Scalable production of precision hydrocarbons from trialkylaluminum via ternary living coordinative chain transfer polymerization

Patent metadata

Field	Value
Publication number	US-9416069-B2
Application number	US-201113520389-A
Country	US
Kind code	B2
Filing date	Jan 4, 2011
Priority date	Jan 4, 2010
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

Disclosed is a method of producing a polyolefin composition comprising contacting a metallocene pre-catalyst, a co-catalyst, a primary surrogate, and a secondary surrogate; adding a first olefin monomer; and polymerizing the first monomer for a time sufficient to form the polyolefin. Also disclosed is a method of producing a block polyolefin composition comprising contacting a metallocene pre-catalyst, a co-catalyst, a primary surrogate, and a secondary surrogate; polymerizing the first monomer for a time sufficient to form the polyolefin; adding a second monomer; and polymerizing the second olefin monomer for a time sufficient to form said block polyolefin composition. The method allows for the production of polyolefins of low molecular weights and narrow molecular weight distributions.

First claim

What is claimed is:

1. A method of producing a polyolefin composition comprising:
(a) contacting a metallocene pre-catalyst, a co-catalyst, of Al(R 8 ) 3 , wherein R 8 is a C 1 -C 10 alkyl, and Zn(R 9 ) 2 , wherein R 9 is a C 1 -C 10 alkyl;
(b) adding a first olefin monomer; and
(c) polymerizing by ternary living coordinative chain transfer said first olefin monomer for a time sufficient to form said polyolefin, wherein Al(R 8 ) 3 and Zn(R 9 ) 2 are added in a ratio of about 1.1:1 to about 100:1.

2. The method of claim 1 , wherein R 8 is selected from the group consisting of ethyl, methyl, iso-butyl, n-hexyl, n-propyl, and t-butyl.

3. The method of claim 2 , wherein R 8 is iso-butyl.

4. The method of claim 2 , wherein R 8 is ethyl.

5. The method of claim 2 , wherein R 8 is n-propyl.

6. The method of claim 1 , wherein R 9 is selected from the group consisting of methyl, ethyl, n-butyl, isoamyl, t-butyl, neopentyl, n-propyl, and iso-propyl.

7. The method of claim 6 , wherein R 9 is ethyl.

8. The method of claim 1 , wherein said ratio is about 9:1.

9. The method of claim 1 , wherein said ratio is about 19:1.

10. The method of claim 1 , wherein said metallocene pre-catalyst is (η 5 -C 5 Me 5 )Hf(Me) 2 [N(Et)C(Me)N(Et)].

11. The method of claim 1 , wherein said co-catalyst is selected from the group consisting of [PhNMe 2 H][B(C 6 F 5 ) 4 ], [PhNMe 2 H][B(C 6 F 5 ) 3 Me], and B(C 6 F 5 ) 3 .

12. The method of claim 1 , wherein the Al(R 8 ) 3 and Zn(R 9 ) 2 are contacted with the metallocene pre-catalyst and the co-catalyst in an inert solvent.

13. The method of claim 12 , wherein said solvent is toluene.

14. The method of claim 1 , wherein the Al(R 8 ) 3 , the Zn(R 9 ) 2 , the metallocene pre-catalyst, and the co-catalyst are contacted at a temperature of about −20° C. to about 25° C.

15. The method of claim 1 , wherein the first olefin monomer is selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, butadiene, isoprene, 3-methylbutene, 3-methyl-1-pentene, vinylcyclohexane, vinylcyclobutane, vinylcyclopentane, vinylcyclooctane, 1-decene, enantiomerically pure β-citronellene, 3,5,5-trimethyl-1-hexene, cyclopentene, vinylcyclohexene, and 4-methyl-1-pentene.

16. The method of claim 1 , wherein the first olefin monomer is selected from the group consisting of ethene, propene, 1-hexene, 1-octene, and 1,5-hexadiene.

17. The method of claim 1 , wherein the polyolefin is an atactic polyolefin having a polydispersity index of about 1.01-1.15.

18. The method of claim 1 , wherein the metallocene pre-catalyst is (η 5 -C 5 Me 5 )Hf(Me) 2 [N(Et)C(Me)N(Et)], R 8 is ethyl, R 9 is ethyl, and the first olefin monomer is propene.

19. The method of claim 1 , wherein the metallocene pre-catalyst is (η 5 -C 5 Me 5 )Hf(Me) 2 [N(Et)C(Me)N(Et)], R 8 is n-propyl, R 9 is ethyl, and the first olefin monomer is propene.

20. The method of claim 1 , wherein the metallocene pre-catalyst is (η 5 -C 5 Me 5 )Hf(Me) 2 [N(Et)C(Me)N(Et)], R 8 is iso-butyl, R 9 is ethyl, the first olefin monomer is propene.

21. The method of claim 20 , wherein the ratio of Al(R 8 ) 3 to Zn(R 9 ) 2 is from about 9:1 to about 19:1.

22. The method of claim 1 , further comprising adding a second olefin monomer; and polymerizing said second monomer for a time sufficient to form a polyolefin block copolymer.

23. The method of claim 22 , wherein said second olefin monomer is selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, butadiene, isoprene, 3-methylbutene, 3-methyl-1-pentene, vinylcyclohexane, vinylcyclobutane, vinylcyclopentane, vinylcyclooctane, 1-decene, enantiomerically pure β-citronellene, 3,5,5-trimethyl-1-hexene, and 4-methyl-1-pentene.

24. The method of claim 22 , wherein said polyolefin block copolymer is an atactic living polyolefin.

25. The method of claim 22 , wherein said polyolefin block copolymer comprises a diblock copolymer having the formula: atactic-poly(first olefin)-co-poly(second olefin).

26. The method of claim 22 , wherein said polyolefin block copolymer has a polydispersity index of about 1.02-1.2.

27. The method of claim 22 , wherein said polyolefin block copolymer is monomodal.

28. The method of claim 22 , wherein the metallocene pre-catalyst is (η 5 -C 5 Me 5 )Hf(Me) 2 [N(Et)C(Me)N(Et)], R 8 is iso-butyl, R 9 is ethyl, the first olefin monomer is propene, and the second olefin monomer is 1-octene.

29. The method of claim 28 , wherein the ratio of Al(R 8 ) 3 to Zn(R 9 ) 2 is about 9:1.

Assignees

• Sita Lawrence R
• Wei Jia
• Univ Maryland

Inventors

• Sita Lawrence R
• Wei Jia

Classifications

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F10/00 Primary

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

• C07C2/30 Primary

  containing metal-to-carbon bond; Metal hydrides · CPC title

• C08F2420/04

  Cp or analog not bridged to a non-Cp X ancillary anionic donor · CPC title

• C08F2500/02

  Low molecular weight, e.g. <100,000 Da. · CPC title