Sodium 4-vinylbenzenesulfonate Research Articles

Molecular Design of Highly Stretchable Ionomers

Application of ionomers is often disturbed by their brittleness originating from limited stretchability of the network strands physically cross-linked by the ionic sites therein. Thus, an effective method of improving the ductility is to increase the length of network strands (and/or entanglements). Considering this point, this study examined linear viscoelasticity (LVE) and nonlinear elongational rheology of unentangled copolymers of hexyl methacrylate (HMA) and the ionic monomer sodium 4-vinylbenzenesulfonate hydrate (SSNa). The ionized SSNa monomer, being randomly distributed along the chain backbone at a concentration ranging from <1 to ∼4 monomers per chain, served as the physical cross-link (or physical branching point). The LVE data showed a sol-to-gel transition, and the ductility of the sample turns out to be strongly related to the degree of gelation. Analysis of those data gave an average length of the network strands, and the ductility of the ionomer samples detected in the nonlinear elongatio...

Proton conducting composite membranes from crosslinked poly(vinyl alcohol) and poly(styrene sulfonic acid)-functionalized silica nanoparticles

Proton conducting membranes based on crosslinked poly(vinyl alcohol) (PVA) and poly (styrene sulfonic acid)-functionalized silica particles (PSSA-Si) were reported. Two-step crosslinking process involving sulfosuccinic acid (SSA) and glutaraldehyde as crosslinking agents was conducted to provide additional proton source and to enhance hydrolytic and mechanical stabilities. PSSA-Si was synthesized from vinyltrimethoxysilane via Stöber method, followed by radical polymerization of sodium 4-vinylbenzenesulfonate on the silica particle. The obtained PSSA-Si was characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The effects of PSSA-Si loading (0, 2.5, 5, and 10%) and PSSA content in PSSA-Si (2, 5, 8, and 12%) on membrane properties including surface morphology, water vapor absorption, water uptake, ion exchange capacity, mechanical and oxidative stabilities, and proton conductivity were investigated and discussed. Proton conductivities of these composite membranes were found to increase with PSSA-Si loading and PSSA content. Promising proton conductivities of ∼0.072 S/cm were obtained from PVA-8%PSSA-Si-10 and PVA-12%PSSA-Si-10 membranes, having PSSA-Si loading of 10%, and PSSA contents of 8%, and 12%, respectively. In addition, these membranes showed good hydrolytic and oxidative stabilities with high storage moduli.

A facile method to prepare a versatile surface coating with fibrinolytic activity, vascular cell selectivity and antibacterial properties.

Clot and thrombus formation on surfaces that come into contact with blood is still the most serious problem for blood contacting devices. Despite many years of continuous efforts in developing hemocompatible materials, it is still of great interest to develop multifunctional materials to enable vascular cell selectivity (to favor rapid endothelialization while inhibiting smooth muscle cell proliferation) and improve hemocompatibility. In addition, biomaterial-associated infections also cause the failure of biomedical implants and devices. However, it remains a challenging task to design materials that are multifunctional, since one of their functions will usually be compromised by the introduction of another function. In the present work, the gold substrate was first layer-by-layer (LbL) deposited with a multilayered polyelectrolyte film containing chitosan (positively charged) and a copolymer of sodium 4-vinylbenzenesulfonate (SS) and the "guest" adamantane monomer 1-adamantan-1-ylmethyl methacrylate (P(SS-co-Ada), negatively charged) via electro-static interactions, referred to as Au-LbL. The chitosan and P(SS-co-Ada) were intended to provide, respectively, resistance to bacteria and heparin-like properties. Then, "host" β-cyclodextrin derivatives bearing seven lysine ligands (CD-L) were immobilized on the Au-LbL surface by host-guest interactions between adamantane residues and CD-L, referred to as Au-LbL/CD-L. Finally, a versatile surface coating with fibrinolytic activity (lysis of nascent clots), vascular cell selectivity and antibacterial properties was developed.

Sulfonate Groups and Saccharides as Essential Structural Elements in Heparin-Mimicking Polymers Used as Surface Modifiers: Optimization of Relative Contents for Antithrombogenic Properties.

Blood compatibility is a long sought-after goal in biomaterials research, but remains an elusive one, and in spite of extensive work in this area, there is still no definitive information on the relationship between material properties and blood responses such as coagulation and thrombus formation. Materials modified with heparin-mimicking polymers have shown promise and indeed may be seen as comparable to materials modified with heparin itself. In this work, heparin was conceptualized as consisting of two major structural elements: saccharide- and sulfonate-containing units, and polymers based on this concept were developed. Copolymers of 2-methacrylamido glucopyranose, containing saccharide groups, and sodium 4-vinylbenzenesulfonate, containing sulfonate groups, were graft-polymerized on vinyl-functionalized polyurethane (PU) surfaces by free radical polymerization. This graft polymerization method is simple, and the saccharide and sulfonate contents are tunable by regulating the feed ratio of the monomers. Homopolymer-grafted materials, containing only sulfonate or saccharide groups, showed different effects on cell-surface interactions including platelet adhesion, adhesion and proliferation of vascular endothelial cells, and adhesion and proliferation of smooth muscle cells. The copolymer-grafted materials showed effects due to both sulfonate and saccharide elements with respect to blood responses, and the optimum composition was obtained at a 2:1 ratio of sulfonate to saccharide units (material designated as PU-PS1M1). In cell adhesion experiments, this material showed the lowest platelet and human umbilical vein smooth muscle cell density and the highest human umbilical vein endothelial cell density. Among the materials investigated, PU-PS1M1 also had the longest plasma clotting time. This material was thus shown to be multifunctional with a combination of properties, suggesting thromboresistant behavior in blood contact.

Cellulose Nanocrystals with Tethered Polymer Chains: Chemically Patchy versus Uniform Decoration

The site-specific surface modification of colloidal substrates, yielding "patchy" nanoparticles, is a rapidly expanding area of research as a result of the new complex structural hierarchies that are becoming accessible to chemists and materials scientists through colloidal self-assembly. The inherent directionality of cellulose chains, which feature a nonreducing and a reducing end, within individual cellulose nanocrystals (CNCs) renders them an interesting experimental platform for the synthesis of asymmetric nanorods with end-tethered polymer chains. Here, we present water-tolerant reaction pathways toward patchy and uniformly modified CNC hybrids based on atom transfer radical polymerization (ATRP) and initiators that were linked to the CNCs with carbodiimide-mediated coupling and Fischer esterification, respectively. Various monomers, including N-isopropylacrylamide (NIPAM), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC), and sodium 4-vinylbenzenesulfonate (4-SS), were polymerized from both types of initiator-modified CNCs, yielding chemically patchy and uniform CNC hybrids, via surface-initiated ATRP (SI-ATRP). Interestingly, the stereochemistry of tethered PNIPAM was affected by the precise location of ATRP initiating sites, as evidenced by 1H NMR and circular dichroism (CD) spectroscopy. This effect may be related to the inherent right-handed chirality of CNCs. CNC/PMETAC hybrids were labeled with gold nanoparticles (AuNPs) in order to visualize the precise location of polymer tethers via cryo-electron microscopy. In some instances, the AuNPs were indeed concentrated at the end groups of the patchy CNC hybrids.

Preparation of high toughness nanocomposite hydrogel with UV protection performance and self-healing property

An ultraviolet shielding hydrogel of P(NaSS-co-MPTC)/TiO2 was prepared by introducing TiO2 nanoparticles (TiO2 NPS) into polyampholyte matrix through photo-initiated radical copolymerization of cationic monomer of 3-(methacrylamide) propyltrimethylammonium chloride (MPTC) and anionic monomer of sodium 4-vinylbenzenesulfonate (NaSS) in the aqueous solution of sodium chloride (NaCl). FTIR, XPS, TEM, XRD, and SEM were used to characterize the morphology and structure of hydrogel of P(NaSS-co-MPTC)/TiO2. The result showed that anatase TiO2 NPS with the size about 15 ~ 20 nm were not just acted as ultraviolet shielding agent and general photo-initiator, they also could be crosslinked in polyampholyte matrix by hydrogen bonding between hydroxyl groups on the surface of TiO2 NPS and sulfonate groups on the polymer chains. Based on two kinds of reversible weak bonds of hydrogen bond and ionic bond, the P(NaSS-co-MPTC)/TiO2 hydrogel exhibited excellent mechanical properties and self-healing ability at ambient conditions, which will greatly increase its service life being a UV inhibitor.

Monodisperse raspberry-like multihollow polymer/Ag nanocomposite microspheres for rapid catalytic degradation of methylene blue

Raspberry-like multihollow polymer microspheres were prepared by seeded swelling polymerization and decorated with silver nanoparticles (AgNPs) in the presence of polyvinylpyrrolidone (PVP) which acted as both reducing and stabilizing agent. Formation mechanism of the raspberry-like multihollow microsphere was discussed on the basis of water absorption of sulfonated groups in the seeded swelling polymerization. Effects of weight ratio of sodium 4-vinylbenzenesulfonate to styrene (NaSS/St) of the seed particles, the concentration of PVP and [Ag(NH3)2]+ ions on the properties of polymer/Ag nanocomposite microspheres were investigated by microscopic observation, nitrogen adsorption/desorption isotherms, UV–vis absorption spectra, X-ray diffraction patterns and thermogravimetric analysis. The results demonstrated that the raspberry-like multihollow microspheres were successfully fabricated by controlling over the NaSS/St of the seed particles in the seeded swelling polymerization by which the fabrication of hollow structure became simple and convenient. The spherical AgNPs were loaded on the polymer microsphere by in-situ chemical reduction due to the stabilization and reduction of PVP and the attraction between sulfonated groups and [Ag(NH3)2]+ ions. The raspberry-like multihollow polymer/Ag microspheres showed good catalytic activity and reusability in the degradation of methylene blue in the presence of NaBH4.

Multi-hollow polymer microspheres with enclosed surfaces and compartmentalized voids prepared by seeded swelling polymerization method

Multi-hollow particles have drawn extensive research interest due to their high specific areas and abundant inner voids, whereas their convenient synthesis still remains challenging. In this paper, we report a simple and convenient method based on seeded swelling polymerization to prepare the multi-hollow microspheres with enclosed surfaces and compartmentalized voids using monodisperse poly (styrene-co-sodium 4-vinylbenzenesulfonate) microspheres as seed particles. A formation mechanism of the multi-hollow structure was proposed involving the processes of water absorption, coalescence and stabilization of water domains, immobilization of multi-hollow structure, and coverage of surface dimples. The influencing parameters on the morphology of the microspheres, including weight ratio of sodium 4-vinylbenzenesulfonate to styrene in the seed particles, dosage of the swelling monomer and the crosslinking agent were systematically investigated. The internal structure of the resultant microspheres could be tuned from solid to multi-hollow by controlling over these parameters. Multi-hollow microspheres with compartmentalized chambers, smooth surfaces and narrow size distributions were obtained as a result.

Graphene Oxide as a Radical Initiator: Free Radical and Controlled Radical Polymerization of Sodium 4-Vinylbenzenesulfonate with Graphene Oxide.

The free radical and controlled radical polymerization of sodium 4-vinylbenzenesulfonate using graphene oxide as a radical initiator was studied. This work demonstrates that graphene oxide can initiate radical polymerization in an aqueous solution without any additional initiator. Poly(sodium 4-vinylbenzenesulfonate) obtained via reversible addition-fragmentation chain transfer polymerization had a controlled molecular weight with a very narrow polydispersity ranging between 1.01 and 1.03. The reduction process of graphene oxide as well as the resulting composite material properties were analyzed in detail.

Synthesis and properties of sodium vinylbenzene sulfonate-grafted poly(vinylidene fluoride) cation exchange membranes for membrane capacitive deionization process

In this study, a poly(vinylidene fluoride)-graft-sodium 4-vinylbenzene sulfonate copolymer (PVDF-g-PSVBS) was prepared by grafting sodium 4-vinylbenzene sulfonate (SVBS) onto dehydrofluorinated poly(vinylidene fluoride) (PVDF). The PVDF-g-PSVBS cation exchange membranes were prepared using a casting method. The structure of the membranes was investigated with Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. Morphology using scanning electron microscope with energy-dispersive X-ray analysis (SEM-EDS) demonstrated as increasing the degree of grafting, the sulfur element is uniformly distributed and increased. The effects annealing temperature on the properties of the PVDF-g-PSVBS membranes were investigated. To prepare the consistent and homogeneous membranes, it was suggested that the annealing temperature of PVDF-g-PSVBS membranes is below 60 °C. The salt removal efficiency for application to the membrane capacitive deionization (MCDI) process was conducted. Open image in new window

Mussel-inspired self-coating at macro-interface with improved biocompatibility and bioactivity via dopamine grafted heparin-like polymers and heparin.

In this study, multifunctional mussel-inspired self-coated membranes with remarkable blood and cell compatibilities are prepared by a facile and green approach. A highly sulfonated linear heparin-like polymer (HepLP, poly(sodium 4-vinylbenzenesulfonate)-co-poly(sodium methacrylate)) and heparin are chosen for the mussel-inspired heparin-mimicking coating, respectively. Firstly, DA is grafted onto the backbone of HepLP or heparin to obtain DA grafted HepLP (DA-g-HepLP) or DA grafted heparin (DA-g-Hep) by means of the carbodiimide chemistry method. Then, the DA-g-HepLP and DA-g-Hep are used to prepare surface coated heparin-mimicking substrates; the polyethersulfone (PES) dialysis membrane is chosen as the model substrate. The coated surface composition, surface morphology, water contact angle, surface zeta-potential, blood compatibility and cell compatibility are systematically investigated. The results of surface spectra, scanning electron microscopy (SEM) and atomic force microscopy (AFM) indicated that the DA-g-HepLP and DA-g-Hep were successfully coated onto the membranes. The coated membranes showed increased hydrophilicity and electronegativity, decreased plasma protein adsorption, and suppressed platelet adhesion compared to the pristine membrane. The cell morphology observation and cytotoxicity assays demonstrated that the surface coated heparin-mimicking membranes showed superior performance in endothelial cell proliferation and morphology differentiation. In addition, the excellent anticoagulant bioactivities indicated that the adhered DA-g-HepLP (or DA-g-Hep) could function or maintain its biological activity after the immobilization. In general, the mussel-inspired protocol of surface self-coating conferred the modified membranes with integrated blood compatibility, cell proliferation and biological activity for multi-biomedical applications, like hemodialysis, blood purification, organ implantation, and cell and tissue cultures.

1H NMR Analysis of Long-Chain-Branched Strong Polyelectrolytes Obtained by Vinyl/Divinyl Monomer Copolymerization in Aqueous Medium

Statistical long-chain branching occurring during the free-radical polymerization of the system sodium 4-vinylbenzenesulfonate (SSNa) and N, N′-methylene-bis(acrylamide) (MBAA) in aqueous medium was studied by ¹H NMR spectroscopy and SEC. The former method yielded the degree of conversion and the content of the three monomer units in the chain, i.e., SSNa, MBAA with pendant vinyl groups, and MBAA as branching points. It was found that the number of individual monomer units per a total of 1000 monomer units does not perceivably change with the degree of conversion and only slightly increases with increasing ratio MBAA/SSNa in the feed.

Two novel nanoscaled bismuth oxido clusters, [Bi38O45(OMc)22(C8H7SO3)2(DMSO)6(H2O)1.5]·2.5H2O and [Bi38O45(HSal)22(OMc)2(DMSO)15(H2O)]·DMSO·2H2O

The synthesis of [Bi 38 O 45 (OMc) 22 (C 8 H 7 SO 3 ) 2 (DMSO) 6 (H 2 O) 1.5 ]·2.5H 2 O ( 1 ·2.5H 2 O) (OMc—methacrylate) and [Bi 38 O 45 (HSal) 22 (OMc) 2 (DMSO) 15 (H 2 O)]·DMSO·2H 2 O( 2 ·DMSO·2H 2 O) (Hsal—salicylate) starting from [Bi 38 O 45 (OMc) 24 (DMSO) 9 ]·2DMSO·7H 2 O and sodium 4-vinylbenzenesulfonate and salicylic acid, respectively, is presented. The bismuth oxido clusters show diameters of 2.9 nm ( 1 ) and 2.4 nm ( 2 ) and molecular weights of 11,440.22 g/mol ( 1 ·2.5H 2 O) and 13,151.92 g/mol ( 2 ·DMSO·2H 2 O). The polynuclear framework of 1 and 2 is quite similar; nevertheless, a comparison of the bismuth and oxygen atom positions of 1 and 2 shows a weighted root mean square deviation of 0.307 and 0.413 Å, respectively, as a result of the different coordination sphere. Both [Bi 38 O 45 ] 24+ cores in 1 and 2 are coordinated by two different anionic ligands with a ligand-to-ligand ratio of 22:2, which might indicate two particularly reactive positions at each bismuth oxido cluster.

SYNTHESIS AND MICELLIZATION BEHAVIOR OF ANIONIC FLUORINE-CONTAINING AMPHIPHILIC GRAFT COPOLYMERS

A novel series of anionic fluorine-containing amphiphilic graft copolymers P(HFMA-co-NaSS)-g-PEG were synthesized by graft copolymerization of poly(ethylene glycol) methyl ether methacrylate(MPEGMA) macromonomer,2,2,3,4,4,4-hexafluorobutyl methacrylate(HFMA) and sodium 4-vinylbenzenesulfonate(NaSS).The molecular structures of the amphiphilic graft copolymer were characterized by FTIR,1H-NMR and 19F-NMR.The critical micelle concentration(CMC) of P(HFMA-co-NaSS)-g-PEG was measured by surface tension technique,indicating that the CMC increased gradually with increasing PEG branched chains and anionic contents in the copolymer.The average hydrodynamic diameter and size distribution of micelles were measured by dynamic light scattering(DLS).The measurement showed that the hydrodynamic diameter increased gradually with increasing the concentration of P(HFMA-co-NaSS)-g-PEG aqueous solution and the content of PEG branched chains in P(HFMA-co-NaSS)-g-PEG.The fluorescence spectrum showed that there was a significant interaction between P(HFMA-co-NaSS)-g-PEG micelles and bovine serum albumin(BSA).The fluorescence intensity of BSA decreased gradually in P(HFMA-co-NaSS)-g-PEG/BSA aqueous solution with increasing the concentration of P(HFMA-NaSS)-g-PEG aqueous solution,HFMA segments and NaSS contents.Transmission electron microscopy(TEM) was used to investigate P(HFMA-co-NaSS)-g-PEG micelles and the aggregates of P(HFMA-co-NaSS)-g-PEG/BSA,the results showed that P(HFMA-co-NaSS)-g-PEG copolymers could self-assemble into core-shell structure micelles.Besides,with the decrease of HFMA contents in the copolymer,the morphology of P(HFMA-co-NaSS)-g-PEG micelles changed from a leaf-like structure to a spherical one.In particular,when BSA was added,the micelles changed from a tight core-shell structure into a loose vesicle-like structure,and the micelle size and size distribution also increased.TEM micrographs of P(HFMA-co-NaSS)-g-PEG/BSA displayed a visible adsorption phenomenon between P(HFMA-co-NaSS)-g-PEG micelles and BSA,and suggested that P(HFMA-co-NaSS)-g-PEG may have potential applications in loading proteins and other bioactive drugs.

Surface Modification of Heteropolyacids (HPAs) for Proton Exchange Membrane Fuel Cells (PEMFCs)

Novel composite proton exchange membranes have been prepared from surface modification of heteropolyacids, namely: silicotungstic acid (SiWA), and sulfonated poly(ether ether ketone) (SPEEK) as a polymer matrix. Atom transfer radical polymerization (ATRP) has been used for surface polymerization of sodium 4-vinyl benzene sulfonate (S4VBS) on SiWA. PEEK has been sulfonated using chlorosulfonic acid. The major outcome of this work was surface coated SiWA-poly(S4VBS) which resulted in homogenous composite membranes as compared with non-surface coated SiWA. The thermal properties of surface polymerized S4VBS have been characterized using differential scanning calorimetry (DSC). The SiWA particles and cross section of the composite membrane have been imaged using DSC. Composite membrane conductivity has been characterized using electrochemical impedance spectroscopy. This route was expected to provide a membrane with high conductivity because of the presence of sulfonic acid groups on the grafted polymer backbone, and to avoid "washing out" of HPA in the fuel cell.

A new type of eco‐friendly resist based on nonchemically amplified system

AbstractNovel water‐processable photopolymers were designed to be useful as environment‐friendly photolithographic materials. By copolymerization of 2‐(2‐diazo‐3‐oxo‐butyryloxy)ethyl methacrylate (DOBEMA), hydroxyethyl methacrylate (HEMA), methacryllic acid (MAA), and sodium 4‐vinylbenzenesulfonate (SVBS), two kinds of polymers, poly(DOBEMA‐co‐HEMA‐co‐SVBS) for negative‐tone resist and poly(DOBEMA‐co‐MAA) for positive‐tone resist, were synthesized and their photolithographic properties were investigated. The single component negative‐tone resist produced 0.8 μm line and space patterns using a mercury‐xenon lamp in a contact printing mode using pure water as casting and developing solvent at a exposure dose of 25 mJ cm−2. On the other hand, the single component positive‐tone resist produced 0.8 μm line and space patterns at a much higher dose of 150 mJ cm−2. Thus, the negative resist showed much improved sensitivity when compared with the positive resist and the reported nonchemically amplified resists. This sensitivity is comparable with those of typical chemically amplified resists. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7534–7542, 2008

Oxidation-resistance of Hydrocarbon Electrolyte Membranes for PEFC.

The polymer electrolyte membranes (AAc/SSS membrane) were synthesized by the radiation-induced graft polymerization of acrylic acid (AAc) and sodium 4-vinylbenzenesulfonate (SSS) on a polyethylene film. The single cells using the synthesized polymer films as the electrolyte were tested continuously. In the case of AAc/SSS membrane contacted directly with the oxidizing catalyst (Pt) in oxygen electrode at 55°C, the cell voltage dropped significantly after only 5 h operation due to an oxidative degradation of the membrane. When the oxygen electrode was impregnated with an ionomer of perfluorocarbon- sulfonic acid to prevent the AAc/SSS membrane from its direct contact with Pt ele ctrocatalysts, the cell worked continuously for 212 h at 55°C and 71 h at 70°C. When a thin fluorinated polymer electrolyte membrane (F-membrane, thickness = 11μm) was sandwiched between the AAc/SSS membrane and the oxygen electrode impregnated with the ionomer, the significant degradation of the AAc/SSS membrane was delayed until 190 h at 70°C. It is considered that the AAc/SSS membrane was oxidized by active oxygen (radical) species and/or hydrogen peroxide produced at the cathode side.