Alkene isomerization as an entry to efficient alternating ring-opening metathesis polymerization (i-AROMP)

Patent metadata

Field	Value
Publication number	US-10487172-B2
Application number	US-201615545580-A
Country	US
Kind code	B2
Filing date	Mar 21, 2016
Priority date	Mar 20, 2015
Publication date	Nov 26, 2019
Grant date	Nov 26, 2019

Abstract

This invention relates to the field of polymers and olefin polymerization, and more specifically olefin metathesis polymerization. Specifically, the present invention provides a polymer comprising rigorously alternating AB subunits and methods of formation of the AB alternating polymers. In the polymers and process of the invention, the A monomer is derived from a cyclobutene derivative, and the B monomer is derived from a cyclohexene derivative. The polymerization takes place in the presence of an olefin metathesis catalyst.

First claim

We claim:

1. A process for producing an alternating AB copolymer comprising the repeating unit I,

comprising:
(1) optionally isomerizing a cyclobutene of structure III in the presence of an olefin metathesis catalyst to form a cyclobutene III′:

(2) polymerization of the cyclobutene III′ with a cyclohexene II:

in the presence of an olefin metathesis catalyst;
wherein R is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;
n is between 2 and 500;
each substituent R 1 through R 4 is independently selected from the group consisting of H, aldehyde, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 6 cycloalkyl, aryl, heterocyclyl, C 1 -C 20 alkoxy, C 1 -C 20 acyloxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, arylamino, and halogen, and adjacent substitutions of R 1 -R 4 may be taken together to form a 5- to 7-membered ring which may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;
and wherein R 5 and R 6 are taken together to form a 5- or 6-membered ring, which may contain up to two heteroatoms in the ring selected from O or N, and which may be unsubstituted or substituted with up to four substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

2. The process according to claim 1 , wherein the alternating AB copolymer comprises the repeating unit Ia

wherein X is O or NH; and
R a is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

3. The process according to claim 1 , wherein R 5 and R 6 are taken together to form a cyclohexyl ring, which may be substituted.

4. The process according to claim 1 , wherein the alternating AB copolymer comprises the repeating unit Ib

wherein
R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

5. The process according to claim 1 , wherein the cyclohexene has the structure IIa:

wherein each substituent R 2 and R 3 is independently selected from H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, arylamino or halogen, and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, and a heterocyclic group, and alternatively R 2 and R 3 are be taken together to form a 5- to 7-membered ring which may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

6. The process according to claim 5 , wherein the cyclohexene has the structure:

7. The process according to claim 1 , wherein the cyclobutene has the structure IIIa or IIIa′, in which the cyclobutene of structure IIIa is isomerized to a cyclobutene of structure IIIa′

in the presence of an olefin metathesis catalyst,
wherein X is selected from O, or NH, and
R a is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

8. The process according claim 1 , wherein the cyclobutene has the structure IIIb or IIIb′, in which the cyclobutene of structure IIIb is isomerized to a cyclobutene of structure IIIb′

in the presence of an olefin metathesis catalyst;
wherein R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

9. The process according to claim 1 , wherein the cyclobutene has the structure IIIc or IIIc′, in which the cyclobutene of structure IIIc is isomerized to a cyclobutene of structure IIIc′

in the presence of an olefin metathesis catalyst;
wherein R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;
m is an intege

Assignees

• Univ New York State Res Found

Inventors

• Sampson Nicole S
• Tan Li
• Parker Kathlyn

Classifications

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G2261/1426

  containing carboxy groups (COOH) and/or -C(=O)O-moieties · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• B01J31/2265

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

• C07C13/32

  with condensed rings · CPC title