Formation of pore-filled ion-exchange membranes within situ crosslinking: Poly(vinylbenzyl ammonium salt)-filled membranes

Abstract

Robust, polyelectrolyte‐filled, microporous membranes were prepared by the introduction and crosslinking of a preformed polymer within the pores of a poly(propylene) host membrane. Specifically, poly(vinylbenzyl chloride) (PVBCl) was reacted with piperazine or 1,4‐diaminobicyclo[2.2.2]octane in an N,N‐dimethylformamide (DMF) solution contained in the pores of the microporous base membrane. The remaining chloromethyl groups were reacted with an amine, such as trimethylamine, to form positively charged ammonium sites. This simple two‐step procedure gave dimensionally stable, anion‐exchange membranes in which the degree of crosslinking and the mass loading were determined by the concentration of PVBCl and crosslinker in the starting DMF solution. The incorporated polyelectrolyte gel was evenly distributed within the pores of the host membrane with no surface layers present. The membranes are fully characterized. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 807–820, 2001

Quaternary ammonium bearing hyper-crosslinked polymer encapsulation on Fe 3 O 4 nanoparticles

“…As can be seen from the data given in Table1, TcO 4 À ions were quantitatively sorbed from 0.5 mol L À1 salt/acid solution except in salt with I À ions which were least hydrated among the anions present in the salt/acid used in this study. The most hydrated anion in the salt/acid listed in Table1is SO 42À anion whose DG hy value is À1080 kJ mol À1 40. As expected from the DG hy value, the sorption efficiency of TcO 4…”

“…It is reported that DABCO is mono-reacted when present in excess, and would not lead to crosslinking. 40 Therefore, DABCO reacted particles were further treated with DBO for the optimum conversion of tertiary amine sites to a quaternary amine. This sequence of chemical treatments and nal structure of the thus formed particles (Fe 3 O 4 @PVB-DABCO-DBO) are shown in Scheme 1.…”

Quaternary ammonium bearing hyper-crosslinked polymer encapsulation on Fe 3 O 4 nanoparticles

“…As can be seen from the data given in Table1, TcO 4 À ions were quantitatively sorbed from 0.5 mol L À1 salt/acid solution except in salt with I À ions which were least hydrated among the anions present in the salt/acid used in this study. The most hydrated anion in the salt/acid listed in Table1is SO 42À anion whose DG hy value is À1080 kJ mol À1 40. As expected from the DG hy value, the sorption efficiency of TcO 4…”

“…It is reported that DABCO is mono-reacted when present in excess, and would not lead to crosslinking. 40 Therefore, DABCO reacted particles were further treated with DBO for the optimum conversion of tertiary amine sites to a quaternary amine. This sequence of chemical treatments and nal structure of the thus formed particles (Fe 3 O 4 @PVB-DABCO-DBO) are shown in Scheme 1.…”

High-Capacity Retention Thermally Reinforced Pore-Filled Anion Exchange Membrane for All-Vanadium Flow Batteries

“…It is well reported in the literature that the formation of a high-molecular-weight polymer in the pores of a substrate dramatically increases its surface roughness. 21,40 Recently, our group 41,42 also reported a commendable change in roughness for a polyaniline and poly(o-anisidine)-coated polypropylene support. The increased surface roughness for the PFAEM suggests the successful entrapment of poly(4-vinyl pyridine) in the voids of the porous PP substrate.…”

Broad-Spectrum Antimicrobial Polymer-Coated Fabrics via Commodity Polystyrene Upcycling

“…The first step of the two-stage PS functionalization sequence involved ZnCl 2 -catalyzed chloromethylation of the pendent phenyl rings (Scheme ). Friedel–Crafts chloromethylation has been previously used to functionalize cross-linked PS derivatives (e.g., PS- co -divinyl-benzene) for ion-exchange membrane modification and in the preparation of solid supports for organic synthesis, e.g., Merrifield resin for peptide synthesis. − However, compared to the chemical modification of insoluble PS derivatives, the chloromethylation of soluble high molecular weight PS has received relatively scant attention. A major reason for this is that CMPS is predominantly made by polymerizing the styrenic monomer 4-vinylbenzyl chloride .…”

Quaternary ammonium bearing hyper-crosslinked polymer encapsulation on Fe 3 O 4 nanoparticles

“…As can be seen from the data given in Table1, TcO 4 À ions were quantitatively sorbed from 0.5 mol L À1 salt/acid solution except in salt with I À ions which were least hydrated among the anions present in the salt/acid used in this study. The most hydrated anion in the salt/acid listed in Table1is SO 42À anion whose DG hy value is À1080 kJ mol À1 40. As expected from the DG hy value, the sorption efficiency of TcO 4…”

“…It is reported that DABCO is mono-reacted when present in excess, and would not lead to crosslinking. 40 Therefore, DABCO reacted particles were further treated with DBO for the optimum conversion of tertiary amine sites to a quaternary amine. This sequence of chemical treatments and nal structure of the thus formed particles (Fe 3 O 4 @PVB-DABCO-DBO) are shown in Scheme 1.…”

High-Capacity Retention Thermally Reinforced Pore-Filled Anion Exchange Membrane for All-Vanadium Flow Batteries

“…It is well reported in the literature that the formation of a high-molecular-weight polymer in the pores of a substrate dramatically increases its surface roughness. 21,40 Recently, our group 41,42 also reported a commendable change in roughness for a polyaniline and poly(o-anisidine)-coated polypropylene support. The increased surface roughness for the PFAEM suggests the successful entrapment of poly(4-vinyl pyridine) in the voids of the porous PP substrate.…”

Broad-Spectrum Antimicrobial Polymer-Coated Fabrics via Commodity Polystyrene Upcycling

“…The first step of the two-stage PS functionalization sequence involved ZnCl 2 -catalyzed chloromethylation of the pendent phenyl rings (Scheme ). Friedel–Crafts chloromethylation has been previously used to functionalize cross-linked PS derivatives (e.g., PS- co -divinyl-benzene) for ion-exchange membrane modification and in the preparation of solid supports for organic synthesis, e.g., Merrifield resin for peptide synthesis. − However, compared to the chemical modification of insoluble PS derivatives, the chloromethylation of soluble high molecular weight PS has received relatively scant attention. A major reason for this is that CMPS is predominantly made by polymerizing the styrenic monomer 4-vinylbenzyl chloride .…”

Quaternary ammonium bearing hyper-crosslinked polymer encapsulation on Fe 3 O 4 nanoparticles

“…As can be seen from the data given in Table1, TcO 4 À ions were quantitatively sorbed from 0.5 mol L À1 salt/acid solution except in salt with I À ions which were least hydrated among the anions present in the salt/acid used in this study. The most hydrated anion in the salt/acid listed in Table1is SO 42À anion whose DG hy value is À1080 kJ mol À1 40. As expected from the DG hy value, the sorption efficiency of TcO 4…”

“…It is reported that DABCO is mono-reacted when present in excess, and would not lead to crosslinking. 40 Therefore, DABCO reacted particles were further treated with DBO for the optimum conversion of tertiary amine sites to a quaternary amine. This sequence of chemical treatments and nal structure of the thus formed particles (Fe 3 O 4 @PVB-DABCO-DBO) are shown in Scheme 1.…”

High-Capacity Retention Thermally Reinforced Pore-Filled Anion Exchange Membrane for All-Vanadium Flow Batteries

“…It is well reported in the literature that the formation of a high-molecular-weight polymer in the pores of a substrate dramatically increases its surface roughness. 21,40 Recently, our group 41,42 also reported a commendable change in roughness for a polyaniline and poly(o-anisidine)-coated polypropylene support. The increased surface roughness for the PFAEM suggests the successful entrapment of poly(4-vinyl pyridine) in the voids of the porous PP substrate.…”

Broad-Spectrum Antimicrobial Polymer-Coated Fabrics via Commodity Polystyrene Upcycling

“…The first step of the two-stage PS functionalization sequence involved ZnCl 2 -catalyzed chloromethylation of the pendent phenyl rings (Scheme ). Friedel–Crafts chloromethylation has been previously used to functionalize cross-linked PS derivatives (e.g., PS- co -divinyl-benzene) for ion-exchange membrane modification and in the preparation of solid supports for organic synthesis, e.g., Merrifield resin for peptide synthesis. − However, compared to the chemical modification of insoluble PS derivatives, the chloromethylation of soluble high molecular weight PS has received relatively scant attention. A major reason for this is that CMPS is predominantly made by polymerizing the styrenic monomer 4-vinylbenzyl chloride .…”