Production method of olefin polymer and olefin polymerization catalyst

Patent metadata

Field	Value
Publication number	US-9540459-B2
Application number	US-201414773638-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Mar 12, 2013
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

To provide a method of efficiently affording olefin polymers having a high molecular weight and a high melting point even under industrially advantageous high-temperature conditions. A production method of an olefin polymer to solve the above problem includes polymerizing monomer(s) including at least one α-olefin having 3 or more carbon atoms at 50° C. to 200° C. in the presence of an olefin polymerization catalyst including; (A) a crosslinked metallocene compound represented by General Formula [I] below; and (B) at least one compound selected from (b-1) an organoaluminum oxy-compound, (b-2) a compound that forms an ion pair by reacting with the crosslinked metallocene compound (A), and (b-3) an organoalunimum compound.

First claim

The invention claimed is:

1. A production method of an olefin polymer, comprising
polymerizing monomer(s) comprising at least one α-olefin having 3 or more carbon atoms at not less than 50° C. and not more than 200° C. in the presence of an olefin polymerization catalyst comprising;
(A) a crosslinked metallocene compound represented by Formula I; and
(B) at least one compound selected from
(b-1) an organoaluminum oxy-compound,
(b-2) a compound that forms an ion pair by reacting with the crosslinked metallocene compound (A), and
(b-3) an organoalunimum compound,

in the formula, R 1 is an adamantyl group derivative; R 2 and R 7 are selected from a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group; R 3 and R 6 are hydrogen atoms; R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, or a halogen-containing hydrocarbon group, and adjacent substituents among R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 optionally form a ring; n is an integer between 1 and 3; M is a Group 4 transition metal; each Q is independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that is bondable with a lone pair; and j is an integer between 1 and 4.

2. The production method according to claim 1 , wherein in Formula I, R 1 is a 1-adamantyl group.

3. The production method according to claim 1 , wherein in Formula I, R 2 and R 7 are hydrocarbon groups having 4 to 10 carbon atoms.

4. The production method according to claim 1 , wherein in Formula I, R 4 and R 5 are hydrogen atoms.

5. The production method according to claim 1 , where in Formula I, R 12 is a hydrocarbon group having 1 to 20 carbon atoms.

6. The production method according to claim 1 , wherein in Formula I, R 8 to R 11 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.

7. The production method according to claim 1 , wherein in Formula I, R 10 and R 11 are hydrogen atoms.

8. The production method according to claim 1 , wherein in Formula I, R 8 and R 9 are hydrocarbon groups having 1 to 20 carbon atoms.

9. The production method according to claim 1 , wherein in Formula I, n is 1.

10. The production method according to claim 1 , wherein at least one of the α-olefins is propylene.

11. The production method according to claim 1 , wherein the olefin polymerization activity under hydrogen-free conditions is not less than 50 kg/mmol-M/h and not more than 1,000,000 kg/mmol-M/h, and wherein the olefin polymer satisfies both of the requirements (i) and (iii) below:
(i) Propylene content (P) is 51 mol %≦P≦100 mol %;
(iii) Intrinsic viscosity [η] in decalin at 135° C. is 1.0 (dl/g)≦[n]≦10 (dl/g).

12. The production method according to claim 11 , wherein the peak melting point (Tm) obtained from the differential scanning calorimetry (DSC) of the olefin polymer is 130° C.≦Tm≦155° C.

13. The production method according to claim 1 , wherein the olefin polymerization activity is not less than 1,000 kg/mmol-M/h and not more than 1,000,000 kg/mmol-M/h, and wherein the olefin polymer satisfies both of the requirements (i) and (iii) below:
(i) Ethylene content (E) is 1 mol %≦E≦10 mol %, and propylene content (P) is 90 mol %≦P≦99 mol % (provided that (E)+(P)=100 mol %); and
(iii) Melt mass-flow rate (MFR; g/10 min.) measured under the conditions of ASTM D1238 is 0.1≦MFR≦150.

14. The production method according to claim 13 , wherein the peak melting point (Tm) obtained from the differential scanning calorimetry (DSC) of the olefin polymer is 110° C.≦Tm≦135° C.

15. The production method according to claim 1 , wherein the above olefin polymerization catalyst further comprises a carrier (C).

16. An olefin polymerization catalyst represented by Formula I,

in the formula, R 1 is an adamantyl group derivative; R 2 and R 7 are selected from a hydrocarbon group, a silicon-containing group, or halogen-containing hydrocarbon group; R 3 and R 6 are hydrogen atoms; R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, or a halogen-containing hydrocarbon group, and adjacent substituents among R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 optionally form a ring; n is an integer between 1 and 3; M is a Group 4 transition metal; each Q is independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that is bondable with a lone pair; and j is an integer between 1 and 4.

17. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 1 is a 1-adamantyl group.

18. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 2 and R 7 are hydrocarbon groups having 4 to 10 carbon atoms.

19. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 4 and R 5 are hydrogen atoms.

20. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 12 is a hydrocarbon group having 1 to 20 carbon atoms.

21. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 8 to R 11 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.

22. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 10 and R 11 are hydrogen atoms.

23. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, R 8 and R 9 are hydrocarbon groups having 1 to 20 carbon atoms.

24. The olefin polymerization catalyst according to claim 16 , wherein in Formula I, n is 1.

Assignees

• Mitsui Chemicals Inc

Inventors

• Ebisawa Ikuko
• Kitagawa Hideo
• Yukita Takashi
• Yamashita Masahiro
• Takeda Kouji
• Kaneyoshi Hiromu

Classifications

• C08F4/65912 Primary

  in combination with an organoaluminium compound · CPC title

• C08F210/06

  Propene · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/00

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

• C08F110/06

  Propene · CPC title