Methods of producing mono- and multi-functional polymers from terpene-based initiators

Patent metadata

Field	Value
Publication number	US-8969484-B2
Application number	US-201113179393-A
Country	US
Kind code	B2
Filing date	Jul 8, 2011
Priority date	Jul 8, 2011
Publication date	Mar 3, 2015
Grant date	Mar 3, 2015

Abstract

Provided herein are methods for the preparation of mono- and multi-functional telechelic polyolefins via polymerization reaction with a terpene-based initiator.

First claim

What is claimed:

1. A method for producing a telechelic polymer, comprising contacting a compound of formula I:
D L-T) n   I

with a Lewis acid in the presence of one or more monomers, wherein:
D is alkaryl, aralkyl, or Y p , where Y is aryl and p is an integer from 1-4;
each L, independently, is:

wherein each A, independently, is hydrocarbylene or a bond; and
the oxygen is bonded to T;

each T, independently, is a terpene;
wherein at least one of the tertiary carbons of the terpene contain a leaving group; and

each n, independently, is an integer from 1-6.

2. The method of claim 1 , wherein D is alkaryl or aralkyl.

3. The method of claim 1 , wherein D is alkaryl of 7-20 carbons.

4. The method of claim 1 , wherein D is aralkyl of 7-20 carbons.

5. The method of claim 1 , wherein D is Z(Y) r ; wherein:
Y, independently, is aryl;
Z is hydrocarbyl;
L is bonded to a Y of the Z(Y) r ; and
r is an integer from 1 to 3.

6. The method of claim 1 , wherein D is Y p , wherein Y is aryl and p is an integer from 1-4.

7. The method of claim 6 , wherein p is 1.

8. The method of claim 6 , wherein Y is phenyl.

9. The method of claim 1 , wherein L is:

10. The method of claim 9 , wherein A is a bond.

11. The method of claim 1 , wherein n is an integer from 1-4.

12. The method of claim 1 , wherein T is a monoterpene, wherein at least one of the tertiary carbons of the monoterpene contains a leaving group.

13. The method of claim 1 , wherein the terpene is not substituted, except for the at least one of the tertiary carbons that contains a leaving group.

14. The method of claim 1 , wherein the terpene is not cyclic.

15. The method of claim 1 , wherein T has the formula (i), (ii), or (iii):

wherein B 1 and B 2 are each, independently, a leaving group or —H;
wherein at least one of B 1 and B 2 is a leaving group; and

if T has formula (i), T is substituted with 1-3 substituents.

16. The method of claim 15 , wherein one of B 1 and B 2 is —H.

17. The method of claim 15 , wherein T is:

18. The method of claim 1 , wherein the leaving group is —Cl or —Br.

19. The method of claim 1 , wherein the compound of formula I has the following formula:

and n is an integer from 1-4.

20. The method of claim 19 , wherein T is a monoterpene, wherein one or more of the tertiary carbons of the monoterpene contain a leaving group.

21. The method of claim 20 , wherein T is:

wherein B 1 is a leaving group.

22. The method of claim 21 , wherein the leaving group is —Cl or —Br.

23. The method of claim 1 , further comprising adding one or more quenching agents.

24. The method of claim 23 , wherein the quenching agent is
(a) allyltrimethylsilane;
(b) methallyltrimethylsilane;
(c) 1,1-diphenylethylene;
(d) furan or a substituted furan;
(e) thiophene or a substituted thiophene;
(f) triphenylamine;
(g) a compound having the following formula:

wherein:
R PY1 and R PY2 are independently in each —(CR PY1 R PY2 )— unit selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms;
m is an integer from 1 to 20; and
X PY is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, alkoxy, heteroaryl, nitro, ureido, —OC(O)R PY3 , —C(O)R PY4 , —C(O)OR PY5 , —C(O)NR PY6 R PY7 , —P(R PY8 ) 3 , —P(OR PY9 ) 3 , —SR PY10 , —OSO 3 R PY11 , and —S(O)R PY12 ;
wherein R PY3 is alkyl or alkenyl; and R PY4 , R PY5 , R PY7 , R PY8 , R PY9 , R PY10 , R PY11 , and R PY12 are alkyl;

(h) a compound having the following formula:

wherein:
R 1 through R 8 are independently hydrogen, alkyl from 1 to 20 carbon atoms, aryl from 6 to about 20 carbon atoms, alkaryl from about 7 to 30 carbon atoms, or aralkyl from about 7 to 30 carbon atoms;
R is hydrogen, alkyl from 1 to 20 carbon atoms, aryl from 6 to about 20 carbon atoms, alkaryl from about 7 to 30 carbon atoms, or aralkyl from about 7 to 30 carbon atoms; and
X is oxygen or sulfur;
with the proviso that when R is hydrogen or methyl then R 1 , R 2 , R 7 and R 8 must be other than hydrogen unless one of R 1 or R 2 and one of R 7 or R 8 is independently branched alkyl of about 3 to 20 carbon atoms, aryl, alkaryl or aralkyl;

(i) a compound having the following formula:
R 1X S—R 2X

wherein R 1X and R 2X , are each, independently, hydrocarbyl;

(j) a compound having the following formula:
R SA S—S—R SB

wherein R SA and R SB are each, independently, alkyl, aryl, aralkyl, alkaryl,

wherein:
X S is halo or a pseudohalide;
R SX is alkyl or aryl;
R S3 is tert-butyl; and
R S4 and R S5 are each, independently, alkyl, aryl, aralkyl, or alkaryl;

(k) a compound having the following formula:

wherein:
R PH1 and R PH2 are each, independently in each —(CR PH1 R PH2 ) unit, —H or alkyl, and
p is an integer from 0-20, wherein:
(1) if p is 0, then R PH3 and R PH4 are each, independently, alkyl, and
X PH is —H;

(2) if p is 1, then R PH3 and R PH4 are each, independently —H, alkyl, or alkoxy, and X PH is —H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, or

wherein R PH5 -R PH7 are each, independently, alkyl or aryl;

(3) if p is 2, then R PH3 and R PH4 are each, independently —H, alkyl, or alkoxy, and X PH is —H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)R PH8 , —C(O)OR PH9 , —C(O)NR PH10 R PH11 , or

wherein:
A 1 is

 or a single bond,
R PH5 to R PH7 are each, independently, alkyl, alkenyl, alkynyl, al

Assignees

• Stokes Casey D
• Chang Young A
• Mcdougall Patrick J
• Chevron Oronite Co

Inventors

• Stokes Casey D
• Chang Young A
• Mcdougall Patrick J

Classifications

• C08F110/10

  Isobutene · CPC title

• C08F10/10 Primary

  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

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F8/20

  Halogenation · CPC title