Methods for synthesis of end-functionalized polyolefins

Patent metadata

Field	Value
Publication number	US-10414903-B2
Application number	US-201715809568-A
Country	US
Kind code	B2
Filing date	Nov 10, 2017
Priority date	Nov 11, 2016
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

A strategy for the synthesis of semi-telechelic polyethylene through the palladium diimine-catalyzed chain transfer polymerization of ethylene using various silanes as chain transfer agents is reported. Polymer molecular weight and end-group chemical structure can be tuned by varying the chain transfer agent as well as its concentration. NMR spectroscopy confirms that the silicon of the chain transfer agent is incorporated into the polymer. The stability of the catalyst toward polar monomer enables the chain transfer polymerization of semi-telechelic poly(ethylene-methyl acrylate) copolymers.

First claim

What is claimed is:

1. A method for preparing an end-functionalized polyolefin by a chain transfer polymerization (CTP) comprising:
combining a tertiary silane chain transfer agent (CTA) of formula HSiR 3 , a late transition metal catalyst, and an olefin, to provide a reaction mixture;
wherein each R of the CTA is independently an organic moiety, the late transition metal catalyst is substantially non-oxyphilic, the olefin comprises an optional functional group; and
the rate of the CTP is regulated by the substituents on the CTA, the degree of polymerization (DP) is regulated by the concentration of the CTA in the reaction mixture, and the reaction mixture provides an end-functionalized polyolefin having an end group comprising a silane moiety of formula —SiR 3 .

2. The method of claim 1 wherein the end functionalized polyolefin is a semitelechelic or a heterotelechelic polymer having a number average molar mass (M n ) and a dispersity (D stroke) that is modulated by the substituents on the CTA.

3. The method of claim 2 wherein each substituent R of the silane moiety at one end of the prepared semitelechelic or the heterotelechelic polymer is independently an alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, alkoxy, hydroxy, aryl, heteroaryl, aryloxy, heteroarlyoxy, an oligomer, or polymer, wherein an aryl or heteroaryl moiety is optionally substituted with one or more substituents, and an aryl or heteroaryl moiety is optionally a fused polyaromatic or fused polyheteroaromatic.

4. The method of claim 3 wherein each substituent R of the silane moiety is independently (C 1 -C 10 )alkyl, O(C 1 -C 10 )alkyl, (C 3 -C 8 )cycloalkyl, O(C 3 -C 8 )cycloalkyl, aryl, O(aryl), heteroaryl, or O(heteroaryl), wherein each aryl or heteroaryl moiety is optionally substituted with one or more of halo, hydroxy, amino, amide, hydrazino, carboxyl, carbonyl, cyano, nitro, alkyl, aryl, or heteroaryl.

5. The method of claim 4 wherein each substituent R of the silane moiety is independently O(C 1 -C 10 )alkyl, O(C 3 -C 8 )cycloalkyl, O(aryl), or O(heteroaryl), wherein R is optionally a dye or a fluorescent molecule.

6. The method of claim 4 wherein each substituent R of the silane moiety is independently (C 1 -C 10 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, or heteroaryl, wherein R is optionally a dye or fluorescent molecule.

7. The method of claim 6 wherein each substituent R of the silane moiety is independently aryl or heteroaryl.

8. The method of claim 4 wherein each substituent R of the silane moiety is independently methyl, ethyl, isopropyl, cyclopropyl, phenyl, tolyl, methoxy, ethoxy, isopropoxy, butoxy, or phenoxy.

9. The method of claim 1 wherein the late transition metal catalyst comprises palladium, nickel, or cobalt.

10. The method of claim 9 wherein the late transition metal catalyst comprises a monodentate ligand or a bidentate ligand.

11. The method of claim 10 wherein the late transition metal catalyst comprises a diimine, a phosphinosulfonate, or a phenanthroline.

12. The method of claim 10 wherein the olefin comprises an organic functional group.

13. The method of claim 12 wherein the functional group comprises a CN, —C—O—C—, —C(═O)C—, or —C(═O)OC— moiety.

14. The method of claim 10 wherein the olefin is ethylene or an acrylate.

15. The method of claim 1 wherein the initial concentration of the CTA in the reaction mixture ranges from about 0.01 millimolar to about 50 millimolar.

16. The method of claim 15 wherein the initial concentration of the CTA ranges from about 0.2 millimolar to about 25 millimolar.

17. The method of claim 2 wherein the CTA is added to the reaction mixture by continuous addition or pulse addition.

18. The method of claim 17 wherein the number of molar equivalents of the CTA added to the mixture ranges from about 0.01 equivalents to about 100 equivalents relative to moles of the late transition metal catalyst.

19. The method of claim 18 wherein the pressure of the reaction mixture ranges from about 15 psi to about 800 psi and the temperature of the reaction mixture ranges from about 0° C. to about 300° C.

20. The method of claim 19 wherein the semitelchelic or the heterotelechelic polymer has a dispersity ranging from about 1 to about 2.

Assignees

• Univ Illinois

Inventors

• Guironnet Damien S
• Hyatt Michael G
• Walsh Dylan J

Classifications

• C08F2438/00

  Living radical polymerisation · CPC title

• C08F20/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08G81/027

  containing polyester or polycarbonate sequences · CPC title

• C08F110/02

  Ethene · CPC title