Alternating ring-opening metathesis polymerization

Patent metadata

Field	Value
Publication number	US-9624338-B2
Application number	US-201414906834-A
Country	US
Kind code	B2
Filing date	Jul 22, 2014
Priority date	Jul 22, 2013
Publication date	Apr 18, 2017
Grant date	Apr 18, 2017

Abstract

The invention relates to the field of polymers and olefin polymerization, and more specifically olefin metathesis polymerization. The invention provides regioregular alternating polymers and methods of synthesizing such polymers. To demonstrate, polymers were synthesized and modified with a FRET pair (Trp/Dansyl) post-polymerization.

First claim

We claim:

1. A method for producing a polymer comprising the repeating unit (Ib) or (Ic):

which comprises contacting an olefin of structure (II) with a cyclobutene of structure (III)

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, C 1 -C 20 alkoxy, C 1 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 1 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be optionally substituted with up to three substituents selected from halo, CN, NO 2 , oxo, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, and a heterocyclic group;
n is a number between 2 and 20;
R 1 through R 6 are 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, or halogen;
R 1 through R 6 may be taken together to form a 5- to 7-membered ring which may be optionally substituted with up to three substituents selected from halo, CN, NO 2 , oxo, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;

A is a C 2 -C 20 alkyl;
with the proviso that any carbon-carbon double bonds in R or in R 1 through R 6 are essentially unreactive toward metathesis reactions with the catalyst.

2. The method of claim 1 , further comprising combining a polymer block comprising repeating units (Ib) or (Ic) into a block copolymer.

3. The method of claim 1 , wherein the catalyst is an alkylidene ruthenium complex of formula (L)(L′)X 2 Ru=CHR′ or (L) 2 (L′)X 2 Ru═CHR′, wherein R′ is selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 6 cycloalkyl, and aryl;
L is a ligand selected from the group consisting of trialkyl phosphines, triarylphosphines, tri(cycloalkyl)phosphines, pyridine and substituted pyridine;
L′ is a ligand selected from the group consisting of trialkyl phosphines, triarylphosphines, tri(cycloalkyl)phosphines, pyridine and substituted pyridine, and imidazolin-2-ylidine carbenes of formula

wherein Ar is an ortho-substituted aryl or an aryl; and
X is F, Cl, or Br.

4. The method of claim 2 , wherein the catalyst is an alkylidene ruthenium complex of formula (L)(L′)X 2 Ru═CHR′ or (L) 2 (L′)X 2 Ru═CHR′, wherein R′ is selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 6 cycloalkyl, and aryl;
L is a ligand selected from the group consisting of trialkyl phosphines, triarylphosphines, tri(cycloalkyl)phosphines, pyridine and substituted pyridine;
L′ is a ligand selected from the group consisting of trialkyl phosphines, triarylphosphines, tri(cycloalkyl)phosphines, pyridine and substituted pyridine, and imidazolin-2-ylidine carbenes of formula

wherein Ar is an ortho-substituted aryl or an aryl; and
X is F, Cl, or Br.

5. The method of claim 3 , wherein L is pyridine or substituted pyridine.

6. The method of claim 4 , wherein L is 3-bromopyridyl, 3-chloropyridyl or pyridine.

7. The method of claim 3 , wherein L′ is an imidazolin-2-ylidine carbene and Ar is selected from the group consisting of phenyl, mesityl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2,3-diisopropylphenyl, 2,6-difluorophenyl, and 3,5-di-t-butylphenyl.

8. The method of claim 1 , wherein the catalyst is a molybdenum or tungsten metathesis catalyst.

Assignees

• Univ New York State Res Found

Inventors

• Sampson Nicole S
• Tan Li
• Parker Kathlyn

Classifications

• A61K9/1075

  Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers (A61K9/0026 takes precedence) · CPC title

• A61K47/32

  Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers {, poly(meth)acrylates, or polyvinyl pyrrolidone} · CPC title

• C08F232/04

  having one carbon-to-carbon double bond · CPC title

• C08G2261/74

  Further polymerisation of the obtained polymers, e.g. living polymerisation to obtain block-copolymers · CPC title

• C08G2261/124

  alternating · CPC title