Procatalyst for polymerization of olefins comprising an aminobenzoate internal donor and a 1,3-diether internal donor in a specific ratio

Patent metadata

Field	Value
Publication number	US-10730971-B2
Application number	US-201615736878-A
Country	US
Kind code	B2
Filing date	Jun 17, 2016
Priority date	Jun 19, 2015
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

A process for preparing a procatalyst for polymerization of olefins, comprising contacting a magnesium-containing support with a halogen-containing titanium compound, a first internal electron donor represented by Formula A, a second internal electron donor represented by Formula B, and an activator; wherein the molar ratio of the first internal donor to the second internal donor is between 0.01 and 0.7;

wherein in Formula A each R 80 group is independently a substituted or unsubstituted aromatic group; and R 81 , R 82 , R 83 , R 84 , R 85 , R 86 and R 87 are each independently selected from a hydrogen or a hydrocarbyl group; wherein in Formula B R 51 and R 52 are each independently selected from a hydrogen or a hydrocarbyl group; and R 53 and R 54 are each independently selected from hydrogen, a halide or a hydrocarbyl group.

First claim

The invention claimed is:

1. A process for preparing a procatalyst for polymerization of olefins, said process comprising contacting a magnesium-containing support with a halogen-containing titanium compound, a first internal electron donor represented by Formula A, a second internal electron donor represented by Formula B, and an activator; wherein the molar ratio of the first internal electron donor to the second internal electron donor is between 0.01 and 0.7;

wherein in Formula A each R 80 group is independently a substituted or unsubstituted aromatic group; R 81 , R 82 , R 83 , R 84 , R 85 , R 86 and R 87 are each independently selected from a hydrogen or a hydrocarbyl group; N is a nitrogen atom; O is an oxygen atom; and C is a carbon atom;
wherein in Formula B R 51 and R 52 are each independently selected from a hydrogen or a hydrocarbyl group; R 53 and R 54 are each independently selected from hydrogen, a halide or a hydrocarbyl group; O is an oxygen atom; and C is a carbon atom; and
wherein said process comprises the steps of:
i) contacting a compound R 4 z MgX 4 2-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR 1 ) x X 1 2-x , wherein R 1 is a hydrocarbyl group, wherein R 4 is butyl; wherein X 4 and X 1 are each independently a halide; z is in a range of larger than 0 and smaller than 2, being 0<z<2;
ii) optionally contacting the solid Mg(OR 1 ) x X 1 2-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w , to obtain a second intermediate product; wherein: M 1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M 1 ; M 2 is a metal being Si; v is the valency of M 2 ; R 2 and R 3 are each independently a hydrocarbyl group; w is smaller than v; and
iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with the halogen-containing Ti-compound, the first internal electron donor according to Formula A, the second internal electron donor according to Formula B, and the activator,
wherein the activator comprises a benzamide activator according to Formula D:

wherein R 70 and R 71 are each independently selected from hydrogen or an alkyl; wherein R 72 , R 73 , R 74 , R 75 , R 76 are each independently selected from hydrogen, a heteroatom, or a hydrocarbyl group.

2. The process according to claim 1 , wherein the first internal electron donor according to Formula A is selected from the group consisting of 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 and 4-(methylamino)pentan-2-yl bis (4-methoxy)benzoate).

3. The process according to claim 1 , wherein the second internal electron donor according to Formula B is selected from the group consisting of 2-isobutyl-2-isobutyl-1,3-dimethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-bis-methoxymethyl-fluorene.

4. The process according to claim 1 , wherein the first internal electron donor is 4-[benzoyl(methyl)amino]pentan-2-yl benzoate and wherein the second internal electron donor is 9,9-bis-methoxymethyl-fluorene.

5. The process according to claim 1 , wherein the ratio between the first internal electron donor and the second internal electron donor is between 0.05 and 0.65.

6. The process according to claim 1 , wherein the first internal electron donor is 4-[benzoyl(methyl)amino]pentan-2-yl benzoate and wherein the second internal electron donor is 9,9-bis-methoxymethyl-fluorene and the activator is N,N-dimethylbenzamide and wherein the ratio between the first internal electron donor and the second internal electron donor is between 0.3 and 0.5.

7. The process according to claim 1 , comprising the steps of:
i) contacting butylmagnesiumchloride with tetraethoxysilane to give said first intermediate reaction product;
ii) contacting said first intermediate reaction product with ethanol as activating electron donor and titanium tetraethoxide as metal alkoxide compounds to obtain a second intermediate reaction product; and
iii) contacting the second intermediate reaction product with titanium tetrachloride, 4-[benzoyl(methyl)amino]pentan-2-yl benzoate as the first internal electron donor, 9,9-bis-methoxymethyl-fluorene as the second internal electron donor, and N,N-dimethylbenzamide as the activator.

8. The process according to claim 7 , wherein step iii) comprises three stages I, II and III of adding titanium tetrachloride and wherein 4-[benzoyl(methyl)amino]pentan-2-yl benzoate, 9,9-bis-methoxymethyl-fluorene, and activator are each added during stage I.

9. The process according to claim 7 , wherein step iii) comprises three stages I, II and III of adding titanium tetrachloride and wherein the activator is added during stage I, 4-[benzoyl(methyl)amino]pentan-2-yl benzoate is added during stage II, and 9,9-bis-methoxymethyl-fluorene is added during stage III.

10. A procatalyst obtained by a process according to claim 1 .

11. A catalyst system for the polymerization of olefins, comprising a procatalyst according to claim 10 ; a co-catalyst; and an external donor.

12. A process for preparing a polyolefin the process comprising contacting an olefin with the catalyst system according to claim 11 .

13. The process according to claim 1 , wherein
v is 3 or 4;
said activator is a benzamide selected from the group consisting of benzaethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate, and benzoic anhydride, benzamide, N-methylbenzamide, N-ethylbenzamide, N,N-dimethylbenzamide, N,N-dimethylbenzamide, and N-methyl-N-ethylbenzamide; and
the ratio between the first internal electron donor and the second internal electron donor is between 0.2 and 0.55.

14. The process according to claim 12 , wherein the olefin is propylene.

15. The process according to claim 1 , R 70 and R 71 are each independently an alkyl.

16. A process for preparing a procatalyst for polymerization of olefins, said process comprising contacting a magnesium-containing support with a halogen-containing titanium compound, a first internal electron donor represented by Formula A, a second internal electron donor represented by Formula B, and an activator; wherein the molar ratio of the first internal electron donor to the second internal electron donor is between 0.01 and 0.7;

wherein in Formula A each R 80 group is independently a substituted or unsubstituted aromatic group; R 81 , R 82 , R 83 , R 84 , R 85 , R 86 and R 87 are each independently selected from a hydrogen or a hydrocarbyl group; N is a nitrogen atom; O is an oxygen atom; and C is a carbon atom; and
wherein in Formula B R 51 and R 52 are each independently selected from a hydrogen or a hydrocarbyl group; R 53 and R 54 are each independently selected from hydrogen, a halide or a hydrocarbyl group; O is an oxygen atom; and C is a carbon atom;
wherein said process comprises the steps of:
i) contacting a co

Assignees

• Sabic Global Technologies Bv

Inventors

• Zuideveld Martin Alexander
• Sergeev Sergei Andreevich
• Zakharov Vladimir Aleksandrovich
• Steinfort Dafne Lise

Classifications

• C07C233/69 Primary

  of an acyclic saturated carbon skeleton · CPC title

• C08F110/06

  Propene · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title