Bionic multisilicon copolymers used as novel cross-linking agents for preparing anion exchange hybrid membranes.

Bionic multisilicon copolymers have long-main chains and many branched chains, and contain multifunctional groups of -N(+)(CH(3))(3)Cl(-) and -Si(OCH(3))(3), which are similar to the stem, branch, fruit, and acetabula of a vine from bionic aspect, respectively. They have high flexibility, charge density, and cross-linking ability and thus can be used as novel cross-linking agents for preparing anion-exchange hybrid membranes. High content of -Si(OCH(3))(3) groups (68-78%) is suitable to enhance membrane stabilities. The membranes are stable in 65 °C water up to 120 h and can keep integrity in 2 mol/L NaOH for 192 h. High content of -N(+)(CH(3))(3)Cl(-) groups (42-55%) is suitable to enhance membrane electrical properties. The membranes have low membrane resistance (R(m), 0.59-0.94 Ω cm(2)) and high diffusion dialysis performance. The acid (H(+)) dialysis coefficients (U(H)) are in the range of 0.007-0.075 m h(-1) at room temperature and 0.015-0.115 m h(-1) at 40 °C. The separation factor (S(H/Fe)) can reach up to 43 at room temerature and 49 at 40 °C. All of the membranes are highly homogeneous, mechanically stable (21-31 MPa, 25-147%), and thermally stable (227-275 °C for halide form membranes, and 157-172 °C for OH(-) form membranes). Hence, the investigation of multisilicon copolymers will give rise to a new developing field in material and membrane sciences.

[1]  K. Shea,et al.  Bridged polysilsesquioxanes. molecular-engineered hybrid organic-inorganic materials , 2001 .

[2]  K. Shea,et al.  A mechanistic investigation of gelation. The sol-gel polymerization of precursors to bridged polysilsesquioxanes. , 2001, Accounts of chemical research.

[3]  R. Slade,et al.  Poly(ethylene-co-tetrafluoroethylene)-Derived Radiation-Grafted Anion-Exchange Membrane with Properties Specifically Tailored for Application in Metal-Cation-Free Alkaline Polymer Electrolyte Fuel Cells , 2007 .

[4]  Tongwen Xu,et al.  Novel anion-exchange organic–inorganic hybrid membranes prepared through sol–gel reaction of multi-alkoxy precursors , 2009 .

[5]  Jing Guo,et al.  Preparation and characterization of inorganic–organic hybrid proton exchange membranes based on phosphorylated PVA and PEG-grafted silica particles , 2008 .

[6]  R. K. Nagarale,et al.  Phosphonic acid functionalized aminopropyl triethoxysilane–PVA composite material: organic–inorganic hybrid proton-exchange membranes in aqueous media , 2005 .

[7]  T. Xu,et al.  Anion exchange hybrid membranes from PVA and multi-alkoxy silicon copolymer tailored for diffusion dialysis process , 2010 .

[8]  H. Zou,et al.  Polymer/silica nanocomposites: preparation, characterization, properties, and applications. , 2008, Chemical reviews.

[9]  S. Woo,et al.  Proton conductivity and methanol permeation in Nafion™/ORMOSIL prepared with various organic silanes , 2004 .

[10]  Soo-young Park,et al.  Preparation, swelling and electro-mechano-chemical behaviors of a gelatin-chitosan blend membrane. , 2008, Soft matter.

[11]  T. Xu,et al.  Multi-step sol-gel process and its effect on the morphology of polyethylene oxide (PEO)/SiO2 anion-exchange hybrid materials , 2007 .

[12]  T. Xu Ion exchange membranes: State of their development and perspective , 2005 .

[13]  Fei Yu,et al.  Novel anion-exchange organic–inorganic hybrid membranes: Preparation and characterizations for potential use in fuel cells , 2008 .

[14]  T. Okada,et al.  New highly proton conductive polymer membranes poly(vinyl alcohol)–2-acrylamido-2-methyl-1-propanesulfonic acid (PVA–PAMPS) , 2005 .

[15]  P. Gómez‐Romero Hybrid Organic–Inorganic Materials—In Search of Synergic Activity , 2001 .

[16]  R. Slade,et al.  Prospects for Alkaline Anion‐Exchange Membranes in Low Temperature Fuel Cells , 2005 .

[17]  T. Xu,et al.  Free-standing anion-exchange PEO–SiO2 hybrid membranes , 2008 .

[18]  R. Slade,et al.  Alkaline anion-exchange radiation-grafted membranes for possible electrochemical application in fuel cells , 2003 .

[19]  V. Shahi,et al.  Preparation of polyvinyl alcohol¿silica hybrid heterogeneous anion-exchange membranes by sol¿gel method and their characterization , 2005 .

[20]  B. P. Tripathi,et al.  Functionalized organic-inorganic nanostructured N-p-carboxy benzyl chitosan-silica-PVA hybrid polyelectrolyte complex as proton exchange membrane for DMFC applications. , 2008, The journal of physical chemistry. B.

[21]  T. Xu,et al.  Preparation and characterization of Type II anion exchange membranes from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) , 2008 .

[22]  A. Zhu,et al.  Performance of organic-inorganic hybrid anion-exchange membranes for alkaline direct methanol fuel cells , 2009 .

[23]  Tongwen Xu,et al.  Diffusion dialysis of hydrochloride acid at different temperatures using PPO–SiO2 hybrid anion exchange membranes , 2010 .

[24]  Guan-Hai Wang,et al.  Using novel polysaccharide-silica hybrid material to construct an amperometric biosensor for hydrogen peroxide. , 2006, The journal of physical chemistry. B.

[25]  T. Xu,et al.  Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: Effect of silica content and the single cell performance , 2010 .

[26]  T. Xu,et al.  PVA–silica anion-exchange hybrid membranes prepared through a copolymer crosslinking agent , 2010 .

[27]  S. Moon,et al.  Characterization of anion‐exchange membranes containing pyridinium groups , 2003 .

[28]  Young Moo Lee,et al.  Proton conductivity and methanol transport behavior of cross-linked PVA/PAA/silica hybrid membranes , 2005 .

[29]  I. Honma,et al.  Organic/inorganic nano-composites for high temperature proton conducting polymer electrolytes , 2003 .

[30]  Xuejun Cui,et al.  Organic–inorganic hybrid proton exchange membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid , 2007 .

[31]  Young Moo Lee,et al.  Preparation and characterization of crosslinked PVA/SiO2 hybrid membranes containing sulfonic acid groups for direct methanol fuel cell applications , 2004 .

[32]  G. Hsiue,et al.  Microstructural and morphological characteristics of PS-SiO2 nanocomposites , 2000 .

[33]  G. Gohil,et al.  Preparation of organic-inorganic composite anion-exchange membranes via aqueous dispersion polymerization and their characterization. , 2005, Journal of colloid and interface science.

[34]  R. Slade,et al.  Comparison of PVDF- and FEP-based radiation-grafted alkaline anion-exchange membranes for use in low temperature portable DMFCs , 2002 .