Cycloalkylnorbornene monomers, polymers derived therefrom and their use in pervaporation

1. A pervaporation membrane comprising a polymer comprising a first type of 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 and 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 and 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 1 to 5 inclusive, phenylene, C 6 H 4 (CH 2 ) s where s is an integer from 1 to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1 to 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 pervaporation membrane according to claim 1 in a form of a tubular composite, hollow fiber, a dense film flat sheet, or a thin film composite.

3. The pervaporation membrane according to claim 1 , which is capable of preferential permeability to a volatile organic over water, said permeability increasing with increasing organic concentration of a feed stream.

4. The pervaporation membrane according to claim 3 , wherein said volatile organic comprises butanol.

5. The pervaporation membrane according to claim 4 having a flux for butanol of at least about 100 g/m 2 ·h from a fermentation broth comprising at least about 1% by weight butanol, wherein the flux for butanol is, an amount of butanol (g) that flows through an unit area (m 2 ) of the pervaporation membrane per unit of time (h).

6. The pervaporation membrane according to claim 3 , wherein said volatile organic comprises phenol.

7. The pervaporation membrane according to claim 1 comprising a polymer selected from:

a homopolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]-heptane;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and hydroxyhexafluoroisopropylmethylnorbornene;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and norbornene; and

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and 5-n-butylbicyclo[2.2.1]hept-2-ene.

8. A method of separating an organic product from a feedstock selected from a fermentation broth or a waste containing the organic product comprising:

charging the feedstock to a pervaporation module containing a pervaporation membrane formed by a polymer according to claim 1 ; and

collecting a permeate vapor containing the organic product from the pervaporation module.

9. The method according to claim 8 , wherein the fermentation broth charged to the pervaporation module has a temperature from about 30° C. to about 110° C.

10. The method according to claim 8 , wherein a vacuum from about 0.1 in Hg to about 25 in Hg is applied to the pervaporation module.

11. The method according to claim 8 , wherein the pervaporation membrane is formed by a polymer selected from:

a homopolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]-heptane;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and hydroxyhexafluoroisopropylmethylnorbornene;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and norbornene; and

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and 5-n-butylbicyclo[2.2.1]hept-2-ene.

12. The method according to claim 8 , wherein the organic product is butanol, ethanol or phenol.

13. A method of separating butanol or phenol from a feedstock selected from a fermentation broth or a waste containing butanol or phenol comprising:

charging the feedstock to a pervaporation module containing a pervaporation membrane formed by a polymer selected from:

a homopolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and hydroxyhexafluoroisopropylmethylnorbornene;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and norbornene; and

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and 5-n-butylbicyclo[2.2.1]hept-2-ene; and

collecting a permeate vapor containing butanol or phenol from the pervaporation module.