Polystyrene Derivatives Research Articles

A novel cathode material based on polystyrene with pendant TEMPO moieties obtained via click reaction and its use in rechargeable batteries

In the present study, a new type of cathode-active polymeric material was synthesized via a synthetic strategy which involves a series of high-yield and simple chemical reactions performed on a commercially available and relatively cheap polymer, poly(p-chloromethylstyrene). Polymeric support for the electro-active TEMPO was obtained by nitroxide-mediated polymerization (NMP) of p-chloromethyl styrene. This polystyrene derivative was converted to a polymer with pendant electro-active TEMPO radical groups via an azidation reaction which was followed by a click reaction with an alkyne functionalized TEMPO derivative. The obtained polystyrene bearing TEMPO radical polymer possessed a high spin density of 1.4 × 1021 spin/g indicating that electro-active TEMPO groups were successfully attached to the polymer with high yield. The composite cathode material obtained by mixing this TEMPO functionalized polymer with graphite showed a reversible electrochemical redox behavior in a cyclic voltammetry (CV) study vs. Li metal anode. The Li-battery constructed using this cathode maintained 83 % of the its initial capacity (35 mAh/g) over 80 cycles with a cell potential of 3.8 V.

Photoalignment behaviour on polystyrene films containing chalcone moieties

A series of polystyrene derivatives containing chalcone (one of the biological compounds) side groups, poly(4-(4-vinylbenzyloxy)chalcone) (PCHAL#), where # is the molar content of chalcone using polymer modification reactions, were prepared in order to study the effect of the chalcone side groups on the liquid crystal (LC) alignment properties. The LC alignment behaviour of the polymer was investigated using photoalignment method. The LC cells made from photoirradiated PCHAL# films exhibited homogeneous planar LC alignment with an extremely low pretilt angle of approximately 0°. We found that LC aligning ability of the LC cells made from photoirradiated PCHAL# films was affected by the molar content of chalcone side groups. For example, the azimuthal anchoring energy of a PCHAL100 (9 × 10−6 J/m2) was found to be much larger than that of PCHAL18 (5 × 10−7 J/m2). In addition the electro-optical characteristics of the LC cells fabricated with PCHAL100 films such as threshold voltage, driving voltage, and response time were as good as those fabricated from rubbed polyimide films, the most commonly used LC alignment layers.

Photoproperties of Novel Polystyrene Derivatives with Oligofluorene Pendants

Two kinds of novel polystyrene derivatives with oligofluorene pendants were synthesized by radical polymerization method. The polymers were soluble in common organic solvents and formed nice films by spin-coating. Photoproperties of the products were studied and small differences in conjugated structures between monomers and polymers according to UV-vis spectra. The polymers showed fewer changes in spectra after annealing compared with main-chain conjugated ones, which indicated better thermal stability.

Liquid Crystal Alignment Behaviors of Polystyrene Derivatives Containing Coumarin Moieties

We synthesized a series of polystyrene derivatives containing coumarin side groups, poly(7-(4-vinylbenzyloxy)coumarin) (P7COU#) and poly(7-(4-vinylbenzyloxy)4-phenylcoumarin) (P7COU4P#), where # is the molar content of 7-hydroxycoumarin and 7-hydroxy-4-phenyl coumarin, respectively, using polymer analogous reaction, in order to study the effect of the 7-hydroxycoumarin and 7-hydroxy-4-phenyl coumarin side groups on the liquid crystal (LC) alignment properties. The LC alignment behavior of these two series was investigated by photoalignment or rubbing alignment. The LC cells made from photoirradiated P7COU# and P7COU4P# films showed homogeneous planar LC alignment. We found that LC aligning ability of the LC cells made from rubbed P7COU# and P7COU4P# films were affected by the structure and molar content of coumarin side groups. For example, anchoring energy of the LC cell fabricated with rubbed P7COU82 (7 × 10−5 J/m2) and P7COU4P81 (7 × 10−7 J/m2) film was increased drastically and slightly compared to polystyrene (10−7−10−8 J/m2), respectively. Particularly, anchoring energy of the LC cell made from rubbed P7COU# having more than 51 mol % of the 7-hydroxycoumarin as a side groups is comparable to that of the conventional polyimide in the LCD industry.

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

AbstractThe preparation of new compounds, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene, is described. 1,1‐Bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α‐bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α‐bis(oxazolyl) polystyrene follows first‐order rate kinetics with respect to monomer consumption. α,ω‐Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post‐ATRP chain‐end‐functionalization reaction which involves the direct addition of 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene to the ω‐terminus of the α‐bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α‐Bis(carboxyl) and α,ω‐tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain‐end‐functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using 1H NMR and 13C NMR spectrometry and Fourier transform infrared spectroscopy, size‐exclusion and thin‐layer chromatography and non‐aqueous titration measurements. © 2014 Society of Chemical Industry

Enhancing Properties of Anionic Poly(ionic liquid)s with 1,2,3-Triazolium Counter Cations

A series of anionic poly(ionic liquid)s with 1,2,3-triazolium counter cations are prepared by cation exchange between tailormade 1,3,4-trialkylated-1,2,3-triazolium iodides and a polystyrene derivative having pendant potassium bis(trifluoromethylsulfonyl)imide groups. The physical and ion-conducting properties of the resulting materials are compared to the parent potassium-containing polyelectrolyte based on 1H NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and broadband dielectric spectroscopy (BDS) measurements. Substitution of the potassium counter cation by 1,2,3-triazolium charge carriers affords polyelectrolytes with improved processability (broader solubility and removal of the crystalline behavior) as well as a substantial increase in anhydrous ionic conductivity.

Synthesis and biocidal activity of novel N-halamine hydantoin-containing polystyrenes

AbstractThree homopolymers containing hydantoin substituents were obtained by chemical modification of reactive p-chloromethylated polystyrene. The prepared polymers were chlorinated to yield N-halamine materials with biocidal properties. The chemical structure of polymers was characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. All of the hydantoin polymers are insoluble in water and common organic solvents. Microbiological investigations prove the high biocidal activity of the obtained chlorinated polystyrene derivatives containing spirohydantoin moieties. The obtained polymers will be useful in designing and constructing medical and pharmaceutical equipment. The ability to crosslink allows to expect easy grafting of these biocidal macrochains, for example, on textiles.

Photo-induced helix–helix transition of a polystyrene derivative

Poly(2,5-bis[4-((S)-2-methylbutyloxy)phenyl]styrene) having a helical conformation underwent helix–helix transition upon photo-irradiation. Conformational transition can significantly alter polymer properties, and so far thermal stereomutation has been studied. However, as for photo-induced mutation, only helix–helix transition (irreversible CD-active to CD-silent helix transition) of a polyacrylate has been explored. Here, we present mutation of the polystyrene derivative. Chiroptical, viscometric, and vibrational spectroscopic analyses indicated the polymer mutated from an optically active helix to another optically inactive helix with a different shape.

Understanding the mechanism of refractive index modulation in materials undergoing photo-Fries rearrangement

Molecules and polymers that undergo a photo-Fries rearrangement are studied by using DFT calculation in order to predict the refractive index modulation which accompanies this light induced process. In particular, monomeric units of polystyrene derivatives (such as poly(p-formyloxystyrene) and poly(4-acetoxystyrene)) are considered and the refractive index calculated starting from the molecular polarizability and following the Lorentz–Lorenz approach. The results demonstrate that the conversion of ester groups to ketone/alcohol provides just a small modulation of the refractive index that does not fit the experimental results reported in the literature. A change in material density is therefore considered as main source of the modulation of the refractive index. Theoretical and experimental evidences are reported to support the picture.

Radiation-grafted, chemically modified membranes part I – Synthesis of a selective aluminum material

Polymeric membranes were styrene grafted by irradiation methods and the obtained material was chemically modified to become aluminum selective. For this purpose, polymeric substrates of PVC (polyvinyl chloride) and PP (polypropylene) were styrene grafted mutually by gamma and electron beam irradiation. The modification process includes three basic reaction paths: Friedel–Crafts acylation, 2-methylanisole coupling and a final oxidation to achieve aluminum selectivity. Although this specific chemical modification in derivatives of polystyrene is not new, the new challenge is to obtain a selective material where original membrane characteristics (physical shape and mechanical resistance) are minimally conserved after such an aggressive treatment.

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

The quantitative syntheses of α-bis and α,ω-tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1-diphenylethylene derivative, 1,1-bis[(4-dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1-bromoethyl)benzene with 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′-bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number-average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω-tetrakis(4-dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α-bis(4-dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1-bis[(4-dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non-aqueous titration measurements. Copyright © 2012 Society of Chemical Industry

Influences of wetting and shrinkage on the phase separation process of polymer mixtures induced by photopolymerization

Phase separation induced by photopolymerization was investigated for a mixture composed of a polystyrene derivative and methyl methacrylate (MMA) monomer. The photopolymerization kinetics of MMA under irradiation with 405 nm visible light was in situ monitored by Fourier-transform infrared spectroscopy (FT-IR). Laser-scanning confocal microscopy (LSCM) combined with 2D-fast Fourier transform (2D-FFT) was utilized to observe and analyze the morphology resulting from the photopolymerization. By using LSCM together with static light scattering, it was found that the phase separation can be induced via either the spinodal decomposition or the nucleation-and-growth processes depending upon the irradiation intensity. A wide variety of stationary morphologies ranging from bi-continuous, salami structures to tri-layer morphology were separately obtained by changing the irradiation intensity. It was also found that the shrinkage of the sample associated with the photo-polymerization plays an important role in the resulting morphology. In addition, the autoacceleration behavior of the polymerization plays a key role in the phase separation kinetics. These experimental results indicate that photopolymerization can be used as an efficient tool not only to control the wetting process during the phase separation, but also to design polymer materials with various morphologies which would be utilized as templates for various practical applications.

The syntheses of aromatic oxazolyl and carboxyl functionalized polymers using 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole in atom transfer radical polymerization reactions

The syntheses of oxazolyl functionalized polymers using 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole in atom transfer radical polymerization (ATRP) reactions are reported. A new oxazolyl initiator system was generated in situ by the atom transfer radical addition (ATRA) reaction of (1-bromoethyl)benzene with 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole and employed as the oxazolyl functionalized initiator for the polymerization of styrene by ATRP methods to produce well defined α-oxazolyl functionalized polystyrene. The polymerization kinetic data for the synthesis of α-oxazolyl functionalized polystyrene shows that the polymerization process follows first order rate kinetics with respect to monomer consumption. The number average molecular weights (Mn=0.61×103–9.8×103g/mol) of the α-oxazolyl functionalized polymers increased linearly with percentage monomer conversion and polymers with narrow molecular weight distributions (Mw/Mn=1.22–1.51) were obtained. The polymerization processes were monitored by gas chromatographic analyses to determine the extent of monomer consumption as a function of time. α,ω-Bis(oxazolyl) functionalized polystyrene was prepared by a new, controlled/living, post ATRP chain end functionalization reaction which involves the direct addition of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole to the ω-terminus of α-oxazolyl functionalized polystyrene, without the isolation and purification of the functionalized polymeric precursor. The quantitative chemical transformation of the oxazoline group of the respective oxazolyl chain end functionalized polystyrene derivative by successive acid and base hydrolysis, followed by final acidification, provides the corresponding well defined aromatic carboxyl chain end functionalized polystyrene. The organic precursor compounds, the oxazolyl functionalized 1,1-diphenylethylene derivative and the functionalized polymers were characterized by 1H NMR and 13C NMR spectrometry, FTIR spectroscopy, size exclusion chromatography, thin layer chromatography and non-aqueous titration measurements.

The conditions of cationic exchange with the use of recycling polystyrene derivative, the product of sulfonation by silica sulfuric acid

AbstractGrowing amount of waste plastics has become an environmental problem on a global scale. This study presents an investigation of the conditions of cleaning water from heavy metal ions using chemically recycled polystyrene. To get effective ion exchangers, the sulfonation of virgin polystyrene and expanded polystyrene wastes were obtained using silica sulfuric acid. As it turned out, the use of this solid sulfonating agent simplifies the separation of the polymeric product from the acid and the solvent in comparison to conventional sulfonation methods. The ion exchange behavior of copper and zinc cations in the yielded sulfonated derivatives of polystyrene was studied. Batch shaking adsorption experiments depending on contact time, pH, temperature, and dosage of adsorbate were carried out. The stability of resin to cyclical adsorption and regeneration (column experiment) was also investigated. We report that resins have a high adsorption efficiency with total ion exchange capacity (IEC) about 2.6 meq g−1, which drops with decreasing pH owing to competition between protons H+ and metal cations, whereas with the increasing resin doses the removal of cations rises for a constant initial metal concentration. The speed of cation exchange for yielded adsorbents was even better than for commercial resins. After 360 cyclical adsorption and regeneration in column, resin had working IEC of about 2.3 meq g−1. The study shows that cation exchange resin from polystyrene wastes can be used as an efficient adsorbent for the removal of heavy metal ions from water. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Fabrication and Arrangement of “Clickable” Nanowires by the Single-Particle Nanofabrication Technique

Focusing of photons or charged particles into a small spatial area has been believed to be indispensable for “top-down” miniaturization in conventional micro- or nanolithographic techniques. Here, we describe a fabrication technique with the concept of “a nanowire produced by a particle”, released from these limitations, using “Clickable” nanowires to construct highly controlled biological macromolecular materials. The present paper demonstrates the formation of nanowires composed of synthetic polymers by the single-particle nanofabrication technique (SPNT). The fabrication of nanowires composed of a polystyrene derivative with an alkyne “click” function, poly(styrene-co-4-ethynylstyrene) (PSES), was confirmed by atomic force microscopy. Alkyne moieties in PSES achieve an extremely high value of cross-linking efficiency compared with unsubstituted polystyrene. Alkyne groups on the surface of PSES nanowires were modified by polymer materials and proteins via copper-catalyzed alkyne/azide cycloaddition reactions and avidin–biotin interactions, respectively. PSES and its nanowires were thus revealed to be suitable materials for the fabrication of nanostructures and the introduction of various functional materials, including biomacromolecules, by surface modification. With “Clickable” nanowires fabricated by SPNT, it should be possible to trigger the development of the architecture of biomacromolecular nanomaterials.

Reversible Cross-Linking and De-Cross-Linking System of Polystyrenes Bearing the Monohydrate Structure of Vicinal Tricarbonyl Group through Water–Alcohol Exchange Reactions at Ambient Conditions

We describe in this paper reversible cross-linking and de-cross-linking system based on a polystyrene derivative bearing monohydrate structure of vicinal tricarbonyl groups with 1,6-hexanediol utilizing the direct water–alcohol exchange reactions on the vicinal tricarbonyl groups. By employing diphenylpropanetrione as a unit model compound for the polymer, we have demonstrated that the water–alcohol exchange reactions could be carried out reversibly in both directions by changing solvents. Notably, the water–alcohol exchange reactions proceeded without any catalysts and under mild conditions. For example, an equimolar mixture of the hydrate of diphenylpropanetrione and benzyl alcohol in chloroform (0.5 M) reached equilibrium after standing at ambient temperature within 48 h, where the content ratio of the benzyl alcohol adduct increased up to 49%. The reaction rate and the position of the equilibrium were highly affected by the concentrations of the substrates as well as the reaction temperature. By virtue of the above characteristic features of the water–alcohol exchange reactions, the polystyrene derivative bearing monohydrate structure of vicinal tricarbonyl group (2.0 M) was cross-linked with 1,6-hexanediol (0.2 equiv of OH group to the tricarbonyl unit) in acetone at ambient temperature for 5 days to afford the networked polymer in almost quantitative yield. On the other hand, the networked polymer was treated with an excess of water at ambient temperature for 3 days to afford the original linear polymer in high yield as a result of de-cross-linking through the water–alcohol exchange reaction. The cross-linking and de-cross-linking behavior was also evidenced by SEC analysis of the reaction mixture.

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

AbstractThe quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry

High‐Heteronucleobase‐Content Polystyrene Copolymers Prepared Using Click Chemistry Form Supramolecular Structures With Melamine Through Complementary Multiple Hydrogen‐Bonding Interactions

AbstractFree‐radical copolymerization is used to synthesize poly[styrene‐co‐(4‐vinylbenzyl azide)] (PS‐co‐PVBN3), followed by click chemistry to react it with propargyl thymine (PT) to obtain a series of high‐performance polystyrene derivatives, poly[styrene‐co‐(4‐vinylbenzyltriazolylmethylmethylthymine)] (PS‐co‐PVBT). The presence of the thymine units on the side chains of the PS copolymers allows specific intermolecular association through self‐complementary T–T interactions. In addition, the thermal and dynamic rheological properties of PS‐co‐PVBT increase significantly when it is blended with melamine (M) because of the strong, complementary, multiple hydrogen‐bonding interactions that occur between the T units and this low‐molecular‐weight compound (M).

Reversible Fixation and Release of Alcohols by a Polymer Bearing Vicinal Tricarbonyl Moieties and Its Application to Synthesis and Reversible Cross-Linking–De-Cross-Linking System of a Networked Polymer

In this paper, we report reversible fixation and release of alcohols by a polystyrene derivative bearing acyclic vicinal tricarbonyl moieties (1) and its application to synthesis and reversible cross-linking-de-cross-linking system of a networked polymer. First the reversible fixation and release behavior of alcohols by an acyclic vicinal tricarbonyl compound, 1,3-diphenylpropanetrione (DPPT) as a model compound of 1 was investigated. On the basis of the results, the fixation of n-hexanol to 1 was carried out to provide the n-hexanol adduct of 1 (1-HexOH), which has a hemiacetal structure. On the other hand, heating 1-HexOHin vacuo enabled successful recovery of 1 to demonstrate the reversible nature of this system. Furthermore, the reaction of 1 with 1,6-hexanediol proceeded smoothly to give networked polymer, which could be de-cross-linked by heating at 50 °C in DMSO/H2O mixture. This result indicates that a novel reversible cross-linking–de-cross-linking system of networked polymer was constructed.

New Applications of Sulfonated Derivatives of Polystyrene Waste

The solid silica sulfuric acid was used to heterogeneous sulfonation of polystyrene waste dissolved in organic solvent. After sulfonation, small suspended particles of polystyrene derivatives were easily separated from much bigger particles of silica sulfuric acid by filtration and from solvent mostly by decantation and additionally by evaporation. The characteristics of adsorption of heavy metal cations on resins from polystyrene were compared with that of commercial resins. It was proved that synthesized resins are effective cation exchangers. The advantage of obtained resins was their high rate of metal removal.