Methods of preparing functionalized polyolefins

Patent metadata

Field	Value
Publication number	US-10544238-B2
Application number	US-201615281906-A
Country	US
Kind code	B2
Filing date	Sep 30, 2016
Priority date	Oct 1, 2015
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

Provided herein are methods for preparing a functionalized polyolefin from an unsaturated polyolefin containing one or more non-aromatic main-chain double bonds and for reducing the size and/or polydispersity index (i.e., increasing the homogeneity) of the unsaturated polyolefin.

First claim

What is claimed:

1. A method for preparing a functionalized polyolefin, comprising reacting an unsaturated polyolefin containing one or more non-aromatic main-chain double bonds with an aromatic compound in the presence of a Lewis acid and protic acid to form the functionalized polyolefin.

2. The method of claim 1 , wherein the functionalized polyolefin has a weight average molecular weight or number average molecular weight smaller than that of the unsaturated polyolefin.

3. The method of claim 1 , wherein the molar ratio of the aromatic compound relative to the number of non-aromatic main-chain double bonds in the unsaturated polyolefin is ranging from about 1 to about 5.

4. The method of claim 1 , wherein the aromatic compound is a substituted benzene.

5. The method of claim 1 , wherein the aromatic compound has the structure of Formula XII:

wherein:
each R 6 and R 7 is independently hydrogen or alkyl;
each R 8 is independently halo, alkyl, or alkoxy;
Z and s are:
i. s is an integer of 0; and
Z is hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocyclyl, or -L-SiR Za R Zb R Zc ,

ii. s is an integer of 1; and
Z is hydrogen, halo, fluoro, chloro, bromo, iodo, —CN, —NC, —NCO, —OCN, —NCS, —SCN, alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocyclyl, —C(O)OR 2a , —C(O)NR 2b R 2c , —OR 2a , alkoxy, —OC(O)R 2a , or -L-SiR Za R Zb R Zc ; or

iii. s is an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,or 20; and
Z is hydrogen, halo, fluoro, chloro, bromo, iodo, —CN, —NC, —NCO, —OCN, —NCS, —SCN, alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocyclyl, —C(O)OR 2a , —C(O)NR 2b R 2c , —OR 2a , alkoxy, —OC(O)R 2a , —NR 2b R 2c or -L-SiR Za R Zb R Zc ;

each L is independently a bond or ethynylene (—C≡C—);
each R Za , R Zb , and R Zc is independently halo, fluoro, chloro, bromo, iodo, alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocyclyl, —OR 2a , hydroxyl, alkoxy, or —NR 2b R 2c ;
t is an integer of 0, 1, 2, 3, 4, or 5; and
each R 2a , R 2b , and R 2c is independently (i) hydrogen; or (ii) alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heterocyclyl; or (iii) R 2b and R 2c together with the N atom to which they are attached form heteroaryl or heterocyclyl;
wherein each alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocyclyl, and alkoxy is independently and optionally substituted.

6. The method of claim 1 , wherein the aromatic compound is anisole, isopropoxybenzene, 2-bromoethoxybenzene, or 3-bromopropoxybenzene.

7. The method of claim 1 , wherein the Lewis acid is a titanium tetrahalide, a boron trihalide, an aluminum trihalide, a tin tetrahalide, a zinc halide, ethyl aluminum dichloride, or a mixture thereof.

8. The method of claim 1 , wherein the protic acid is formed in situ.

9. The method of claim 1 , wherein the method is performed at a temperature ranging from about −120 ° C. to about 50 ° C.

10. The method of claim 1 , wherein the method is performed in a solvent.

11. The method of claim 10 , wherein the solvent is a hydrocarbon, a halogenated hydrocarbon, or a mixture thereof.

12. The method of claim 1 , wherein the unsaturated polyolefin is a copolymer of an olefin and a comonomer.

13. The method of claim 12 , wherein the olefin is isobutylene.

14. The method of claim 1 , wherein the unsaturated polyolefin has the structure of Formula III:

wherein:
R 1 ,R 2 , and R 3 are each independently hydrogen, alkyl, or aryl;
n is an integer ranging from about 1 to about 2,000;
x is an integer ranging from about 10 to about 200; and
y is an integer of 0 or 1;
wherein each alkyl and aryl is independently and optionally substituted.

15. The method of claim 1 , wherein the functionalized polyolefin comprises a compound having the structure of Formula XXI, XXIa, or XXIb:

wherein:
R 1 , R 2 , and R 3 are each independently hydrogen, alkyl, or aryl, where the alkyl and aryl is independently and optionally substituted;
each R A is independently aryl or heteroaryl, each independently and optionally substituted;
x is an integer ranging from about 10 to about 200;
y is an integer of 0 or 1; and
each q is independently an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

16. The method of claim 15 , wherein y is an integer of 1.

17. The method of claim 15 , wherein R 1 , R 2 , and R 3 are each independently hydrogen, methyl, or phenyl.

18. The method of claim 1 , wherein the unsaturated polyolefin has the structure of Formula XI:

wherein:
n is an integer ranging from about 1 to about 2,000; and
each x is independently an integer ranging from about 10 to about 200.

19. The method of claim 1 , wherein the functionalized polyolefin comprises a compound having the structure of Formula XXXIII, XXXIIIa, or XXXIIIb:

wherein:
each R A is independently aryl or heteroaryl, each independently and optionally substituted;
each q is independently an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; and
each x is independently an integer ranging from about 10 to about 200.

Assignees

• Chevron Oronite Co
• The Univ Of Southern Mississippi

Inventors

• Storey Robson F
• Ummadisetty Subramanyam
• Campbell Christopher Garrett
• Stokes Casey D
• Chang Young

Classifications

• C08F8/26

  Removing halogen atoms or halogen-containing groups from the molecule · CPC title

• C08F8/50

  Partial depolymerisation · CPC title

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F10/10

  Isobutene · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title