Solid catalyst component for polymerization of olefins, method for producing solid catalyst component for polymerization of olefins, catalyst for polymerization of olefins, method for producing polymer of olefin, method for producing polymer propylene copolymer and propylene copolymer

Patent metadata

Field	Value
Publication number	US-11236189-B2
Application number	US-201716338517-A
Country	US
Kind code	B2
Filing date	Oct 3, 2017
Priority date	Oct 3, 2016
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

A solid catalyst component for polymerization of olefins is disclosed which can produce a polymer having low stickiness (tackiness) of polymer particles, excellent flowability, and favorable particle size distribution. The solid catalyst component for polymerization of olefins includes titanium, magnesium, a halogen atom and an internal electron donor, wherein the solid catalyst component has a multimodal pore volume distribution measured by a mercury intrusion method and has one or more peak tops in each of a pore radius range from 0.002 μm to 1 μm and a pore radius range from larger than 1 μm to 30 μm or smaller, and a ratio represented by pore volume V1 derived from pores in the radius range from 0.002 μm to 1 μm/pore volume V2 derived from pores in the radius range from larger than 1 μm to 30 μm or smaller is 0.30 to 0.65.

First claim

The invention claimed is:

1. A solid catalyst component for polymerization of olefins, comprising
titanium, magnesium, a halogen atom and an internal electron donor, wherein
the solid catalyst component has a multimodal pore volume distribution measured by a mercury intrusion method and has one or more peak tops in each of a pore radius range from 0.002 μm to 1 μm and a pore radius range from larger than 1 μm to 30 μm or smaller, and
a ratio represented by pore volume V1 derived from pores in the radius range from 0.002 μm to 1 μm/pore volume V2 derived from pores in the radius range from larger than 1 μm to 30 μm or smaller is 0.30 to 0.65.

2. The solid catalyst component for polymerization of olefins according to claim 1 , wherein a total pore volume measured by the mercury intrusion method is 0.65 to 2.00 cm 3 /g.

3. The solid catalyst component for polymerization of olefins according to claim 1 , wherein the pore volume V1 derived from pores in the radius range from 0.002 μm to 1 μm is 0.1 to 0.8 cm 3 /g.

4. The solid catalyst component for polymerization of olefins according to claim 1 , wherein the pore volume V2 derived from pores in the radius range from larger than 1 μm to 30 μm or smaller is 0.3 to 1.5 cm 3 /g.

5. The solid catalyst component for polymerization of olefins according to claim 1 , wherein a specific surface area measured by a BET method is 1 to 500 m 2 /g.

6. The solid catalyst component for polymerization of olefins according to claim 1 , wherein the internal electron donor is one or more compounds selected from an ester compound, an ether compound and a carbonate compound.

7. A method for producing a solid catalyst component for polymerization of olefins according to claim 1 , comprising the step of
bringing a magnesium compound having an alkoxy group, a titanium halide compound and an internal electron donor into contact with each other, wherein
for the contact between the magnesium compound having an alkoxy group and the titanium halide compound, the magnesium compound having an alkoxy group is added to the titanium halide compound or alternatively the titanium halide compound is added to the magnesium compound having an alkoxy group continuously or intermittently over 2 hours or longer while a temperature of 15° C. or lower is kept.

8. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group is dialkoxy magnesium.

9. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group has a spherical or ellipsoidal particle shape, has a multimodal pore volume distribution defined by the mercury intrusion method, and has one or more peak tops in each of a pore radius range from 0.002 μm to 1 μm and a pore radius range from larger than 1 μm to 30 μm or smaller.

10. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group has a total pore volume of 1.3 to 3.0 cm 3 /g defined by the mercury intrusion method.

11. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group has a pore volume of 0.3 cm 3 /g or larger derived from pores in a pore radius range from 0.002 μm to 1 μm, defined by the mercury intrusion method.

12. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group has a pore volume of 0.5 to 2.0 cm 3 /g derived from pores in a pore radius range from larger than 1 μm to 30 μm or smaller, defined by the mercury intrusion method.

13. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the magnesium compound having an alkoxy group comprises 0.1 to 1.5 parts by mass of an alcohol per 100 parts by mass of the magnesium compound having an alkoxy group.

14. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein in the step of bringing the magnesium compound having an alkoxy group and the titanium halide compound into contact with each other, the magnesium compound having an alkoxy group is added to the titanium halide compound continuously or intermittently over 2 hours or longer while a temperature of 15° C. or lower is kept.

15. The method for producing a solid catalyst component for polymerization of olefins according to claim 7 , wherein the internal electron donor is brought two or more times into contact with the magnesium compound having an alkoxy group, the titanium halide compound or a mixture of the magnesium compound having an alkoxy group and the titanium halide compound.

16. A catalyst for polymerization of olefins, comprising a contact product of a solid catalyst component for polymerization of olefins according to claim 1 , an organoaluminum compound represented by the following general formula (I):
R 1 p AlQ 3-p   (I)

wherein R 1 is an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom or a halogen atom; p is a real number of 0<p≤3; when a plurality of R 1 moieties are present, these R 1 moieties are the same as or different from each other; and when a plurality of Q moieties are present, these Q moieties are the same as or different from each other,
and an external electron-donating compound.

17. The catalyst for polymerization of olefins according to claim 16 , wherein the external electron-donating compound is at least one organosilicon compound selected from the following general formula (II):
R 2 q Si(OR 3 ) 4-q   (II)

wherein R 2 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group or an aralkyl group, and a plurality of R 2 moieties are the same or different; R 3 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, a vinyl group, an allyl group or an aralkyl group, and a plurality of R 3 moieties are the same or different; and q is an integer of 0≤q≤3,
and the following general formula (III):
(R 4 R 5 N) s SiR 6 4-s   (III)

wherein R 4 and R 5 each are a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group and are the same or different, or R 4 and R 5 are optionally bonded to each other to form a ring; R 6 is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group; when a plurality of R 6 moieties are present, the plurality of R 6 moieties are the same or different; and s is an integer of 1 to 3.

18. A method for producing a polymer of an olefin, comprising polymerizing the olefin in the presence of a catalyst for polymerization of olefins according to claim 16 .

19. A method for producing a propylene copolymer, comprising polymerizing propylene using a catalyst for polymerization of olefins according to claim 16 , and subsequently copolymerizing two or more olefins.

Assignees

• Toho Titanium Co Ltd

Inventors

• Umebayashi Hidetoshi

Classifications

• C08F297/083 Primary

  the monomers being ethylene or propylene · CPC title

• C08F210/06

  Propene · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F4/6546

  organo-magnesium compounds · CPC title

• C08F4/654

  with magnesium or compounds thereof · CPC title