Functionalized linear and cyclic polyolefins

Patent metadata

Field	Value
Publication number	US-10619003-B2
Application number	US-201815860906-A
Country	US
Kind code	B2
Filing date	Jan 3, 2018
Priority date	Sep 4, 2013
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

Abstract

This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

First claim

The claimed invention is:

1. A method for making a linear polypentenamer, contacting a first olefin monomer with an olefin metathesis catalyst; and subjecting the first olefin monomer and the olefin metathesis catalyst to conditions effective to promote a first olefin metathesis reaction, wherein,
the first olefin monomer is of the formula (A*):

where R A1* is selected from H, OH, NH 2 , CH 2 OH, C(CH 3 ) 3 , or Si(CH 3 ) 3 ; the linear polypentenamer is of formula:

where n is an integer;
such that the linear polypentenamer has a number average molecular weight Mn in the range of 0.4 kDa to 500 kDa;
and wherein the method further comprises contacting a second olefin monomer with the first olefin monomer and the olefin metathesis catalyst wherein the second olefin monomer is of formula (E*):

2. The method of claim 1 , wherein linear polypentenamer is a polyhydroxy-polypentenamer of structure

wherein,
n is an integer;
z is an integer; and
m is an integer, such that the linear polyhydroxy-polypentenamer has a number average molecular weight M n in the range of 0.4 kDa to 500 kDa.

3. The method of claim 2 , wherein the olefin metathesis catalyst is a Group 8 transition metal complex of formula (I)

in which:
M is ruthenium;
n is 0;
m is 0;
k is 1;

L 1 and L 2 are trisubstituted phosphines independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); or L 1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L 2 is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph);
X 1 and X 2 are chloride; and
R 1 is hydrogen and R 2 is phenyl or CH═C(CH 3 ) 2 or thienyl; or R 1 and R 2 are taken together to form 3-phenyl-1H-indene.

Assignees

• California Inst Of Techn

Inventors

• Tuba Robert
• Grubbs Robert H

Classifications

• C08G2261/419

  Acyclic diene metathesis [ADMET] · CPC title

• C08G61/08 Primary

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

• C08G2261/3342

  derived from cycloolefins containing heteroatoms · CPC title

• C08G2261/1422

  containing OH groups · CPC title

• C08G2261/142

  Side-chains containing oxygen · CPC title