Polar comonomer enchainment in olefin polymerization reactions

Patent metadata

Field	Value
Publication number	US-11359039-B2
Application number	US-201816648526-A
Country	US
Kind code	B2
Filing date	Oct 5, 2018
Priority date	Oct 6, 2017
Publication date	Jun 14, 2022
Grant date	Jun 14, 2022

Abstract

A method for forming polar-functionalized polyolefins may comprise contacting an unsubstituted α-olefin monomer and an amino-olefin monomer of formula H2C═CH(CH2)n(CHR)mNR′2, wherein R is H or an unsubstituted linear or branched alkyl group having from 1 to 10 carbons, each R′ is an independently selected unsubstituted linear or branched alkyl group having from 1 to 10 carbons, m is an integer from 1 to 11, and n is an integer from 1 to 11, in the presence of a rare earth catalyst and a cocatalyst under conditions to induce a heteropolymerization reaction between the unsubstituted oc-olefin and amino-olefin monomers to provide a polar-functionalized poly olefin.

First claim

What is claimed is:

1. A method for forming a polar-functionalized polyolefin, the method comprising contacting an unsubstituted α-olefin monomer and an amino-olefin monomer of formula H 2 C═CH(CH 2 ) 2 (CHR) m NR′ 2 , wherein R is H or an unsubstituted linear or branched alkyl group having from 1 to 10 carbons, each R′ is an independently selected unsubstituted linear or branched alkyl group having from 1 to 10 carbons, m is an integer from 0 to 11, and n is an integer from 1 to 11, in the presence of a rare earth catalyst and a cocatalyst under conditions to induce a heteropolymerization reaction between the unsubstituted α-olefin and amino-olefin monomers to provide a polar-functionalized polyolefin.

2. The method of claim 1 , wherein the amino-olefin monomer has formula H 2 C═CH(CH 2 ) n NR′ 2 , wherein each R′ is an independently selected unsubstituted linear or branched alkyl group having from 1 to 10 carbons and n is an integer from 1 to 11.

3. The method of claim 1 , wherein each R′ group of the amino-olefin monomer is the same.

4. The method of claim 2 , wherein the alkyl group of the amino-olefin monomer is a linear alkyl group.

5. The method of claim 1 , wherein the unsubstituted α-olefin monomer is of formula H 2 C═CHR, wherein R is selected from H and (CH 2 ) n CH 3 , wherein n is an integer between 0 and 10.

6. The method of claim 1 , wherein the unsubstituted α-olefin monomer is ethylene.

7. The method of claim 1 , wherein the rare earth catalyst is selected from a group consisting of a mononuclear organoscandium catalyst, a binuclear organoscandium catalyst, a mononuclear organoyttrium catalyst, a binuclear organoyttrium catalyst, a mononuclear organoytterbium catalyst, a binuclear organoytterbium catalyst a mononuclear organolutetium catalyst, a binuclear organolutetium catalyst, and combinations thereof.

8. The method of claim 7 , wherein the rare earth catalyst is of Formula 6 or Formula 7,

wherein M is selected from Sc, Y, Yb, and Lu and n is 0 or 2.

9. The method of claim 8 , wherein M is selected from Sc, Y, and Yb.

10. The method of claim 9 , wherein the rare earth catalyst is of Formula 6.

11. The method of claim 10 , wherein M is Sc.

12. The method of claim 1 , wherein the heteropolymerization reaction is carried out in the presence of an exogenous Lewis base.

13. The method of claim 12 , wherein the exogenous Lewis base is a tertiary amine.

14. A method for forming a polar-functionalized polyolefin, the method comprising contacting an olefin monomer of formula H 2 C═CHR, wherein R is selected from H and (CH 2 ) n CH 3 , wherein n is an integer between 0 and 10, and an amino-olefin monomer of formula H 2 C═CH(CH 2 ) n NR′ 2 , wherein each R′ is the same linear, unsubstituted alkyl group having from 1 to 10 carbons and n is an integer from 1 to 11, in the presence of a rare earth catalyst and a cocatalyst under conditions to induce a heteropolymerization reaction between the olefin and amino-olefin monomers to provide a polar-functionalized polyolefin, wherein the rare earth catalyst is of Formula 6 or Formula 7,

wherein M is selected from Sc, Y, Yb, and Lu and n is 0 or 2.

15. The method of claim 14 , wherein the olefin monomer is ethylene.

16. The method of claim 14 , wherein M is selected from Sc, Y, and Yb.

17. The method of claim 16 , wherein the rare earth catalyst is of Formula 6.

18. The method of claim 17 , wherein M is Sc.

19. The method of claim 14 , wherein the heteropolymerization reaction is carried out in the presence of an exogenous Lewis base.

20. The method of claim 19 , wherein the exogenous Lewis base is a tertiary amine.

Assignees

• Univ Northwestern

Inventors

• Marks Tobin J
• Chen Jiazhen
• Lohr Tracy L

Classifications

• C08F210/02 Primary

  Ethene · CPC title

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F4/61927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F2420/12

  Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge · CPC title