Polynorbornene-based polycations
A multiblock, cationic-functionalized norbornene copolymer is formed by a process including performing a vinyl addition polymerization in the presence of a metal catalyst of a first norbornene monomer substituted with a first alkyl group and a second norbornene monomer substituted with a second alkyl group by adding a predetermined amount of the first norbornene monomer and a predetermined amount of the second norbornene monomer sequentially to the reaction to form blocks of an intermediate norbornene multiblock copolymer. The second alkyl group includes a substituent which undergoes a reaction with a precursor for a cationic group having a volume less than 0.25 cm 3 /mol. The process further includes reacting the precursor for the cationic group with the intermediate norbornene multiblock copolymer to form the multiblock, cationic-functionalized norborene copolymer.
1 . A multiblock, ammonium-functionalized norbornene copolymer formed by a process comprising: performing a controlled vinyl addition polymerization in the presence of a metal catalyst of a first norbornene monomer substituted with a first alkyl group and at least a second norbornene monomer substituted with a second alkyl group by adding a predetermined amount of the first norbomene monomer and a predetermined amount of the second norbornene monomer sequentially to the reaction to form blocks of an intermediate norbornene multiblock copolymer, the second alkyl group comprising a substituent which undergoes a substitution reaction with a tertiary precursor of an ammonium cationic group, and reacting the tertiary precursor for the ammonium cationic group with the intermediate norbornene multiblock copolymer to form the multiblock, ammonium-functionalized norbornene copolymer, wherein the first alkyl group is a C1-C20 alkyl group and the second alkyl group is a C1-C20 alkyl group, and wherein the multiblock, ammonium-functionalized norbornene copolymer comprises an odd number of blocks and wherein a first block and a last block of the multiblock, ammonium-functionalized norbornene copolymer are formed from the first norbornene monomer.
2 . The multiblock, ammonium-functionalized norbornene copolymer of claim 1 wherein the substituent of the second alkyl group is a halo atom, a mesylate group, or tosylate group.
3 . The multiblock, ammonium-functionalized norbornene copolymer of claim 2 wherein the first alkyl group is a C1-C12 alkyl group and the second alkyl group is a C1-C12 alkyl group.
4 . The multiblock, ammonium-functionalized norbornene copolymer of claim 2 wherein the intermediate norbornene multiblock copolymer has a number average molecular weight above the entanglement molecular weight thereof.
5 . The multiblock, ammonium-functionalized norbomene copolymer of claim 2 wherein the ammonium-functionalized norbornene copolymer has a polydispersity less than 1.5.
6 . The multiblock, ammonium-functionalized norbomene copolymer of claim 2 wherein the multiblock, ammonium-functionalized norbornene copolymer includes no crosslinks.
7 . The multiblock, ammonium-functionalized norbomene copolymer of claim 4 wherein the multiblock, ammonium-functionalized norbornene copolymer is solution processible.
8 . A method of synthesizing a multiblock, ammonium-functionalized norbornene copolymer comprising: performing a controlled vinyl addition polymerization in the presence of a metal catalyst of a first norbornene monomer substituted with a first alkyl group and at least a second norborene monomer substituted with a second alkyl group by adding a predetermined amount of the first norborene monomer and a predetermined amount of the second norbornene monomer sequentially to the reaction to form blocks of an intermediate norbornene multiblock copolymer, the second alkyl group comprising a substituent which undergoes a substitution reaction with a tertiary amine precursor of an ammonium cationic group, and reacting the tertiary amine precursor for the ammonium cationic group with the intermediate norbornene multiblock copolymer to form the multiblock, ammonium-functionalized norbornene copolymer, wherein the first alkyl group is a C1-C20 alkyl group and the second alkyl group is a C1-C20, and wherein the multiblock, ammonium-functionalized norbornene copolymer comprises an odd number of blocks and wherein a first block and a last block of the multiblock, ammonium-functionalized norborene copolymer are formed from the first monomer.
9 . The method of claim 8 wherein the substituent of the second alkyl group is a halo atom, a mesylate group, or tosylate group.
10 . The method of claim 8 wherein the first alkyl group is a C1-C12 alkyl group and the second alkyl group is a C1-C12 alkyl group.
11 . The method of claim 8 wherein the intermediate norbornene multiblock copolymer has a number average molecular weight above the entanglement molecular weight thereof.
12 . The method of claim 11 wherein the multiblock, ammonium-functionalized norbornene copolymer has a polydispersity less than 1.5.
13 . The method of claim 11 wherein the multiblock, ammonium-functionalized norbornene polymer includes no crosslinks.
14 . The method of claim 11 wherein the multiblock, ammonium-functionalized norbornene copolymer is solution processible.
15 . The method of claim 14 further comprising casting a film of the multiblock, ammonium-functionalized norbornene copolymer from solution.
16 . A membrane formed from solution casting of a multiblock, ammonium-functionalized norbornene copolymer formed by a process comprising: performing a controlled vinyl addition polymerization in the presence of a metal catalyst of a first norbornene monomer substituted with a first alkyl group and at least a second norbornene monomer substituted with a second alkyl group by adding a predetermined amount of the first norbornene monomer and a predetermined amount of the second norbornene monomer sequentially to the reaction to form blocks of an intermediate norbornene multiblock copolymer, the second alkyl group comprising a substituent which undergoes a substitution reaction with a tertiary precursor of an ammonium cationic group, and reacting the tertiary precursor for the ammonium cationic group with the intermediate norborene multiblock copolymer to form the multiblock, ammonium-functionalized norbornene copolymer, wherein the first alkyl group is a C1-C20 alkyl group and the second alkyl group is a C1-C20 alkyl group, and wherein the multiblock, ammonium-functionalized norbornene copolymer comprises an odd number of blocks and wherein a first block and a last block of the multiblock, ammonium-functionalized norbornene copolymer are formed from the first norbornene monomer.