Thioguanidine group IV transition metal catalysts and polymerization systems

Patent metadata

Field	Value
Publication number	US-10647799-B2
Application number	US-201716333071-A
Country	US
Kind code	B2
Filing date	Sep 14, 2017
Priority date	Sep 30, 2016
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

Catalyst compositions and polymerization systems include at least one thioguanidine complex according to Formula (I): MQ a X 4_a (I) in which M is Ti, Zr, or Hf; a is 1 or 2; each group Q of the thioguanidine complex is a bidentate thioguanidine ligand bound to the metal center and having Formula (1a) or Formula (1b), In Formulas (1a) and (1b), each group R 1 , R 2 , and R 3 is independently chosen from alkyl groups or aryl groups; each group Z 1 is independently chosen from alkylene groups. If a=2, groups R 3 of the two groups Q are optionally linked to each other through at least one covalent bond. Each X is covalently bonded or coordinated to the metal center and is independently chosen from alkyl groups or halides. The polymerization systems may be configured to copolymerize ethylene and α-olefins.

First claim

The invention claimed is:

1. A composition comprising at least one thioguanidine complex according to Formula (I):
MQ a X 4-a   (I)

where:
M is a metal center chosen from Ti, Zr, or Hf;
a is 1 or 2;
each group Q of the at least one thioguanidine complex is a bidentate thioguanidine ligand bound to the metal center, the thioguanidine ligand having Formula (Ia) or Formula (Ib):

each group R 1 , R 2 , and R 3 in the at least one thioguanidine complex is independently chosen from alkyl groups or aryl groups;
each group Z 1 in the at least one thioguanidine complex is independently chosen from alkylene groups;
if a=2, groups R 3 of the two groups Q are optionally linked to each other through at least one covalent bond; and
each X is covalently bonded or coordinated to the metal center and is independently chosen from alkyl groups, halides, or amides.

2. The composition of claim 1 , wherein a is 1, and the at least one thioguanidine complex has Formula (IIa) or Formula (IIb):

where M, R 1 , R 2 , R 3 , Z 1 , and X are as defined in Formula (I).

3. The composition of claim 2 , wherein R 1 of Formula (IIa) and R 3 of Formulas (IIa) and (IIb) are independently chosen from groups according to the formula

where A 1 and A 2 are independently hydrogen or a (C 1 -C 10 ) alkyl group.

4. The composition of claim 3 , wherein A 1 and A 2 are independently hydrogen or methyl.

5. The composition of claim 2 , wherein the at least one thioguanidine complex comprises compound C1:

where each Bn is benzyl (—CH 2 —C 6 H 5 ).

6. The composition of claim 1 , wherein a is 2 and the at least one thioguanidine complex has Formula (IIIa), Formula (IIIb), or Formula (IIIc):

where M, R 1 , R 2 , R 3 , Z 1 , and X are as defined in Formula (I).

7. The composition of claim 6 , wherein each R 1 is independently chosen from phenyl or a (C 1 -C 10 ) alkyl group.

8. The composition of claim 6 , wherein each R 1 is independently chosen from phenyl or n-butyl.

9. The composition of claim 6 , wherein each R 3 is independently chosen from groups according to the formula

where A 1 and A 2 are independently a (C 1 -C 10 ) alkyl group.

10. The composition of claim 9 , wherein both A 1 and A 2 are methyl.

11. The composition of claim 6 , wherein the at least one thioguanidine complex is chosen from compounds C2 or C3 or combinations thereof:

where each Bn in compounds C2 and C3 is benzyl (—CH 2 —C 6 H 5 ).

12. The composition of claim 1 , wherein:
a is 2;
R 3 of the two groups Q are linked to each other as a bridging group Z 2 ; and
the at least one thioguanidine complex has Formula (IVa), Formula (IVb), or Formula (IVc):

where M, R 1 , R 2 , Z 1 , and X are as defined in Formula (I) and Z 2 is an alkylene group.

13. The composition of claim 12 , wherein Z 2 is —(CH 2 ) n —, where n is from 4 to 10.

14. The composition of claim 12 , wherein Z 2 is —(CH 2 ) n —, where n is 4 or 5.

15. The composition of claim 12 , wherein each R 1 is independently chosen from groups having the formula:

where A 1 and A 2 are independently a (C 1 -C 10 ) alkyl group.

16. The composition of claim 15 , wherein both A 1 and A 2 are methyl.

17. The composition of claim 12 , wherein the at least one thioguanidine complex is chosen from compounds C4, C5, C6, or C7, or combinations thereof:

where each Bn in compounds C4 and C5 is benzyl (—CH 2 —C 6 H 5 ).

18. A polymerization method comprising:
reacting ethylene and an α-olefin comonomer in the presence of a catalytic amount of the composition of claim 1 to form an ethylene-co-alkylene copolymer, wherein the α-olefin comonomer comprises at least one C 3 -C 12 α-olefin.

19. The polymerization method of claim 18 , wherein the composition comprises at least one thioguanidine complex chosen from compounds C1, C2, C3, C4, C5, C6, C7, or combinations thereof:

where each Bn in compounds C1, C2, C3, C4, and C5 is benzyl (—CH 2 —C 6 H 5 ).

20. The polymerization method of claim 19 , wherein the α-olefin comonomer is 1-octene.

Assignees

• Dow Global Technologies Llc

Inventors

• Krasovskiy Arkady L
• Szuromi Endre

Classifications

• C08F4/64186

  Dianionic ligand · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F210/16 Primary

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

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title

• C08F4/64044

  NN · CPC title