Pervaporation membranes derived from polycyclo-olefinic block copolymers

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 block copolymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
• a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
• a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C4F9NB-b-BuDMMINB);
• a block copolymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]kept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBANB);
• a block copolymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB);
• a block terpolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB);
• and
• a block terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB);
• and
• collecting a permeate vapor containing butanol or phenol from the pervaporation module.

A method of forming a membrane comprising:

• pouring a solution of a block copolymer of the formula (VI):
• (A)m-b-(B)n (VI)
• onto a suitable substrate;
• where each of m and n is an integer of at least 15;
• b denotes a bond;
• A and B are different from each other and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV):
• wherein:
• denotes a place of bonding with another repeat unit;
• p is an integer 0, 1 or 2;
• R3, R4, R5 and R6 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C1-C16)alkyl, hydroxy(C1-C16)alkyl, perfluoro(C1-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C3)alkyl, di(C1-C2)alkylmaleimide(C3-C6)alkyl, di(C1-C2)alkylmaleimide(C2-C6)alkoxy(C1-C2)alkyl, hydroxy, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C5-C10)heteroaryloxy(C1-C3)alkyl, (C6-C10)aryloxy, (C5-C10)heteroaryloxy or (C1-C6)acyloxy, where each of the aforementioned substituents are optionally substituted with halogen or hydroxy;
• and
• drying the substrate at a suitable temperature to form the membrane.