Supported membranes by thermal and uv inititated mass polymerization

A kit for forming an anion exchange membrane comprising:

• a) one or more monomers of formula (I):
• wherein:
• Y and Y′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
• m is an integer from 0 to 3;
• at least one of R1, R2, R3 or R4 is a group of the formula R-X,
• where R is selected from the group consisting of (C1-C10)alkylene, (C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkylene, (C1-C10)alkylene(C6-C10)arylene and (C1-C10)alkylene(C6-C10)arylene(C1-C10) alkylene;
• X is selected from the group consisting of halogen, hydroxy, (C1-C10)alkoxy and (C6-C12)aryloxy;
• and
• the remaining R1, R2, R3 and R4 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl (C6-C10)aryl;
• b) optionally one or more monomers of formula (II):
• wherein:
• Z and Z′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
• n is an integer from 0 to 3;
• and
• R8, R9, R10 and R11 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
• c) one or more monomer of formula (III):
• wherein:
• a is an integer 0, 1 or 2;
• b is an integer from 1 to 10;
• and
• K and K′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2—, —O— and —S—;
• d) a photoactive palladium catalyst comprising:
• i) a palladium compound of formula (V):
• Pd (OCOR17)2(P(R18)3)2 (V)
• wherein:
• each occurrence of R17 is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl and (C6-C12)aryl;
• and
• each occurrence of R18 is independently selected from the group consisting of (C3-C10)cycloalkyl and (C6-C12)aryl;
• and
• ii) a photoinitiator selected from the group consisting of:
• a compound of formula (VII):
• a compound of formula (VIII):
• wherein:
• d is an integer from 0 to 5;
• An⊖ is selected from the group consisting of Cl⊖, Br⊖, I⊖, BF4⊖, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate, phenyltris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-1]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]--5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF6⊖, SbF6⊖, AsF6⊖, n-C4F9SO3⊖, CF3SO3⊖, (CF3SO2)2N⊖, (CF3SO2)3C⊖ and p-CH3(C6H4)—SO3⊖:
• R19, R20, R21, R22 and R23 are the same or different and each independently selected from the group consisting of halogen, hydrogen, methyl, ethyl, linear or branched (C3-C20)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl (C1-C3)alkyl, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C6-C10)-aryloxy, (C6-C10)thioaryl, (C1-C6)alkanoyl(C6-C10)thioaryl, (C1-C6)alkoxy (C6-C10)aroyl(C1-C6)alkyl and (C6-C10)thioaryl-(C6-C10)diarylsulfonium salt;
• and
• wherein the amount of monomer of formula (III) present is no more than 3 mole percent based on the total combined moles of monomer of formula (I), monomer of formula (II), if present, and monomer of formula (III).

A method for forming an anion exchange membrane comprising:

• forming a solution comprising:
• a) one or more monomers of formula (I):
• wherein:
• Y and Y′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
• m is an integer from 0 to 3;
• at least one of R1, R2, R3 or R4 is a group of the formula R—X,
• where R is selected from the group consisting of (C1-C10) alkylene, (C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkylene, (C1-C10)alkylene(C6-C10)arylene and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkylene;
• X is selected from the group consisting of halogen, hydroxy, (C1-C10)alkoxy and (C6-C12)aryloxy;
• and
• the remaining R1, R2, R3 and R4 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
• b) optionally one or more monomers of formula (II):
• wherein:
• Z and Z′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
• n is an integer from 0 to 3;
• and
• R8, R9, R10 and R11 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10) alkyl(C6-C10)aryl
• c) one or more monomer of formula (III):
• wherein:
• a is an integer 0, 1 or 2;
• b is an integer from 1 to 10;
• and
• K and K′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2—, —O— and —S—;
• d) a photoactive palladium catalyst comprising:
• i) a palladium compound of formula (V):
• Pd(OCOR17)2(P(R18)3)2 (V)
• wherein:
• each occurrence of R17 is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl and (C6-C12)aryl;
• and
• each occurrence of R18 is independently selected from the group consisting of (C3-C10)cycloalkyl and (C6-C12)aryl;
• and
• ii) a photoinitiator selected from the group consisting of:
• a compound of formula (VII):
• a compound of formula (VIII):
• wherein:
• d is an integer from 0 to 5;
• An⊖ is selected from the group consisting of Cl⊖, Br⊖, I⊖, BF4⊖, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate, phenyltris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-1]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]--5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF6⊖, SbF6⊖, AsF6⊖, n-C4F9SO3⊖, CF3SO3⊖, (CF3SO2)2N⊖, (CF3SO2)3C⊖ and p-CH3(C6H4)—SO3⊖;
• R19, R20, R21, R22 and R23 are the same or different and each independently selected from the group consisting of halogen, hydrogen, methyl, ethyl, linear or branched (C3-C20)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C6-C10)-aryloxy, (C6-C10)thioaryl, (C1-C6)alkanoyl(C6-C10) thioaryl, (C1-C6)alkoxy (C6-C10)aroyl(C1-C6)alkyl and (C6-C10)thioaryl-(C6-C10)diarylsulfonium salt;
• and
• coating said solution onto a membrane support;
• heating the coated membrane support to a temperature from about 80° C. to about 120° C. for about 30 minutes to about 90 minutes;
• treating the heated membrane support with aqueous tri-(C1-C4)alkylamine solution at a temperature from about 20° C. to about 50° C. for about 2 days to about 5 days to form a quaternized anion exchange membrane;
• and
• washing the quaternized anion exchange membrane with water;
• and
• soaking the quaternized anion exchange membrane in alkali solution to form the anion exchange membrane;
• and wherein the amount of monomer of formula (III) present is no more than 3 mole percent based on the total combined moles of monomer of formula (I), monomer of formula (II), if present, and monomer of formula (III).