Cycloalkylnorbornene monomers, polymers derived therefrom and their use in pervaporation

Patent metadata

Field	Value
Publication number	US-10227433-B2
Application number	US-201615257634-A
Country	US
Kind code	B2
Filing date	Sep 6, 2016
Priority date	Aug 7, 2012
Publication date	Mar 12, 2019
Grant date	Mar 12, 2019

Abstract

A variety of polycycloalkyl polynorbornene monomers and polymers derived therefrom are disclosed and claimed. The polymers and copolymers as disclosed herein are useful for forming pervaporation membranes, among other uses.

First claim

What is claimed is:

1. A compound of formula (I):

wherein:
each occurrence of X independently represents —CH 2 —or —CH 2 —CH 2 —;
m is an integer from 0 to 5 inclusive;
at least one of R 1 , R 2 , R 3 and R 4 independently represents -L-(C 7 -C 14 )tricycloalkyl or a group of formula (A):

 wherein:
each occurrence of Y independently represents —CH 2 —or —CH 2 —CH 2 —;
n is 1; and
R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 1 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 1 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;
L represents a bond; or

R 1 and R 3 taken together with the carbon atom to which they are attached form a substituted or unsubstituted (C 5 -C 7 )cycloalkyl or (C 6 -C 12 )bicycloalkyl ring;
remaining one or more of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 ))aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;
wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein:
D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene,
C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;
E is methyl, ethyl, CF 3 or C 2 F 5 ; and
R 13 is hydrogen or (C 1 -C 5 )alkyl.

2. The compound according to claim 1 , wherein X is CH 2 , m is 0;
each of R 2 , R 3 and R 4 is hydrogen, R 1 being a group of formula (A),
wherein Y is CH 2 , n is 1, and is represented by formula (II):

wherein:
each occurrence of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, -n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CF 3 , phenyl, benzyl, hydroxy, acetoxy, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, PhOH, PhOAc, C(CF 3 ) 2 OH , CH 2 C(CF 3 ) 2 OH, (CH 2 ) 2 C(CF 3 ) 2 OH, (CH 2 ) 3 C(CF 3 ) 2 OH, or PhC(CF 3 ) 2 OH.

3. The compound according to claim 1 , which is selected from the group consisting of:
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane;
2-(bicyclo[2.2.1]hept-5-en-2-yl)-5-phenyl-bicyclo[2.2.1]heptane;
2-(bicyclo[2.2.1]hept-5-en-2-yl)decahydro-1,4:5,8-dimethanonaphthalene;
2-(bicyclo[2.2.1]heptenyl)-6-bicyclo[2.2.1]heptylbicyclo[2.2.1]heptane;
3-(bicyclo[2.2.1]hept-5-en-2-yl)tricyclo[2.2.1.0 2,6 ]heptane; and
1-(bicyclo[2.2.1]hept-5-en-2-yl)adamantane.

4. A compound of formula (III):

wherein:
each occurrence of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CF 3 , bicycloheptyl, or phenyl.

5. The compound according to claim 4 , which is selected from the group consisting of:
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane;
2-(bicyclo[2.2.1]hept-5-en-2-yl)-5-phenyl-bicyclo[2.2.1]heptane; and
2-(bicyclo[2.2.1]heptenyl)-6-bicyclo[2.2.1]heptylbicyclo[2.2.1]heptane.

6. A polymer comprising a first repeating unit represented by formula (IA), said repeating unit is derived from a monomer of formula (I):

wherein:
each occurrence of X independently represents —CH 2 —or —CH 2 —CH 2 —;
m is an integer from 0 to 5 inclusive;
at least one of R 1 , R 2 , R 3 and R 4 independently represents a group of formula (A):

wherein:
each occurrence of Y independently represents —CH 2 —or —CH 2 —CH 2 —;
n is 0 or 1; and
R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl,(C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;
L represents a bond; or

R 1 and R 3 taken together with the carbon atom to which they are attached form a substituted or unsubstituted (C 5 -C 7 )cycloalkyl or (C 6 -C 12 )bicycloalkyl ring;
remaining one or more of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 3 - 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;
wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein:
D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene, C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;
E is methyl, ethyl, CF 3 or C 2 F 5 ; and
R 13 is hydrogen or (C 1 -C 5 )alkyl.

7. The polymer according to claim 6 , wherein R 1 is a group of formula (A), R 5 is hydrogen or phenyl, X and Y are CH 2 , m is 0, n is 0 or 1, L is a bond, and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are each hydrogen.

8. The polymer according to claim 6

Assignees

• Promerus Llc

Inventors

• Bell Andrew
• Langsdorf Leah
• Burtovyy Oleksandr

Classifications

• C07C13/605

  with a bridged ring system · CPC title

• B01D71/76

  Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 (rubbers in general B01D71/24) · CPC title

• C07C2603/62

  containing three- or four-membered rings · CPC title

• C07C39/04

  Phenol · CPC title

• B01D71/26

  Polyalkenes · CPC title