Synthesis and flocculation properties of poly(diallyldimethyl ammonium chloride–vinyl trimethoxysilane) and poly(diallyldimethyl ammonium chloride–acrylamide–vinyl trimethoxysilane)

Poly(diallyldimethyl ammonium chloride–vinyl trimethoxysilane) [P(DADMAC–VTMS)] and poly(diallyldimethyl ammonium chloride–acrylamide–vinyl trimethoxysilane) [P(DADMAC–AM–VTMS)], the latter a new cationically charged and hydrophobically modified flocculant, were obtained by radical polymerization initiated by potassium persulfate. The effects of the vinyl trimethoxysilane (VTMS) feed ratio on the intrinsic viscosity and solubility of the polymers were examined. The effects of the flocculants on turbidity removal, decolorization, and oil removal in water treatment were also studied. The introduction of VTMS increased the intrinsic viscosities of P(DADMAC–VTMS) and P(DADMAC–AM–VTMS) in comparison with the viscosities of poly(diallyldimethyl ammonium chloride) and poly(diallyldimethyl ammonium chloride–acrylamide), respectively, but reduced their solubilities. The introduction of VTMS also enhanced the flocculation properties of P(DADMAC–VTMS) and P(DADMAC–AM–VTMS), including turbidity removal, decolorization, and oil removal. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 335–342, 2002; DOI 10.1002/app.10339     

Synthesis of double‐hydrophilic poly(methylacrylic acid)–poly(ethylene glycol)–poly(methylacrylic acid) triblock copolymers and their micelle formation

The aim of the work reported was to synthesize a series of double‐hydrophilic poly(methacrylic acid)‐block‐poly(ethylene glycol)‐block‐poly(methacrylic acid) (PMAA‐b‐PEG‐b‐PMAA) triblock copolymers and to study their self‐assembly behavior. These copolymeric self‐assembly systems are expected to be potential candidates for applications as carriers of hydrophilic drugs. Bromo‐terminated difunctional PEG macroinitiators were used to synthesize well‐defined triblock copolymers of poly(tert‐butyl methacrylate)‐block‐poly(ethylene glycol)‐block‐poly(tert‐butyl methacrylate) via reversible‐deactivation radical polymerization. After the removal of the tert‐butyl group by hydrolysis, double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers were obtained. pH‐sensitive spherical micelles with a core–corona structure were fabricated by self‐assembly of the double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers at lower solution pH. Transmission electron microscopy and laser light scattering studies showed the micelles were of nanometric scale with narrow size distribution. Solution pH and micelle concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible reason for the formation of the micelles is proposed. Copyright © 2010 Society of Chemical Industry     

Synthesis of poly(dodecyl methacrylate)s and their drag‐reducing properties

Dodecyl methacrylate was synthesized as the intermediate monomer for the preparation of poly(dodecyl methacrylate)s, which were synthesized with emulsion polymerization techniques. The intrinsic viscosities were measured, and the viscosity‐average molecular weights were calculated. Polymers of dodecyl methacrylate with ultrahigh molecular weights (viscosity‐average molecular weight > 10⁷) were synthesized through orthogonal experiments. The drag‐reduction properties of these polymers were studied in kerosene. The drag‐reducing behavior of these polymers exhibited a strong dependence on the molecular weight and Reynolds number, and these polymers could be used as effective oil‐soluble drag reducers and had good shear stabilities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1622–1626, 2003     

Surface characterization of poly(styrene‐co‐ fluoroalkylfumarate): XPS and contact angle measurement study

We studied styrene and fluoroalkylfumarate (FAF) copolymers and their surfaces by means of contact angle measurement and X‐ray photoelectron spectroscopy (XPS). The surfaces of the copolymers were very hydrophobic (even with a small amount of FAF) because of the concentration of FAF segments at the surface. The hydrolyzed surfaces of the copolymers became slightly hydrophilic compared to the as cast. The XPS data suggested that the fluoroalkyl groups seemed to be primarily hydrolyzed. The surfaces with a large amount of FAF changed their characteristics to hydrophobic again under atmospheric conditions. This phenomenon was due to the inversion of the carboxyl and the fluoroalkyl groups. These hydrolyzed surfaces seemed to be useful for modifying polymer surfaces by attaching to other functional molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1049–1054, 1999     

Thin films of insoluble copolymer derived from poly(phenylene‐vinylene) obtained by thermal evaporation under vacuum

A new copolymer, referred to as poly(phenylene‐vinylene) (PPV)‐ether, built as PPV a polymer with some (? CH?CH? ) links changed into (? CH₂? O? CH₂? ) ethylic‐ether links, is insoluble in common solvents. PPV‐ether films are deposited by the thermal evaporation technique. X‐ray photoelectron spectroscopy for chemical analysis measurements indicate that the surface contamination decrease in the case of vacuum‐evaporated PPV‐ether. The scanning electron micrographs indicate that the surface of these vacuum‐deposited PPV‐ether are uniform. By comparison to the reference powder, the modification of the properties of the evaporated PPV‐ether are related to the decrease of the chain length and surface contamination. The results of the photoluminescence measurements reveal a shifting of the luminescence to blue in the vacuum‐evaporated PPV‐ether. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3091–3099, 2003     

End‐functional polymers,thiocarbonylthio group removal/transformation and reversible addition–fragmentation–chain transfer (RAFT) polymerization

This review focuses on processes for thiocarbonylthio group removal/transformation of polymers synthesized by radical polymerization with reversible addition‐fragmentation‐chain transfer (RAFT). A variety of processes have now been reported in this context. These include reactions with nucleophiles, radical‐induced reactions, thermolysis, electrocyclic reactions and ‘click’ processes. We also consider the use of RAFT‐synthesized polymers in the construction of block or graft copolymers, functional nanoparticles and biopolymer conjugates where transformation of the thiocarbonylthio group is an integral part of the process. This includes the use of RAFT‐synthesized polymers in other forms of radical polymerization such as atom transfer radical polymerization or nitroxide‐mediated polymerization, and the ‘switching’ of thiocarbonylthio groups to enable control over polymerization of a wider range of monomers in the RAFT process. With each process we provide information on the scope and, where known, indicate the mechanism, advantages and limitations. Copyright © 2011 Society of Chemical Industry     

Controlling the surface wettability of poly(sulfone) films by UV‐assisted treatment: benefits in relation to plasma treatment

Hydrophilic and superhydrophilic surfaces of poly(sulfone) (PSU) thin films were prepared by UV irradiation in the presence of O₂ or acrylic acid (AA) vapor. Treated surfaces were then investigated by water contact angle measurements, Fourier transformed IR spectroscopy in attenuated total reflectance mode (FTIR‐ATR), X‐ray photoelectron spectroscopy (XPS), near‐edge X‐ray absorption fine structure (NEXAFS) and AFM. Water contact angle values of treated PSU films using either O₂ or AA vapor as the reactive atmosphere reached about 6° after more than 120 min of irradiation. FTIR‐ATR, XPS and NEXAFS analysis showed incorporation of oxygenated groups onto the surface that led to its hydrophilic characteristics. In addition, when AA vapor was used as the reactive atmosphere, a photopolymerization process of poly(acrylic acid) onto the surface of the PSU was observed. AFM analysis showed a very low level of roughness after the treatments. A comparison of UV‐assisted surface modifications of PSU films with traditional plasma treatments showed excellent qualitative agreement between the two techniques. Our results show that UV‐assisted treatments in the presence of AA vapor or O₂ are efficient ways of controlling the surface wettability and functionalities grafted on the surface of PSU films. This treatment can be considered as a permanent dry grafting method that resists aging and uses a simple experimental setup. © 2012 Society of Chemical Industry     

Synthesis and surface properties of polydimethylsiloxane‐based block copolymers: poly[dimethylsiloxane‐block‐ (ethyl methacrylate)] and poly[dimethylsiloxane‐block‐(hydroxyethyl methacrylate)]

A polydimethylsiloxane (PDMS) macroazoinitiator was synthesized from bis(hydroxyalkyl)‐terminated PDMS and 4,4′‐azobis‐4‐cyanopentanoic acid by a condensation reaction. The bifunctional macroinitiator was used for the block copolymerization of ethyl methacrylate (EMA) and 2‐(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) monomers. The poly(DMS‐block‐EMA) and poly(DMS‐block‐TMSHEMA) copolymers thus obtained were characterized using Fourier transform infrared and ¹H NMR spectroscopy and differential scanning calorimetry. After the deprotection of trimethylsilyl groups, poly(DMS‐block‐HEMA) and poly(DMS‐block‐EMA) copolymer film surfaces were analysed using scanning electron microscopy and X‐ray photoelectron spectroscopy. The effects of the PDMS concentration in the copolymers on both air and glass sides of films were examined. The PDMS segments oriented and moved to the glass side in poly(DMS‐block‐EMA) copolymer film while orientation to the air side became evident with increasing DMS content in poly(DMS‐block‐HEMA) copolymer film. The block copolymerization technique described here is a versatile and economic method and is also applicable to a wide range of monomers. The copolymers obtained have phase‐separated morphologies and the effects of DMS segments on copolymer film surfaces are different at the glass and air sides. Copyright © 2010 Society of Chemical Industry     

Adsorption of amyloid beta (1-40) peptide at phospholipid monolayers

The folding of amyloid beta (1-40) peptide into beta-sheet-containing fibrils is thought to play a causative role in Alzheimer's disease. Because of its amphiphilic character, the peptide can interact with phospholipid membranes. Langmuir monolayers of negatively charged DPPS, DPPG, and DMPG, and also of zwitterionic DPPC and DMPC, have been used to study the influence of the peptide on the lipid packing and, vice versa, the influence of phospholipid monolayers on the peptide secondary structure by infrared reflection absorption spectroscopy and grazing incidence X-ray diffraction. The peptide adsorbs at the air/water (buffer) interface, and also inserts into uncompressed phospholipid monolayers. When adsorbed at the interface, the peptide adopts a beta-sheet conformation, with the long axis of these beta-sheets oriented almost parallel to the surface. If the lipid exhibits a condensed monolayer phase, then compression of the complex monolayer with the inserted peptide leads to the squeezing out of the peptide at higher surface pressures (above 30 mN m(-1)). The peptide desorbs completely from zwitterionic monolayers and negatively charged DPPG and DPPS monolayers on buffer, but remains adsorbed in the beta-sheet conformation at negatively charged monolayers on water. This can be explained in terms of electrostatic interactions with the lipid head groups. It also remains adsorbed at, or penetrating into, disordered anionic monolayers on buffer. Additionally, the peptide does not influence the condensed monolayer structure at physiological pH and modest ionic strength.     

Synthesis and characterization of polystyrene/poly(4‐vinylpyridine) triblock copolymers by reversible addition–fragmentation chain transfer polymerization and their self‐assembled aggregates in water

Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (M_w/M_n < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003     

X‐ray photoelectron,infrared, and Raman spectroscopy studies of novel submicrometric poly[(methacrylato)aluminum(III)]

Poly[(methacrylato)aluminum(III)] was prepared by applying γ‐radiation to the corresponding aluminum(III) methacrylate monomer. Scanning electron microscopy images show pellets of ～ 500 nm for the aluminum(III) methacrylate monomer, and submicrometric fibers‐made granules for the aluminum‐containing polymers. X‐ray photoelectron spectroscopy measurements reveal two peaks in the Al 2p core‐level spectra of the monomer and of the poly[(methacrylato)aluminum(III)], which means that two different coordination modes for the Al(III) ions might be present in these compounds. Infrared and Raman spectroscopy studies confirmed that the structure for this novel coordination polymer consists of hexa‐coordinated Al(III) ions linked by the carboxylate groups of methacrylate ligands, along with hydroxyl groups and coordinated water, in a combination of monodentate and bridging bidentate coordination modes. Hence, combination of spectroscopic methods is a helpful tool to get valuable information on the structure of nonmacrocrystalline coordination polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5212–5223, 2006     

Synthesis of novel polymethacrylate bearing an (S)‐(+)‐1‐cyclohexylethyl urea group in the side chain and its chiral recognition ability

A new chiral methacrylate, (S)‐(+)‐1‐cyclohexylethyl‐(2‐methacryloyloxyethyl)urea (CEMOU), was synthesized from 2‐methacryloyloxyethyl isocyanate (MOI) and (S)‐(+)‐cyclohexylethylamine. Radical homopolymerization of CEMOU was performed in several solvents to obtain the corresponding chiral polymers having hydrogen bonds based on urea moieties. Specific optical rotations of poly(CEMOU) were slightly changed by the measurement temperature, which may be attributed in part to a change of conformation caused by hydrophobic interaction between the cyclohexyl groups. From the results of radical copolymerization of CEMOU (M₁) with styrene (ST, M₂) or methyl methacrylate (MMA, M₂), monomer reactivity ratios (r₁, r₂) and Alfrey–Price Q–e values were determined: r₁ = 0.89, r₂ = 0.12, Q₁ = 2.45, e₁ = 0.68 for the CEMOU–ST system; r₁ = 0.48, r₂ = 0.18, Q₁ = 8.39, e₁ = 1.97 for the CEMOU–MMA system. The chiroptical property of the poly(CEMOU‐co‐ST) was slightly influenced by the co‐units. Poly(CEMOU)‐bonded silica gel as the chiral stationary phase (CSP) was prepared for high‐performance liquid chromatography (HPLC). The CSP resolved trans‐2‐dibenzyl‐4,5‐di(o‐hydroxyphenyl)‐1,3‐dioxolane in normal phase such as n‐hexane/2‐propanol by HPLC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1018–1025, 2003     

Synthesis of a biocompatible poly(2‐hydroxyethyl methacrylate)–chitosan core–shell hydrogel latex

Core–shell hydrogel latexes, composed of a poly(2‐hydroxyethyl methacrylate) (PHEMA) core chemically coated with chitosan (CS) shell, were synthesized via an emulsifier‐free emulsion polymerization, free radically initiated by a redox couple of tert‐butyl hydroperoxide and amine groups on CS itself. The variation of some polymerization parameters [e.g., polymerization time, CS/2‐hydroxyethyl methacrylate (HEMA) weight ratio, and content of crosslinker] was systematically investigated in this study. We found that the weight ratios between CS and the HEMA monomer influenced the course of polymerization, which was traced by the change in percentage monomer conversions, and the colloidal stability of the PHEMA–CS hydrogel latexes obtained. Moreover, the polymerization time affected their particle sizes and surface charges. For the colloidally stable PHEMA–CS hydrogel latexes, their sizes and charges ranged from 600 to 689 nm and from 32 to 51 mV, respectively. N,N′‐Methylene bisacrylamide was used as a crosslinking agent for the core component; this was found to be able to enhance the hydrogels' thermal stability and water uptake. Moreover, the 3‐[4,5‐dimethylthiazol‐2‐yl]‐2,5‐diphenyltetrazolium bromide assay showed that 100% cell viability was achieved during the treatment of the PHEMA–CS latex (0.2–2.5 mg/mL) with Caco‐2 cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40003.     

The structure characterization of thermosensitive poly(N‐isopropylacrylamide‐co‐2‐hydroxypropyl methacrylate) hydrogel

The goal of this work was to investigate a possible way of crosslinking polymer chains and the potential formation of intramolecular hydrogen bonds in thermosensitive poly(N‐isopropylacrylamide‐co‐2‐hydroxypropyl methacrylate) (p(NIPAM‐HPMet)) hydrogels obtained by radical polymerization. The chemical structure of the synthesized hydrogels was investigated by Fourier transform infrared (FTIR) spectroscopy and XRD. The FTIR spectrum confirmed the presence of hydrogen bonds formed between the chains in the copolymer. XRD analysis confirmed the amorphous ? crystalline structure of the copolymer. A three‐glass transition and two melting temperatures were detected by DSC. It was found that the addition of HPMet increased the glass transition and melting temperatures of the p(NIPAM‐HPMet) copolymer. The swelling transport mechanism of p(NIPAM‐HPMet) changed from non‐Fickian at 20 °C to case III or zero‐order time‐independent kinetics characterized by a linear mass uptake with time with increasing temperature at 40 °C. © 2013 Society of Chemical Industry     

侧链含芘基的聚N-异丙基丙烯酰胺的合成及性能

将N-异丙基丙烯酰胺（NIPAM）和甲基丙烯酸-β-(1-芘丁酰氧基)乙酯（PyBEMA）通过自由基溶液共聚合成了侧链含芘基的聚N-异丙基丙烯酰胺共聚物，并采用红外光谱、紫外光谱、核磁共振氢谱对共聚物进行了结构表征。研究了不同投料比对共聚物收率、组成和相对分子质量及其分布的影响。共聚物水溶液温敏性研究表明，共聚物是一类具有低临界溶解温度（LCST）温敏性聚合物，随着共聚物中的芘基含量的升高，其LCST下降；加入α-环糊精（α-CD）会引起共聚物LCST略微升高，而加入β-CD和γ-CD，会导致LCST降低，而且γ-CD引起LCST的降低更显著。共聚物水溶液荧光性能研究表明，共聚物在水中有轻微的疏水聚集，出现侧链芘基激基缔合物荧光。室温下，加入β-CD能够降低共聚物侧链芘基之间的疏水聚集。随着温度的升高，芘基的荧光强度（IM）先下降，后突然升高，然后达到稳定并略微下降；而芘激基缔合物的荧光强度（IE）先出现略微升高，然后基本保持不变，接着缓慢下降。I1/I3荧光强度比值随着温度的升高呈现下降趋势，在聚合物发生相转变时的温度区间内迅速降低。     

Anomalous behavior of the dielectric and electrical properties of polymeric nanodielectric poly(vinyl alcohol)–titanium dioxide films

The complex dielectric permittivity, alternating‐current electrical conductivity, electric modulus, and impedance spectra of polymeric nanocomposite (PNC) films consisting of a poly(vinyl alcohol) (PVA) matrix dispersed with nanosize particles of titanium dioxide (TiO₂); (i.e., PVA–x wt % TiO₂, where x is 0, 1, 3, or 5) were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. A detailed analysis of the results showed that the values of the dielectric and electrical parameters of these PNC‐based nanodielectric films varied anomalously with increasing TiO₂ concentration. The temperature‐dependent dielectric characterization of the PVA–3 wt % TiO₂ film revealed that the dielectric polarization at a fixed frequency increased nonlinearly with increasing temperature. The temperature‐dependent electric modulus relaxation time values of the nanodielectric film obeyed Arrhenius behavior. The X‐ray diffraction study confirmed that the crystalline phase of the PVA matrix decreased with increasing TiO₂ concentration; this suggested that the interaction of the TiO₂ nanoparticles caused some destruction of the hydroxyl group dipolar ordering in the hydrogen‐bonded crystalline structure of the pristine PVA matrix. The intensities of the diffraction peaks of the TiO₂ nanofiller were enhanced as its concentration increased in these nanodielectrics; this confirmed the existence of TiO₂ nanoparticles inside the crystalline phases of the PVA matrix. The surface morphology of the films was examined by the study of their scanning electron micrographs. The feasibility of using these flexible polymeric nanodielectric films as electrical insulators and dielectric substrates in low‐power microelectronic devices operated at audio‐ and radio‐frequency electric fields was explored. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44568.     

Anionomeric waterborne poly(urethane semicarbazide) dispersions and their adhesive properties

Aqueous polyurethane dispersions were prepared from isocyanate‐terminated ionic polyurethane prepolymers by chain extension with dihydrazides. These water‐borne dispersions had excellent adhesive properties and were used to bond leather and canvas. The base polymers were varied with respect to (1) the ionic content with the same chain extender and (2) the nature of the chain extender with the ionic content kept constant. Studies on the particle size and viscosity revealed that the ionic content had an influence on the aforementioned properties: the particle size decreased and the viscosity increased with increasing ionic content. The polarity of the films cast from the dispersions were determined with contact‐angle measurements: hydrophilic character was exhibited by all the compositions. X‐ray studies revealed that the increase in the ionic content led to increasing intensities of the diffraction peaks due to increased secondary forces of bonding. The tensile strength measurements showed that the films were highly elastomeric and had good mechanical strength, which varied with the composition. A shear strength and peel strength analysis of specimens obtained through the bonding of leather to leather, leather to canvas, and canvas to canvas revealed that the waterborne dispersions were excellent adhesives for bonding leather surfaces. Thus, a very efficient, ecofriendly waterborne dispersion of polyurethane that could find applications in bonding leather in the footwear industry was prepared successfully. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and catalytic activity of the thermoresponsive polymers having pyrrolidine side chains as base functionalities

Optically active polymers having chiral 2‐aminomethylpyrrolidine side chains have been newly synthesized by a radical homopolymerization of the corresponding protected acrylamide monomer and copolymerization with N‐isopropylacrylamide followed by deprotection. The resulting polymers were found to be thermoresponsive showing lower critical solution temperatures (LCSTs) at 27–65°C in their aqueous solutions. The pyrrolidine side chains of the resulting thermoresponsive polymer promoted aldol reaction between cyclohexanone and p‐nitrobenzaldehyde in water, and the reaction proceeded most smoothly at its LCST. Moreover, the diastereomeric ratio (syn : anti) of the aldol adducts obtained at the reaction at 40°C was 22 : 78, whereas the diastereomeric ratio (syn : anti) was 55 : 45 at 20°C. These results indicate that the pyrrolidine side chains catalyze the aldol reactions in the relatively hydrophobic field generated by the thermoresponsive polymer at its LCST. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

X‐ray photoelectron spectroscopy and electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid as a function of the synthetic method

X‐ray photoelectron spectroscopy (XPS) has been employed to investigate the protonation degree of polyaniline doped with dodecylbenzenesulfonic acid (Pani. DBSA) obtained by different synthetic methods. The protonation degree has been compared to electrical conductivity. Pani.DBSA prepared through the redoping process in an agate mortar displays conductivity values within the range of 1 S/cm. A protonation level of 48% with almost all imine groups being protonated. Pani.DBSA was also synthesized by oxidative polymerization of aniline in the presence of DBSA, which acts simultaneously as a surfactant and as protonating agent. This in situ doping polymerization was carried out in aqueous or toluene media. In both cases, protonation degrees higher than 50% have been achieved, indicating that a substantial portion of amine units have also been protonated. Higher doping degree has been achieved by aqueous dispersion polymerization of aniline. The C/N and S/N molar ratios obtained by XPS analysis indicate that the polyaniline chains obtained by in situ polymerization are protonated by both sulfonate and hydrogen sulfate anions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 556–565, 2001     

Synthesis and characterization of calcium‐containing poly(urethane‐urea)s

A calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)2] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Four different bisureas like hexamethylene bis(ω,N‐hydroxyethylurea), tolylene 2,4‐bis(ω,N‐hydroxyethylurea), hexamethylene bis(ω,N‐hydroxypropylurea), and tolylene 2,4‐bis(ω,N‐hydroxypropylurea) were prepared by reacting ethanolamine or propanolamine with hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI). Calcium‐containing poly(urethane‐urea)s (PUUs) were synthesized by reacting HMDI or TDI with 1:1 mixtures of Ca(HEEP)2 and each of the bisureas using di‐n‐butyltin dilaurate as a catalyst. The PUUs were well characterized by Fourier transform infrared, 1H‐ and 13C‐NMR (nuclear magnetic resonance), solid‐state 13C cross‐polarization–magic angle spinning NMR, viscosity, solubility, elemental, and X‐ray diffraction studies. Thermal properties of the polymers were also studied by using thermogravimetric analysis and differential scanning calorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3488–3496, 2003