bluuebunny/crossref_metadata_2025_split huggingface dataset:
Copolymers of N‐alkyl‐ and N‐arylalkylacrylamides with acrylamide: influence of hydrophobic structure on associative properties. Part I: viscometric behaviour in dilute solution and drag reduction performance
Authors: Camail Michel , Margaillan André , Martin Isabelle 
Published: November 2008

AbstractBACKGROUND: Drag reduction properties from dilute aqueous polymer solution are obtained with very high molecular weight water‐soluble polymers. The aim of this work was to examine the potential of acrylamide polymers modified with small amounts of N‐alkyl‐ and N‐arylalkylacrylamides (0.5 and 1 mol%).RESULTS: The associative properties improve with the length of the graft alkyl chain, and with its proportion in the copolymer and with the presence of aromatic groups. The drag reduction efficiency of these copolymers in very dilute solution was measured to relate the activity to the molecular parameters.CONCLUSION: The results obtained indicate that the persistent drag reduction activity can be linked to the presence of strong intramolecular associations. Copyright © 2008 Society of Chemical Industry
Photopolymerization of thiol‐ene systems based on oligomeric thiols
Authors: Clark Tolecia , Kwisnek Luke , Hoyle Charles E. , Nazarenko Sergei 
Published: November 2008

AbstractThiol oligomers were copolymerized with a triallyl ether by a photoinduced polymerization process. These oligomeric thiol‐ene systems comprise the same components as a photopolymerized thiol‐ene‐acrylate ternary system, yet the photopolymerized networks have much lower glass transition temperatures. An investigation into the effect of oligomeric thiol design on network formation was conducted by analyzing the reaction kinetics and thermal/mechanical properties of the thiol‐ene networks. Real‐time FTIR analysis shows that total conversion is >90% for all thiols investigated. Photo‐DSC analysis shows that the maximum exotherm rate is roughly equivalent for all of the thiols when the equivalent weight of the thiol is taken into account. As would be expected, the glass transition temperature and tensile strength increase with thiol functionality and lower thiol equivalent weight for thiols with functionality from 2 to 4. Films made using the oligomeric thiols have essentially the same glass transition temperatures and tensile modulus values regardless of thiol design. These results distinguish the method for generation of networks consisting of an initial Michael reaction of thiols and acrylates followed by a photoinitiated copolymerization with a multifunctional ene from the traditional photolysis of the corresponding thiol‐ene‐acrylate ternary systems with no Michael reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 14–24, 2009
Solid‐supported amphiphilic triblock copolymer membranes grafted from gold surface
Authors: Rakhmatullina Ekaterina , Mantion Alexandre , Bürgi Thomas , Malinova Violeta , Meier Wolfgang 
Published: November 2008

AbstractGold‐supported amphiphilic triblock copolymer brushes composed of two hydrophilic poly(2‐hydroxyethyl methacrylate) (PHEMA) blocks and a hydrophobic poly(n‐butyl methacrylate) (PBMA) middle part were synthesized using a surface‐initiated ATRP. Attenuated total reflectance Fourier transform infrared spectroscopy, polarization modulation infrared reflection absorption spectroscopy (PM‐IRRAS), ellipsometry, contact angle measurements, and atomic force microscopy were used for the characterization of PHEMA‐co‐PBMA‐co‐PHEMA brushes. The PM‐IRRAS analysis revealed an increase of the chain tilt toward the gold surface during growth of the individual blocks. We suggest that the orientation of the amphiphilic polymer brushes is influenced by both the chain length and the interchain interactions. Additionally, a detachment of the polymer membranes from the solid support and subsequent gel permeation chromatography analyses allowed us to establish their compositions. We applied block‐selective solvents (water and hexane) as well as a good solvent for the whole polymer chain (ethanol) to study the morphology and solvent responsive behavior of the amphiphilic brushes. The presented results could serve as a good starting point for the fabrication of functional solid‐supported membranes for biosensing applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1–13, 2009
Evaluation of automated synthesis for chain and step‐growth polymerizations: Can robots replace the chemists?
Authors: Rojas Ramiro , Harris Nicole K. , Piotrowska Karolina , Kohn Joachim 
Published: November 2008

AbstractThis article explores current challenges in the use of automated parallel synthesizers in polymeric materials research. Four types of polymerizations were investigated: carbodiimide‐mediated polyesterification, diphenol phosgenation, free radical, and reversible addition‐fragmentation chain‐transfer (RAFT). Synthetic challenges of condensation polymerization, such as liquid and solid dispensing accuracy, dropwise addition, and toxic chemical handling, were successfully met using the automated synthesizer. Both solid and liquid dosing of the diphenol and diacid were successful for polyarylate synthesis. The high precision of liquid dispensing made it possible to achieve stoichiometric balance using reagent stock solutions. For all reactions, molecular weights and their reproducibility were comparable to those obtained with manual synthesis. For RAFT polymerizations, solvent and mol ratio of chain transfer reagent to initiator were successfully optimized on the automated synthesizer and a library of over 60 polymethacrylate copolymer compositions was generated. Considerable savings in time relative to manual methods were achieved when generating polymer libraries (e.g., 4.5× faster for 96 polymethacrylates and 20× faster for 45 for polycarbonates). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 49–58, 2009
Model‐based design and synthesis of gradient MMA/tBMA copolymers by computer‐programmed semibatch atom transfer radical copolymerization
Authors: Zhao Ying , Luo Ying‐Wu , Ye Changhuai , Li Bo‐Geng , Zhu Shiping 
Published: November 2008

AbstractMethyl methacrylate (MMA)/tert‐butyl methacrylate (tBMA) gradient copolymers having linear and hyperbolic composition profiles were synthesized. These special copolymer products were achieved via a model‐based computer‐controlled semibatch atom transfer radical copolymerization (ATRcoP) process. A simple ATRcoP model was developed based on the terminal model. The equilibrium constants in the ATRP of MMA and tBMA were estimated by the data correlation. The model was verified by batch experiments and was found to give good correlation for the polymerization rate, molecular weight, and copolymer composition data. The model coupled with a reactor model was then applied to the semibatch ATRcoP and was used to calculate comonomer feeding rates for the targeted gradient composition profiles. It was found that the experimental monomer conversion, molecular weight, and cumulative copolymer composition were in good agreement with their targeted theoretical values. The gradient copolymers had low polydispersities close to 1.1. This work demonstrated the feasibility of the model‐based semibatch ATRcoP in fine‐tuning gradient copolymer composition profiles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 69–79, 2009
Linear and comb‐like acrylonitrile/N‐isopropylacrylamide copolymers synthesized by the combination of RAFT polymerization and ATRP
Authors: Wan Ling‐Shu , Lei Hao , Ding Yao , Fu Lei , Li Jing , Xu Zhi‐Kang 
Published: November 2008

AbstractWe describe the synthesis of three novel thermoresponsive copolymers of acrylonitrile (AN) with N‐isopropylacrylamide (NIPAM) by a combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Linear copolymer polyacrylonitrile (PAN)‐b‐PNIPAM was directly prepared by RAFT polymerization. Comb‐like copolymers were synthesized by ATRP using brominated AN/2‐hydroxyethyl methacrylate copolymers as macroinitiators, which were prepared by RAFT polymerization. FT‐IR, NMR, and GPC were employed to characterize the synthesized copolymers. Results indicate that the polymerization processes can be well controlled and the resultant copolymers have well‐defined structures as well as narrow polydispersity. Then dense films were fabricated from these thermoresponsive copolymers and the surface wettability was evaluated by water contact angle measurements at different temperatures. It is found that the surface wettability is temperature‐dependant and both the transition temperature and decrement of water contact angle are affected by the copolymer shapes as well as the length of PNIPAM blocks. Considering the excellent fiber‐ and membrane‐forming properties of PAN‐based copolymers, the obtained thermoresponsive copolymers are latent materials for functional fibers and membranes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 92–102, 2009
Field‐effect transistors based on PPV derivatives as a semiconducting layer
Authors: Lee Woo‐Hyung , Kong Hoyoul , Oh Se‐Young , Shim Hong‐Ku , Kang In‐Nam 
Published: November 2008

AbstractA series of modified thiophene groups containing PPV‐based semiconducting materials, poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(2,2′bithienylenevinylene)] (PPBT), poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(5,5‐thiostilylenevinylene)] (PPTVT), have been synthesized through a Horner coupling reaction. From the FTIR and 1H NMR spectroscopy, the configuration of the vinylene groups in the polymers was all trans (E) geometry. The weight‐average molecular weights (Mw) of PPBT and PPTVT were found to be 11,700 and 11,800, with polydispersity indices of 2.51 and 2.53, respectively. PPBT and PPTVT thin films exhibit UV–visible absorption maxima at 538 and 558 nm, respectively, and the strong absorption shoulder peaks at 578 and 602 nm, respectively. Solution processed field‐effect transistors (FET) fabricated using all the polymers showed p‐type OTFT characteristics. The field‐effect mobility of the PPTVT was obtained up to 2.3 × 10−3 cm2 V−1 s−1, an on/off ratio of 1.0 × 105 with ambient air stability. Studies of the atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis of the polymer thin films revealed that all the polymers were amorphous structure. The greater planarity and rigidity of PPTVT compared to PPBT results in elongation of conjugation length and better π–π stacking of polymer chains in amorphous region, which leads to improved FET performance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 111–120, 2009
Synthesis of original para‐sulfonic acid aminoethylthioethylbenzenesulfonic by telomerization, and its grafting onto poly(VDF‐co‐HFP) copolymers for proton exchange membrane for fuel cell
Authors: Taguet Aurelie , Ameduri Bruno , Boutevin Bernard 
Published: November 2008

AbstractThe synthesis of a novel aromatic sulfonic acid bearing an amino function H2NC2H4SC2H4C6H4SO3Na (1) from the radical addition of mercaptoethylamine hydrochloride onto styrene sodium sulfonate, and its subsequent grafting onto poly(vinylidene fluoride‐co‐hexafluoropropylene), poly(VDF‐co‐HFP), copolymer are presented. First, the radical telomerization, carried out under radical conditions and in water, led to various products [monoadduct (1), multiadducts, and polymers], the amounts of which depend on the experimental conditions and [mercaptan]0/[monomer]0 initial molar ratio (R0). An R0 ≥ 1 led to the monoadduct (1) only and achieved in ∼85% yield. The zwitterionic isomer was obtained mainly and its chemical modification was possible to get an original aromatic sodium sulfonate containing an amino end group. A kinetic study of the telomerization was presented for R0 < 1. Thermogravimetric analysis of the telomer showed that this compound was stable up to 200 °C. Second, the grafting of (1) onto poly(VDF‐co‐HFP) copolymer was also investigated. Such a grafting proceeded as expected by a classic mechanism of grafting of amines. Molar percentages of grafted telomer were assessed by 1H NMR spectroscopy and by elemental analysis. Ion exchange capacity (IEC) values of the membranes were deduced from the mol % grafted telomer. Scanning electron microscopy pictures showed a good homogeneity in the cross‐section of membranes, and energy dispersive X‐ray evidenced that all SO3Na groups of the grafted amine were changed into SO3H after treatment with concentrated HCl. Method involving an impedance analyzer, working at increasing high frequencies was used to assess the protonic conductivities, σ. These values were lower than that of Nafion117®, but σ increased with the IEC to 0.4 mS/cm at room temperature and 95% relative humidity. Water and methanol uptakes were also assessed, and it was shown that σ increased when water uptakes increased. Membranes started to decompose from 170 °C under air. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 121–136, 2009
Synthesis, characterization, and application of light‐emitting copolyfluorenes slightly doped with distyrylbenzene derivatives
Authors: Liao Chiung‐Feng , Hsieh Bar‐Yuan , Chen Yun 
Published: November 2008

AbstractCopolyfluorenes PFG1∼PFG4 slightly doped with 0.006–0.5 mol % of 2,5‐dihexyloxy‐1,4‐bis(2‐phenyl‐2‐cyanovinyl)benzene (green chromophore) were synthesized by the Suzuki coupling reaction to be evaluated as hosts for white‐light electroluminescent (EL) devices. Their optical, thermal and electrochemical properties were almost identical to those of polyfluorene (PF) due to minimal chromophore content. However, the electroluminescent (EL) spectra of the PFGn were very different from photoluminescence spectra in film state. Relative intensity of green emission (ca. 521 nm) in EL spectra are much stronger than those in PL spectra, which can be attributed to charges trapping in the chromophores due to its narrow band gap (Eg ≈ 2.56 eV). The performance of EL devices [ITO/PEDOT:PSS/polymer/Ca (50 nm)/Al (100 nm)] were improved with an increase in chromophore content. The PFG4 device revealed the best performance (6790 cd/m2, 1.69 cd/A), and the PFG1 and PFG2 devices exhibited comparable intensity in blue and green emissions. Blend EL devices were fabricated by using the PFGn as the hosts and a red iridium complex [Ir(piq)2(acac)] as dopant. By controlling the amount of the iridium complex, the white‐light emitting device was achieved with PFG2, with maximum brightness and CIE coordinate being 4120 cd/m2 and (0.31, 0.28), respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 149–160, 2009
Cinnamate‐functionalized poly(ester‐carbonate): Synthesis and its UV irradiation‐induced photo‐crosslinking
Authors: Hu Xiuli , Chen Xuesi , Cheng Haibo , Jing Xiabin 
Published: November 2008

AbstractA functionalized cyclic carbonate monomer containing a cinnamate moiety, 5‐methyl‐5‐cinnamoyloxymethyl‐1,3‐dioxan‐2‐one (MC), was prepared for the first time with 1,1,1‐tri(hydroxymethyl) ethane as a starting material. Subsequent polymerization of the new cyclic carbonate and its copolymerization with L‐lactide (LA) were successfully performed with diethyl zinc (ZnEt2) as initiator/catalyst. NMR was used for microstructure identification of the obtained monomer and copolymers. Differential scanning calorimetry (DSC) was used to characterize the functionalized poly(ester‐carbonate). The results indicated that the copolymers displayed a single glass transition temperature (Tg) and the Tg decreased with increasing carbonate content and followed the Fox equation, indicative of a random microstructure of the copolymer. The photo‐crosslinking of the cinnamate‐carrying copolymer was also demonstrated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 161–169, 2009
Syntheses of aliphatic polyesters catalyzed by lanthanide triflates
Authors: Garaleh Mazen , Lahcini Mohammed , Kricheldorf Hans R. , Weidner Steffen M. 
Published: November 2008

AbstractPolycondensations of 1,6‐hexane diol and sebacic acid were conducted in bulk with addition of a lanthanide triflate as acidic catalyst. With exception of promethium triflate all lanthanide triflates were studied. A particularly low molecular weight was obtained with neodym triflate and the best results with samarium triflate. With Sm(OTf)3 weight average (Mw) values up to 65 kDa (uncorrected SEC data) were achieved after optimization of the reaction conditions. Comparison of these results with those obtained from bismuth, magnesium, and zinc triflates, on the one hand, and comparison with the acidities of all catalysts, on the other, indicates that the esterification mechanism involves complexation of monomer by metal ions. Preparation of multiblock copoly(ether ester)s failed due to insufficient incorporation of poly(tetrahydrofuran) diols. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 170–177, 2009
Multiarm star block copolymers via Diels‐Alder click reaction
Authors: Dag Aydan , Durmaz Hakan , Tunca Umit , Hizal Gurkan 
Published: November 2008

AbstractTwo types of multiarm star block copolymers: (polystyrene)m‐poly(divinylbenzene)‐poly(methyl methacrylate)n, (PS)m‐polyDVB‐(PMMA)n and (polystyrene)m‐poly(divinylbenzene)‐poly(tert‐butyl acrylate)k, (PS)m‐polyDVB‐(PtBA)k were successfully prepared via a combination of cross‐linking and Diels–Alder click reactions based on “arm‐first” methodology. For this purpose, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross‐linking reaction of divinyl benzene using α‐anthracene end functionalized polystyrene (PS‐Anth) as a macroinitiator. Thus, obtained multiarm star polymer was then reacted with furan protected maleimide‐end functionalized polymers: PMMA‐MI or PtBA‐MI at reflux temperature of toluene for 48 h resulting in the corresponding multiarm star block copolymers via Diels–Alder click reaction. The multiarm star and multiarm star block copolymers were characterized by using 1H NMR, SEC, Viscotek triple detection SEC (TD‐SEC) and UV. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 178–187, 2009
Block copolymer micelles as nanoreactors for single‐site polymerization catalysts
Authors: Bouilhac Cécile , Cloutet Eric , Taton Daniel , Deffieux Alain , Borsali Redouane , Cramail Henri 
Published: November 2008

AbstractNew micelle‐like organic supports for single site catalysts based on the self‐assembly of polystyrene‐b‐poly(4‐vinylbenzoic acid) block copolymers have been designed. These block copolymers were synthesized by sequential atom transfer radical polymerization (ATRP) of styrene and methyl 4‐vinylbenzoate, followed by hydrolysis. As evidenced by dynamic light scattering, self‐assembly in toluene that is a selective solvent of polystyrene, induced the formation of micelle‐like nanoparticles composed of a poly(4‐vinylbenzoic acid) core and a polystyrene corona. Further addition of trimethylaluminium (TMA) afforded in situ MAO‐like species by diffusion of TMA into the core of the micelles and its subsequent reaction with the benzoic acid groups. Such reactive micelles then served as nanoreactors, MAO‐like species being efficient activators of 2,6‐bis[1‐{(2,6‐diisopropylphenyl)imino}ethyl]pyridinyl iron toward ethylene polymerization. These new micelle‐like organic supports enabled the production of polyethylene beads with a spherical morphology and a high bulk density through homogeneous‐like catalysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 197–209, 2009
Nearly monochromatic red electroluminescence from a nonconjugated polymer containing carbazole segments and phenanthroline [Eu(β‐diketonate)3] moieties
Authors: Zhang Zhi‐guo , Yuan Ji‐bing , Tang Huai‐jun , Tang Hao , Wang Li‐na , Zhang Ke‐Li 
Published: November 2008

AbstractA novel nonconjugated copolymer (PVKEu) with carbazole segments and phenanthroline [Eu(β‐diketonate)3] moieties was synthesized via free radical copolymerization, and characterized by FTIR, 1H NMR spectroscopy, GPC, ICP, and elemental analysis. The copolymer exhibited good solubility, as well as good thermal stability and high glass transition temperature. The photoluminescence (PL) of this polymer in solution and in solid film has been studied. A multi‐layer device with the configuration of ITO/PEDOT: PSS (40 nm)/PVKEu (70 nm)/BCP (15 nm)/AlQ3 (30 nm)/LiF/Al exhibited nearly monochromatic red emission at 615 nm and voltage‐independent spectral stability. Our results suggest that enhancing the ligand‐mediated energy transfer between the matrix polymer and europium complex is a potential method to improve the electroluminescence performance of the Eu‐chelated polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 210–221, 2009
Hyperbranched copolymer containing triphenylamine and divinyl bipyridyl units for fluorescent chemosensors
Authors: Feng Jichang , Li Yang , Yang Mujie 
Published: November 2008

AbstractA fluorescent hyperbranched copolymer (HTP) and a linear copolymer (PTP) as a reference sample to HTP both containing triphenylamine and divinyl bipyridyl units were synthesized via Heck coupling reaction from 5,5′‐Divinyl‐2,2′‐bipyridyl with tris(4‐bromophenyl)amine and with 4,4′‐dibromotriphenylamie, respectively. The chemical structure of HTP was confirmed by FTIR, 1H NMR, and 13C NMR. The polymer HTP had a number‐average molecular weight of 1895 and a weight‐average molecular weight of 2315, and good solubility in conventional organic solvents, such as THF, DMF, and chloroform, and exhibited good thermal stability. The UV–vis absorption and photoluminescence (PL) spectra exhibited absorption maximum at 428 nm and emissive maximum at 531 nm for the HTP solution. The spectroscopic results of HTP and PTP indicated that hyperbranched conjugated structure increases the effective conjugation length, as compared with corresponding linear conjugated structure. The fluorescence of the polymer in solution can be quenched by various transition metal ions. The effect of backbone structure of the conjugated polymer‐based chemosensors on the sensitivity and selectivity in metal ions sensing have been investigated, and the quenching effect of HTP is more sensitive toward transition metal than linear copolymer PTP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 222–230, 2009
A novel hydroxy functionalized polyester obtained by ring opening copolymerization of L‐lactide with a pyrolysis product of cellulose
Authors: Dobrzynski Piotr , Fabbri Daniele , Torri Cristian , Kasperczyk Janusz , Kaczmarczyk Bozena , Pastusiak Malgorzata 
Published: November 2008

AbstractA hydroxylactone ((1R,5S)‐1‐hydroxy‐3,6‐dioxabicyclo [3.2.1] octan‐2‐one, abbreviated as LAC) obtained from catalytic pyrolysis of cellulose was investigated as a monomer in the synthesis of polyesters by ring‐opening polymerization (ROP) with L‐lactide. Although stannous octoate resulted inactive, ROP initiated by zirconium (IV) acetylacetonate afforded novel copolyesters from LAC and lactide mixtures in the bulk at 110 °C. Copolymers were obtained with different LAC content (from 19 to 45%) with a random microstructure as established by detailed NMR analysis. FTIR spectrometry confirmed the presence in the polymer chain of the OH groups originally present in LAC, which do not react during polymerization due to steric hindrance and inter/intramolecular hydrogen bonding. Reaction with trichloroacetylisocyanide proved that OH groups of the polyesters can be readily derivatized. The application of LAC as a comonomer enables the insertion of the alcohol functionality in polylactide avoiding protection/deprotection steps and potentially expanding the realm of biomaterials affordable from carbohydrate feedstock. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 247–257, 2009