Metathesis depolymerization using acrylates

Patent metadata

Field	Value
Publication number	US-9409850-B2
Application number	US-201314422740-A
Country	US
Kind code	B2
Filing date	Aug 20, 2013
Priority date	Aug 20, 2012
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

Olefin metathesis between an acrylate monomer and a polyene comprising molecule or polymer is employed as a method of cross-metathesizing or depolymerizing the molecule. The metathesis reaction forms a telechelic acrylate molecule that is a monomer, oligomer or polymer. The telechelic acrylate molecule can be employed as a monomer for condensation polymerization.

First claim

We claim:

1. A method of depolymerization comprising:
providing a polyene comprising molecule;
providing an olefin metathesis catalyst, wherein the olefin metathesis catalyst further comprises CuI;
providing an acrylic monomer;
combining the polyene comprising molecule with the olefin metathesis catalyst and the acrylic monomer; and
removing an alkene; wherein an acrylic diene comprising monomer, oligomer, or polymer results, wherein the acrylic diene comprising monomer mixture has a plurality of acrylic units on each of the acrylic diene comprising monomers.

2. The method of claim 1 , wherein the polyene comprising molecule is polybutadiene, polyisoprene, or other polyalkylene diene.

3. The method of claim 1 , wherein the polyene comprising molecule is a polyunsaturated naturally occurring oil.

4. The method of claim 3 , wherein the polyunsaturated naturally occurring oil is castor oil, linseed oil, corn oil, cotton seed oil, peanut oil, soybean oil, sunflower oil, grape seed oil, sesame oil, or hemp oil.

5. The method of claim 1 , wherein the olefin metathesis catalyst comprises Grubb's 1 st generation catalyst, Grubb's 2 nd generation catalyst, Hoveyda-Grubb's 1st generation catalyst, or Hoveyda-Grubb's 2 nd generation catalyst.

6. The method of claim 1 , wherein the acrylic monomer is an unsubstituted or substituted acrylic acid, acryloyl halide, acrylate, acrylamide, or mono acrylic anhydride.

7. The method of claim 1 , further comprising a solvent.

8. A polymer, comprising:

wherein: m>0.01; n≧1; X′ is O NH, or NR; R 1 and R 2 are independently H, methyl, ethyl, C 3 to C 14 alkyl, C 6 to C 14 aryl, C 7 to C 14 alkylaryl, or C 7 to C 14 arylalkyl, unsubstituted or substituted with one or more hydroxy, halo, C 1 -C 14 alkoxy, C 6 to C 14 aryloxy, C 7 to C 14 alkylaryloxy, C 7 to C 14 arylalkoxy, cyano, alkylcarboxy, arylcarboxy, amino, C 1 -C 14 alkylamino, C 6 -C 14 arylamino, C 2 -C 14 dialkylamino, C 12 -C 16 diarylamino, C 7 -C 14 alkylarylamino, carboxyhydroxy, C 1 -C 14 alkoxycarboxy, C 6 to C 14 aryloxycarboxy, C 1 -C 14 alkylcarboxyoxy, or C 6 to C 14 arylcarboxyoxy, wherein the substituent is optionally further substituted with one or more hydroxy, fluoro, chloro, bromo, or iodo; R 3 and R 5 are independently C 1 to C 14 alkylene, C 6 to C 14 arylene, C 7 to C 14 alkylarylene, or any combination thereof connected by ester, amide, ether, amine, or carbonyl linkages, unsubstituted or substituted independently with one or more OH, fluoro, chloro, bromo, iodo, OR, NHR, NR 2 , or RC(O)O; and R is independently methyl, ethyl, C 3 to C 14 alkyl, C 6 to C 14 aryl, C 7 to C 14 alkylaryl, C 7 to C 14 arylalkyl, unsubstituted or substituted independently with one or more hydroxy, halo, C 1 -C 14 alkoxy, C 6 to C 14 aryloxy, C 7 to C 14 alkylaryloxy, C 7 to C 14 arylalkoxy, cyano, alkylcarboxy, arylcarboxy, amino, C 1 -C 14 alkylamino, C 6 -C 14 arylamino, C 2 -C 14 dialkylamino, C 12 -C 16 diarylamino, C 7 -C 14 alkylarylamino, carboxyhydroxy, C 1 -C 14 alkoxycarboxy, C 6 to C 14 aryloxycarboxy, C 1 -C 14 alkylcarboxyoxy, or C 6 to C 14 arylcarboxyoxy; wherein the substituent on the R is optionally substituted with one or more hydroxy, fluoro, chloro, bromo, or iodo, and wherein, independently, each of the R 1 can be situated cis or trans to an adjacent R 2 , and wherein x is greater than 3.

9. The polymer of claim 8 , wherein X′ is O, NH, or NR, R is methyl or ethyl, m is 0.015 to 34.57, n is 1, and R 1 is H, R 2 is H, and R 3 is C 2 alkylene, and R 5 is C 6 to C 12 alkylene or C 6 arylene.

10. A method of preparing a polymer according to claim 8 , comprising:
providing a acrylic diene comprising monomer mixture, comprising the structure:

wherein: m>0.01; n≧1; X is OH, Cl, Br, I, OR, NHR, NR 2 , or RC(O)O; R 1 and R 2 are independently H, methyl, ethyl, C 3 to C 14 alkyl, C 6 to C 14 aryl, C 7 to C 14 alkylaryl, or C 7 to C 14 arylalkyl, unsubstituted or substituted with one or more hydroxy, halo, C 1 -C 14 alkoxy, C 6 to C 14 aryloxy, C 7 to C 14 alkylaryloxy, C 7 to C 14 arylalkoxy, cyano, alkylcarboxy, arylcarboxy, amino, C 1 -C 14 alkylamino, C 6 -C 14 arylamino, C 2 -C 14 dialkylamino, C 12 -C 16 diarylamino, C 7 -C 14 alkylarylamino, carboxyhydroxy, C 1 -C 14 alkoxycarboxy, C 6 to C 14 aryloxycarboxy, C 1 -C 14 alkylcarboxyoxy, or C 6 to C 14 arylcarboxyoxy, wherein the substituent is optionally further substituted with one or more hydroxy, fluoro, chloro, bromo, or iodo; R 3 is a C 1 to C 14 alkylene, C 6 to C 14 arylene, C 7 to C 14 alkylarylene, or any combination thereof connected by ester, amide, ether, amine, or carbonyl linkages, unsubstituted or substituted independently with one or more OH, fluoro, chloro, bromo, iodo, OR, NHR, NR 2 , or RC(O)O; and R is independently methyl, ethyl, C 3 to C 14 alkyl, C 6 to C 14 aryl, C 7 to C 14 alkylaryl, C 7 to C 14 arylalkyl, unsubstituted or substituted independently with one or more hydroxy, halo, C 1 -C 14 alkoxy, C 6 to C 14 aryloxy, C 7 to C 14 alkylaryloxy, C 7 to C 14 arylalkoxy, cyano, alkylcarboxy, arylcarboxy, amino, C 1 -C 14 alkylamino, C 6 -C 14 arylamino, C 2 -C 14 dialkylamino, C 12 -C 16 diarylamino, C 7 -C 14 alkylarylamino, carboxyhydroxy, C 1 -C 14 alkoxycarboxy, C 6 to C 14 aryloxycarboxy, C 1 -C 14 alkylcarboxyoxy, or C 6 to C 14 arylcarboxyoxy, wherein the substituent on the R is optionally substituted with one or more hydroxy, fluoro, chloro, bromo, or iodo;
providing a complementary comonomer of the structure:

wherein: X″ is OH, NH 2 or NHR; R 5 is C 1 to C 14 alkylene, C 6 to C 14 arylene, C 7 to C 14 alkylarylene, or any combination thereof connected by ester, amide, ether, amine, or carbonyl linkages, unsubstituted or substituted independently with one or more OH, fluoro, chloro, bromo, iodo, OR, NHR, NR 2 , or RC(O)O; and R is independently methyl, ethyl, C 3 to C 14 alkyl, C 6 to C 14 aryl, C 7 to C 14 alkylaryl, C 7 to C 14 arylalkyl, unsubstituted or substituted independently with one or more hydroxy, halo, C 1 -C 14 alkoxy, C 6 to C 14 aryloxy, C 7 to C 14 alkylaryloxy, C 7 to C 14 arylalkoxy, cyano, alkylcarboxy, arylcarboxy, amino, C 1 -C 14 alkylamino, C 6 -C 14 arylamino, C 2 -C 14 dialkylamino, C 12 -C 16 diarylamino, C 7 -C 14 alkylarylamino, carboxyhydroxy, C 1 -C 14 alkoxycarboxy, C 6 to C 14 aryloxycarboxy, C 1 -C 14 alkylcarboxyoxy, or C 6 to C 14 arylcarboxyoxy; wherein the substituent on the R is optionally substituted with one or more hydroxy, fluoro, chloro, bromo, or iodo;
combining the monomer mixture, the comonomer, and optionally a solvent into a polymerization mixture;
optionally adding a catalyst to the polymerization mixture; and
optionally promoting polymerization by heating and/or removal of a condensation product.

Assignees

• Univ Florida

Inventors

• Wagener Kenneth Boone
• Schulz Michael

Classifications

• C07C51/60 Primary

  by conversion of carboxylic acids or their anhydrides {or esters, lactones, salts} into halides with the same carboxylic acid part · CPC title

• C08F236/02

  the radical having only two carbon-to-carbon double bonds · CPC title

• C07C67/475

  by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• B01J31/2265

  Carbenes or carbynes, i.e.(image) · CPC title