system obtained by the process; a process for preparing a polyolefin by contacting at least one olefin with the catalyst system; a polyolefin obtained thereby; a composition comprising a propylene-ethylene copolymer; a shaped article thereof; and use of polyolefin.

Claims

1-12. -12. (canceled)

13. A process for the preparation of a catalyst system suitable for olefin polymerization, wherein the process comprises:

A) providing said procatalyst obtainable 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 between 1 and 20 carbon atoms;

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

), chloride (Cl⁻

), bromide (Br⁻

) or iodide (I⁻

); and

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

z<

2;

ii) optionally contacting the solid Mg(OR¹)_xX_2-x obtained in step i) with at least one activating compound selected from activating electron donors and metal alkoxide compounds of formula M¹(OR²)_v-w(OR³)_w or M²(OR²)_v-w(R³)_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, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof;

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

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

B) contacting said procatalyst with a co-catalyst and the at least one external electron donor that is diethylaminotriethoxysilane.

14. The process according to claim 13, wherein the process is essentially phthalate free.

15. The process according to claim 13, wherein the optional internal electron donor is present and is an aminobenzoate according to formula XI

16. The process according to claim 15, wherein

R₈₃, R₈₄, R₈₅ and R₈₆ are independently selected from C₁-C₁₀ straight and branched alkyl and phenyl;

and

R₈₈ is a substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisol group.

17. The process according to claim 16, wherein

R_83, R₈₄, R₈₅ and R₈₆ are are independently selected from methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and phenyl groups;

and

R₈₈ is phenyl.

18. The process according to claim 13, wherein the optional internal electron donor is present, and is selected from 4-[benzoyl(methyl)amino]pentan-2-yl benzoate;

2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate;

4-[benzoyl (ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate), 3-[benzoyl(cyclohexyl)amino]-1-phenylbutyl benzoate, 3-[benzoyl(propan-2-yl)amino]-1-phenylbutyl, 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl, 3-(methylamino)-1,3-diphenylpropan-1-ol dibenzoate, 3-(methyl)amino-propan-1-ol dibenzoate;

3-(methyl)amino-2,2-dimethylpropan-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate).

19. The process according to claim 13, wherein the one or more internal electron donor is present and is activated by an activator.

20. The process according to claim 19, wherein the activator is a benzamide according to formula X

21. The process according to claim 19, wherein R⁷⁰ and R⁷¹ are each independently selected from hydrogen and an alkyl having between 1 and 6 carbon atoms.

22. The process according to claim 21 wherein the activator is N,N-dimethylbenzamide.

23. The process according to claim 20, wherein the benzamide according to formula X is present in the procatalyst in an amount from 0.1 to 4 wt. % as determined using HPLC.

24. A catalyst system obtained by the process of claim 13.

25. A process for preparing a polyolefin, comprising contacting at least one olefin with the catalyst system according to claim 24.

26. The process according to claim 25, wherein the olefin is propylene or a combination of propylene and ethylene.

27. A polyolefin obtained by the process for preparing a polyolefin according to claim 25.

28. The polyolefin according to claim 26, wherein the polyolefin is a polypropylene or a propylene-ethylene copolymer.

29. The process of claim 13, wherein

the optional internal electron donor is present and is an aminobenzoate according to formula XI

30. The process of claim 28, wherein

the optional internal electron donor is selected from 4-[benzoyl(methyl)amino]pentan-2-yl benzoate;

2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate;

4-[benzoyl (ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate), 3-[benzoyl(cyclohexyl)amino]-1-phenylbutyl benzoate, 3-[benzoyl(propan-2-yl)amino]-1-phenylbutyl, 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl, 3-(methylamino)-1,3-diphenylpropan-1-ol dibenzoate, 3-(methyl)amino-propan-1-ol dibenzoate;

3-(methyl)amino-2,2-dimethylpropan-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate); and

the activator is N,N-dimethylbenzamide, and is present in in the procatalyst an amount from 0.1 to 1.5 wt. % as determined using HPLC.

31. A catalyst system obtained by the process of claim 28.

32. A process for preparing a polypropylene or a propylene-ethylene copolymer, comprising contacting propylene or a combination of propylene and ethylene with the catalyst system according to claim 30.

33. A polyolefin obtained by the process for preparing a a polypropylene or a propylene-ethylene copolymer according to claim 31.

34. A composition comprising a propylene-ethylene copolymer having a xylene soluble content of less than 7.5 wt. %, wherein the xylene soluble content is measured according to ASTM D 5492-10.

35. The composition of claim 34, having a haze increase over 21 days at 50°

C. of less than 12, wherein the haze increase over 21 days at 50°

C. is the difference between the haze value of the sample before heating and the haze value after heating the sample at 50°

C. for 21 days measured according to ASTM D 1003-00, procedure A.

36. The composition of claim 34, wherein the amount of ethylene in the propylene-ethylene copolymer is in the range from 1 to 8 wt. % based on the weight of the propylene-ethylene copolymer.