bluuebunny/crossref_metadata_2025_split huggingface dataset:
Functionalization of polymeric organolithium compounds with formaldehyde
Authors: Quirk Roderic P. , Guo Ya , Wesdemiotis Chrys , Arnould Mark A. 
Published: July 2003

AbstractFunctionalizations of poly(styryl)lithium (PSLi), poly(butadienyl)lithium (PBDLi), and poly(isoprenyl)lithium (PILi) with formaldehyde were investigated in benzene solutions at room temperature. Dimer and unfunctionalized products, in addition to the expected products, were found in the PSLi functionalization with formaldehyde. The byproducts were analyzed by 1H NMR, 13C NMR, size exclusion chromatography (SEC), and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) and showed evidence for Cannizzaro reactions and electron‐transfer reactions. A molecular weight dependence of the dimer formation was found for PSLi functionalizations for number‐average molecular weights of less than 20,000; the dimer formation decreased as the molecular weight increased. Changing the reaction conditions did not eliminate dimer formation in the PSLi functionalization. The reactions of PBDLi and PILi with formaldehyde effected quantitative functionalizations, as determined by SEC, 1H NMR, 13C NMR, MALDI‐TOF MS, quantitative column chromatography, and end‐group titration. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2435–2453, 2003
Mechanical property and biodegradability of solution‐cast films prepared from amphiphilic polylactide‐grafted dextran
Authors: Ouchi Tatsuro , Kontani Tomohiro , Ohya Yuichi 
Published: July 2003

AbstractPolylactide (PLA)‐grafted dextran was synthesized with a trimethylsilyl protection method to produce novel biodegradable, biomedical materials. PLA‐grafted dextrans with various lengths and numbers of graft chains were synthesized. The properties of solution‐cast films prepared from PLA‐grafted dextrans were investigated with thermal and dynamic mechanical analyses. The graft‐copolymer films exhibited lower glass‐transition temperatures, melting temperatures (Tm's), and crystallinities as well as higher viscosity properties as compared with poly‐L‐lactide film. The Tm and crystallinity and mechanical properties at 37 °C could be adjusted by controlling the molecular structure such as the lengths and numbers of graft chains. Furthermore, the biodegradability of PLA‐grafted dextran films was investigated through the weight change of film and the molecular weight change of polymer during the in vitro degradation test. PLA‐grafted dextrans exhibited different degradation behavior from poly‐L‐lactide with the introduction of a polysaccharide segment and branched structure as well as the change of end‐functional group. The degradation rate of PLA‐grafted dextran and the cast film prepared from PLA‐grafted dextran could be adjusted by controlling the sugar content or the length of graft chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2462–2468, 2003
Seeded semicontinuous emulsion copolymerization of methyl methacrylate, butyl acrylate, and phosphonated methacrylates: Kinetics and morphology
Authors: Gaboyard Manuel , Jeanmaire Thomas , Pichot Christian , Hervaud Yves , Boutevin Bernard 
Published: July 2003

AbstractA series of methyl methacrylate, butyl acrylate, and phosphonated methacrylate (MAPHOS) copolymers were prepared by seeded semicontinuous emulsion polymerization under monomer‐starved conditions by varying the amount and nature of phosphonated methacrylates (diester, monoacid, and diacid). The effects on the kinetics, molecular weight distribution, and particle size distribution were investigated. The molecular weights and particle growth were affected by the amount of acidic MAPHOS in the recipe. Secondary nucleation occurred above a critical concentration of acidic MAPHOS (5 wt %). Characterization of the latices by elemental analysis provided information on the phosphonic acid location and showed that phosphonic oligomers were formed in the aqueous phase. Particle size data and electrophoretic behavior of the latex afforded a discussion on the particle surface morphology. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2469–2480, 2003
Synthesis and properties of bismaleimide‐modified novolak resin/silsesquioxane nanocomposites
Authors: Lu Guotao , Huang Ying , Yan Yehai , Zhao Tong , Yu Yunzhao 
Published: July 2003

AbstractBismaleimide‐modified novolak resin/silsesquioxane (BMI‐PN/SiO3/2) nanocomposites were prepared by the sol–gel process. The reactions in the sol–gel synthesis were characterized by Fourier transform infrared spectroscopy. It was found by field emission scanning electron microscopy and atomic force microscopy studies that the particle size of the dispersed phase was about 100 nm, and there existed particle aggregates. The proportion of bismaleimide in the BMI‐PN/SiO3/2 nanocomposites showed an important effect on the thermal properties of the composites, as demonstrated by thermogravimetric analysis and dynamical mechanical analysis. Major improvements in the glass‐transition temperature and the heat resistance of the material were achieved by the introduction of the nanosized SiO3/2 inorganic phase, and the modulus at high temperatures was improved too. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2599–2606, 2003
Synthesis and characterization of chiral liquid‐crystalline polyesters containing sugar‐based diols via melt polymerization
Authors: Lin Qin , Pasatta Jeremy , Long Timothy E. 
Published: July 2003

AbstractLiquid‐crystalline (LC) polyesters based on hexanediol or butanediol, dimethyl 4,4′‐biphenyldicarboxylate, and a sugar‐based diol, isosorbide or isomanide, were prepared with conventional melt polymerization. 1H NMR spectroscopy confirmed that 50 mol % of the charged sugar diol was successfully incorporated into various copolyesters. Modest molecular weights were obtained, although they were typically lower than those of polyester analogues that did not contain sugar‐based diols. Thermogravimetric analysis demonstrated that the incorporation of isosorbide or isomanide units did not reduce the thermal stability in a nitrogen atmosphere. Melting points that ranged from 190 to 270 °C were achieved as a function of the copolyester composition. The lined focal conic fan textures, typical indications of a chiral smectic C LC phase, were observed upon the shearing of the LC melt under polarized light microscopy. Atomic force microscopy revealed that the twisted molecular orientation in the chiral LC phase induced periodically soft lamellar structures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2512–2520, 2003
The fast and the curious: High‐throughput experimentation in synthetic polymer chemistry
Authors: Hoogenboom Richard , Schubert Ulrich S. 
Published: July 2003

AbstractThe application of automated synthetic parallel methods in polymer chemistry is described. A brief overview of all different polymerization techniques that have been used is provided. Furthermore, the equipment and methodologies that were used in our approach for automated parallel polymerization reactions are discussed followed by detailed insight into recent developments on automated cationic ring‐opening polymerization, atom transfer radical polymerization, and emulsion polymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2425–2434, 2003
Diffusion coefficients of the monomer and oligomers in hydroxyethyl methacrylate
Authors: Strauch Jelica , McDonald James , Chapman Bogdan E. , Kuchel Philip W. , Hawkett Brian S. , Roberts G. Evan , Tonge Matthew P. , Gilbert Robert G. 
Published: July 2003

AbstractThe diffusion coefficients are reported of rubbery ternary systems consisting of the polymer, its monomer analogue (i.e., the saturated equivalent of the monomer), and trace quantities of oligomers (dimer, trimer, tetramer and hexamer) for 2‐hydroxyethyl methacrylate (HEMA). These have been obtained with pulsed‐field‐gradient NMR spectroscopy with a polymer weight fraction (fp) of 0 ≤fp≤ 0.4. The oligomers are macromonomers synthesized with a cobalt catalytic chain‐transfer agent. The diffusion coefficients are about an order of magnitude smaller than those for monomers such as methyl methacrylate; this effect is ascribed to hydrogen bonding in HEMA. The diffusion coefficientDiof ani‐meric oligomer has been fitted with moderate accuracy by an empirical universal scaling relation,Di(fp)/D1(fp) ≈i, previously found to provide an adequate fit to corresponding data for styrene and for methyl and butyl methacrylates. The approximate empirical scaling relation seems to hold for a remarkably wide range of types of monomer/polymer systems. These results are of use in modeling rates and molecular weight distributions in free‐radical polymerization, particularly for termination (which is chain‐length‐dependent and is controlled by the diffusion coefficient of chains of the low degrees of polymerization studied here). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2491–2501, 2003
13Carbon nuclear magnetic resonance of ethylene–propylene–1‐decene terpolymers
Authors: Escher Fernanda F. Nunes , Galland Griselda Barrera , Ferreira Márcio 
Published: July 2003

AbstractMany studies have been reported on the 13C NMR characterization of ethylene–α‐olefin copolymers, but only a few have been reported on terpolymers. The incorporation of an α‐olefin into the polyethylene chain changes the structure and, consequently, the properties of the polymer obtained. Looking for new products, we obtained a series of ethylene–propylene–1‐decene terpolymers with the metallocenic system rac‐ethylene bisindenyl zirconium dichloride/methylaluminoxane. We performed a complete 13C NMR characterization of these terpolymers qualitatively and quantitatively. Here we present a detailed study of the 13C NMR chemical shifts, triad sequence distributions, monomer average sequence lengths, and reactivity ratios for these terpolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2531–2541, 2003
Graftlike interpolymer complexes from poly(2‐vinylpyridine) and end‐sulfonic acid polystyrene and polyisoprene: Intermediates to noncovalently bonded block copolymer‐like micelles
Authors: Orfanou Katerina , Topouza Dimitra , Sakellariou George , Pispas Stergios 
Published: July 2003

AbstractThe complexation between narrow molecular weight distribution poly(2‐vinylpyridine) (P2VP) and polystyrene (suPS) or polyisoprene (suPI) end‐functionalized with one sulfonic acid group was examined in tetrahydrofuran dilute solutions by a combination of static and dynamic laser light scattering. Both apparent weight‐average molecular weight (Mw,app) and hydrodynamic radius (Rh) of the complexes exhibited a maximum at a certain molar ratio of suPS chains to P2VP monomeric units. This indicated that the P2VP backbone may be saturated by the grafted end‐functionalized chains because of repulsion between the grafted chains. By changing the molar mass of P2VP from 100,000 to 30,000 g/mol, the values of Mw,app and Rh decreased. When suPI was used instead of suPS, similar trends were observed. In the latter case, it was possible to prepare block copolymer‐like micelles by transferring the P2VP/suPI blend solutions in decane, which is a selective solvent for PI. The non‐covalent‐bonded polymeric micelle characteristics were investigated as a function of sulfonic acid/2‐vinylpyridine units ratio as well as temperature. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2454–2461, 2003
Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction
Authors: Wang S. J. , Meng Y. Z. , Tjong S. C. , Hlil A. R. , Hay A. S. 
Published: July 2003

AbstractHigh‐molecular‐weight poly(phthalazinone)s with very high glass‐transition temperatures (Tg's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers (7a–e) were synthesized from 2‐(4‐chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited Tg's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4‐flurophenyl) sulfone demonstrated the highest Tg of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4′‐isopropylidenediphenol and 4,4′‐(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly‐(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481–2490, 2003
Synthesis of conjugated copolymers containing phenothiazinylene vinylene moieties and their electrooptic properties
Authors: Han Yoon Soo , Kim Sang Dae , Park Lee Soon , Kim Dong Uk , Kwon Younghwan 
Published: July 2003

AbstractFour different types of conjugated copolymers, consisting of alternating structures of phenothiazinylene vinylene and phenylene vinylene derivatives such as phenylene vinylene, 1,1′‐biphenyl‐4,4′‐ylene vinylene, 2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene, and 9,10‐anthrylene vinylene, were prepared by Horner–Emmons condensation between appropriate diphosphonates and dialdehydes. Single‐layer and double‐layer light‐emitting diodes were fabricated with the synthesized conjugated polymers, and their electroluminescent properties were investigated. Poly(N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐9,10‐anthrylene vinylene), containing phenothiazinylene vinylene and anthrylene vinylene as repeat units, emitted a reddish‐orange color with Commission Internationale de l'Eclairage coordinates of x = 0.6173 and y = 0.3814 that was very similar to the National Television System Committee standard red, and it showed a bipolar carrier‐injection/transporting capability caused by electron‐withdrawing anthracene and electron‐donating amino groups. Poly[N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene], containing phenothiazinylene vinylene and dialkoxy phenylene vinylene moieties, showed excellent hole‐injection/transporting capability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2502–2511, 2003
Liquid‐crystalline thermosets by the curing of dimeric liquid‐crystalline epoxyimine monomers with 2,4‐toluene diisocyanate
Authors: Ribera David , Serra Angels , Mantecón Ana 
Published: July 2003

AbstractWe studied the curing processes of several series of dimeric liquid‐crystalline epoxyimine monomers with 2,4‐toluene diisocyanate (TDI) alone or with added catalytic proportions of 4‐(N,N‐dimethylamino)pyridine. We obtained isotropic materials or liquid‐crystalline thermosets with different degrees of order, which depended on the structures of the monomers. To fix ordered networks, we had to do the curing in two steps when TDI was used alone as the curing agent. However, when a tertiary amine was added in catalytic proportions, the ordered networks were fixed in just one step. In this way, we were able to fix both nematic and smectic mesophases. The significance of the polarization of the mesogen for obtaining liquid‐crystalline thermosets was demonstrated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2521–2530, 2003
Synthesis and characterization of crosslinked uniform polymeric microspheres containing a polyimide prepolymer by a new emulsification process
Authors: Ma Guang‐Hui , Fujiwara Junichiro , Su Zhi‐Guo , Omi Shinzo 
Published: July 2003

AbstractA highly crosslinked poly(styrene–divinyl benzene–trimethyolpropane trimethacrylate) microsphere containing a polyimide prepolymer (PIP) was prepared by a new emulsification method, Shirasu porous glass (SPG) membrane emulsification, and a subsequent radical suspension polymerization. That is, a mixture of styrene, divinyl benzene, trimethyol propane trimethacrylate (TMPTMA), and PIP containing an initiator was permeated through the uniform pores of the SPG membrane into a continuous phase containing a stabilizer to form uniform droplets. Then, the suspension polymerization was carried out at 65 °C for 24 h. The trifunctional crosslinker TMPTMA was added to enhance the destructive strength of the microsphere, and PIP was incorporated into the microsphere to provide an adhesion force by a known self‐curing reaction at 220 °C. The effects of the feed amounts of TMPTMA and PIP on the monomer conversion, size distribution, and destructive strength of the microsphere were investigated. The monomer conversion increased with an increase in TMPTMA. The particle size distribution became narrower as the TMPTMA feed amount increased, but it became broader with an increase in PIP. The destructive strength increased with increases in TMPTMA and PIP. After a heat treatment at 220 °C, the destructive strength decreased because of the heat degradation of the polymer. The addition of TMPTMA suppressed the heat degradation, and PIP could undergo self‐curing at 220 °C. The obtained highly crosslinked uniform microsphere containing PIP has potential applications in liquid‐crystal displays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2588–2598, 2003
Self‐curable polyester by a reaction of glycidol with maleic anhydride
Authors: Bicak Niyazi , Karagoz Bunyamin , Tunca Umit 
Published: July 2003

AbstractThe controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003
Synthesis of miktoarm star and miktoarm star block copolymers via a combination of atom transfer radical polymerization and stable free‐radical polymerization
Authors: Celik Cigdem , Hizal Gurkan , Tunca Umit 
Published: July 2003

AbstractA trifunctional initiator, 2‐phenyl‐2‐[(2,2,6,6‐tetramethyl)‐1‐piperidinyloxy] ethyl 2,2‐bis[methyl(2‐bromopropionato)] propionate, was synthesized and used for the synthesis of miktoarm star AB2 and miktoarm star block AB2C2 copolymers via a combination of stable free‐radical polymerization (SFRP) and atom transfer radical polymerization (ATRP) in a two‐step or three‐step reaction sequence, respectively. In the first step, a polystyrene (PSt) macroinitiator with dual ω‐bromo functionality was obtained by SFRP of styrene (St) in bulk at 125 °C. Next, this PSt precursor was used as a macroinitiator for ATRP of tert‐butyl acrylate (tBA) in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 80 °C, affording miktoarm star (PSt)(PtBA)2 [where PtBA is poly(tert‐butyl acrylate)]. In the third step, the obtained St(tBA)2 macroinitiator with two terminal bromine groups was further polymerized with methyl methacrylate by ATRP, and this resulted in (PSt)(PtBA)2(PMMA)2‐type miktoarm star block copolymer [where PMMA is poly(methyl methacrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.38). All polymers were characterized by gel permeation chromatography and 1H NMR. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2542–2548, 2003
Photoinduced and thermally induced cationic polymerizations using S,S‐dialkyl‐S‐(3,5‐dimethylhydroxyphenyl)sulfonium salts
Authors: Crivello James V. , Ahn Jinseo 
Published: July 2003

AbstractA study of the photoinitiated and thermally initiated cationic polymerizations of several monomer systems with S,S‐dialkyl‐S‐(3,5‐dimethylhydroxyphenyl)sulfonium salt (HPS) photoinitiators bearing different lengths of alkyl chains on the positively charged sulfur atom has been conducted. HPS photoinitiators are capable of photoinitiating the cationic polymerization of a wide variety of epoxy and vinyl ether monomers directly on irradiation with short‐wavelength UV light. Aryl ketone photosensitizers are effective in extending the spectral response of these photoinitiators into the long‐wavelength UV region. Kinetic studies with real‐time infrared spectroscopy show that HPS photoinitiators exhibit good efficiency in the polymerization of epoxide and vinyl ether monomers. Comparative studies also demonstrate that S,S‐dimethyl‐S‐(3,5‐dimethyl‐2‐hydroxyphenyl)sulfonium salts are more active photoinitiators than their isomeric S,S‐dimethyl‐S‐(3,5‐dimethyl‐4‐hydroxyphenyl)sulfonium salt counterparts. Both types of HPS photoinitiators display reversible photolysis as a result of facile termination reactions that take place between the growing chains ends with the photogenerated sulfur ylides. Preliminary studies have shown that HPS photoinitiators can also be employed as thermal initiators for the cationic ring‐opening polymerization of epoxides at moderate temperatures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2570–2587, 2003
Synthesis and characterization of second‐generation S,S‐dialkyl‐S‐(dimethylhydroxyphenyl)sulfonium salt photoinitiators
Authors: Crivello James V. , Ahn Jinseo 
Published: July 2003

AbstractA new, simplified method has been developed for the synthesis of S,S‐dialkyl‐S‐(dimethylhydroxyphenyl)sulfonium salt cationic photoinitiators. This novel method has successfully been used for the preparation of S,S‐dialkyl‐S‐(3,5‐dimethyl‐4‐hydroxyphenyl)sulfonium and S,S‐dialkyl‐S‐(3,5‐dimethyl‐2‐hydroxyphenyl)sulfonium salts showing a wide variation in the length and structure of the alkyl chains on the positively charged sulfur atom. These photoinitiators can also be prepared with a wide variety of different anions. The manipulation of the lengths of the alkyl chains permits the design of compatible photoinitiators for highly nonpolar monomers and oligomers such as epoxy‐functional silicones, epoxidized polybutadiene, and epoxidized vegetable oils. This article describes the synthesis and characterization of these photoinitiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2556–2569, 2003