bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Poly(p‐Benzenesulphonamide). Part III Solution Polymerisation
Authors: Contreras Jordi , Jones J. Idris 
Published: July 2010

AbstractPoly (p‐benzene sulphonamide) has been prepared from N‐sulphinylaniline‐4‐sulphoch‐loride, aniline‐4‐sulphochloride, and aniline‐4‐sulphochloride hydrochloride by solution polymerisation at low temperatures in the presence of a base. In the case of aniline‐4‐sulphochloride and its hydrochloride, clear evidence has been obtained of the intermediacy of a sulphene species, 4‐imino‐cyclohexadiene sulphene. With the addition of one equivalent of water in the polymerisation of the N‐sulphinyl monomer, aniline‐4‐sulphochloride is first formed and polymerisation ensues through the same sulphene intermediate. Poly(p‐benzene‐N‐methylsulphonamide) similarly results from the solution polymerisation of N‐methylaniline‐4‐sulphochloride hydrochloride. Polymerisation of crystalline aniline‐4‐sulphochloride hydrochloride has also been effected in the solid state in a non solvent.Certain amide solvents, which have proved to be very effective in the polymerisation of 4‐aminobenzoyl chloride hydrochloride to give poly(p‐benzamide), do not appear to be suitable for the polymerisation of aniline‐4‐sulphochloride hydrochloride. With dimethyl formamide and N‐methyl pyrrolidone, aniline‐4‐sulphochloride hydrochloride undergoes a condensation reaction. With tetramethyl urea, some polymerisation occurs but the yield and molecular weight of the polymer are low. A copoly (amide‐sulphonamide) has been prepared by polymerising molar equivalents of 4‐aminobenzoyl hydrochloride and aniline 4‐sulphochloride hydrochloride in pyridine.
Incorporation of a conjugated side‐chain in regioregular polythiophenes: Chiroptical properties and selective oxidation
Authors: Peeters Helmuth , Verbiest Thierry , Koeckelberghs Guy 
Published: July 2010

AbstractThe synthesis, aggregation, and optical properties of a chiral, regioregular polythiophene, substituted with a conjugated substituent, are described. The polymer was prepared using a Stille coupling reaction. The fact that the side‐chain contributes to the absorption (UV‐vis), emission (fluorescence), and redox behavior (cyclic voltammetry) of the material demonstrates that the substituent contributes to the electronic properties. It was shown that the conjugated side‐chain chirally stacks in conditions in which the polymer backbone aggregates, which demonstrates the ability of conjugated polymers to induce a (chiral) lamellar organization of conjugated moieties, present in their side‐chain. The aggregation of both the side‐chain and the backbone was monitored using UV‐vis and CD spectroscopy. Finally, it is shown that the conjugated side‐chain can selectively be oxidized, without oxidizing the polythiophene backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1891–1900, 2009
Block copolymers of poly(ethylene oxide) and poly(vinyl alcohol) synthesized by the RAFT methodology
Authors: Tong Yin‐Yin , Dong Yong‐Quan , Du Fu‐Sheng , Li Zi‐Chen 
Published: July 2010

AbstractA methodology for the synthesis of well‐defined poly(ethylene oxide)‐block‐poly(vinyl alcohol) (PEO‐b‐PVA) and PVA‐b‐PEO‐b‐PVA polymers was reported. Novel xanthate end‐functionalized PEOs were synthesized by a series of end‐group transformations. They were then used to mediate the reversible addition–fragmentation chain transfer polymerization of vinyl acetate to obtain well‐defined poly(ethylene oxide)‐b‐poly(vinyl acetate) (PEO‐b‐PVAc) and PVAc‐b‐PEO‐b‐PVAc. When these block copolymers were directly hydrolyzed in methanol solution of sodium hydroxide, polymers with brown color were obtained, which was due to the formation of conjugated unsaturated aldehyde structures. To circumvent these side reactions, the xanthate groups were removed by adding a primary amine before hydrolysis and the products thus obtained were white powders. The polymers were characterized by gel permeation chromatography, 1H NMR spectroscopy and FT‐IR. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1901–1910, 2009
Synthesis and evaluation of new dental monomers with both phosphonic and carboxylic acid functional groups
Authors: Sahin Gorkem , Albayrak Aylin Ziylan , Bilgici Zeynep SaraylI , Avci Duygu 
Published: July 2010

AbstractNovel dental monomers containing both phosphonic and carboxylic acid functional groups were prepared. The monomers were based on t‐butyl α‐bromomethacrylate (t‐BuBMA) and synthesized in three steps: The reaction of o‐hydroxyaryl phosphonates [diethyl (2‐hydroxyphenyl) phosphonate, tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) diphosphonate and tetraethyl 5,5′‐(propane‐2,2‐diyl)bis(2‐hydroxy‐5,1‐ phenylene) diphosphonate] with t‐BuBMA, the hydrolysis of phosphonate groups to phosphonic acid using trimethyl silylbromide, and the hydrolysis of the t‐butyl groups to carboxylic acid with trifluoroacetic acid. The monomers were solids and soluble in water and ethanol. The structures of the monomers were determined by Fourier transform infrared (FTIR), 1H, 13C, and 31P nuclear magnetic resonance (NMR) spectroscopy. The copolymerization behaviors of the synthesized monomers with glycerol dimethacrylate were first investigated in bulk using photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. Then, the solution copolymerization of the monomers with acrylamide in ethanol and water was studied, indicating that the synthesized monomers are incorporated into the copolymers. The acidic nature of the aqueous solutions of these monomers (pH values 1.72–1.87) is expected to give them etching properties important for dental applications. The interaction of the monomers with hydroxyapatite was investigated using 13C NMR and FTIR techniques. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1953–1965, 2009
Preparation of comb‐like copolymers with amphiphilic poly(ethylene oxide)‐b‐polystyrene graft chains by combination of “graft from” and “graft onto” strategies
Authors: Sun Ruiming , Wang Guowei , Liu Chao , Huang Junlian 
Published: July 2010

AbstractA novel method for preparation the comb‐like copolymers with amphihilic poly(ethylene oxide)‐block‐poly(styrene) (PEO‐b‐PS) graft chains by “graft from” and “graft onto” strategies were reported. The ring‐opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out first using α‐methoxyl‐ω‐hydroxyl‐poly(ethylene oxide) (mPEO) and diphenylmethyl potassium (DPMK) as coinitiation system, then the EEGE units on resulting linear copolymer mPEO‐b‐Poly(EO‐co‐EEGE) were hydrolyzed and the recovered hydroxyl groups were reacted with 2‐bromoisobutyryl bromide. The obtained macroinitiator mPEO‐b‐Poly(EO‐co‐BiBGE) can initiate the polymerization of styrene by ATRP via the “Graft from” strategy, and the comb‐like copolymers mPEO‐b‐[Poly(EO‐co‐Gly)‐g‐PS] were obtained. Afterwards, the TEMPO‐PEO was prepared by ring‐opening polymerization (ROP) of EO initiated by 4‐hydroxyl‐2,2,6,6‐tetramethyl piperdinyl‐oxy (HTEMPO) and DPMK, and then coupled with mPEO‐b‐[Poly(EO‐co‐Gly)‐g‐PS] by atom transfer nitroxide radical coupling reaction in the presence of cuprous bromide (CuBr)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) via “Graft onto” method. The comb‐like block copolymers mPEO‐b‐[Poly(EO‐co‐Gly)‐g‐(PS‐b‐PEO)] were obtained with high efficiency (≥90%). The final product and intermediates were characterized in detail. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1930–1938, 2009
Precision synthesis and characterization of thymine‐functionalized polyisobutylene
Authors: Sen Mustafa Y. , Puskas Judit E. , Dabney David E. , Wesdemiotis Chrys , Absalon Christelle 
Published: July 2010

AbstractA new two‐step synthesis of polyisobutylene (PIB) with precisely one thymine functionality per chain (PIB‐T) is reported. The primary hydroxyl‐functionalized PIB (PIB‐OH) precursor was prepared by direct functionalization via living carbocationic polymerization of isobutylene initiated by the α‐methylstyrene epoxide/TiCl4 system. Matrix assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐ToF MS) of a low molecular weight PIB‐OH precursor demonstrated the effectiveness of direct functionalization by this method. A PIB‐acrylate precursor (PIB‐Ac) was obtained from such a PIB‐OH, and the PIB‐T was subsequently prepared by Michael addition of thymine across the acrylate double bond. MALDI‐ToF MS of the products verified that all polymer chains carried precisely one thymine group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3501–3506, 2010
Synthesis of polyethylene and polypropylene containing fluorene units in the side chain
Authors: Naga Naofumi , Sakai Hiroki , Usui Chiharu , Tomoda Haruhiko 
Published: July 2010

AbstractCopolymerizations of ethylene or propylene and allyl monomers containing 9‐fluorenyl group, diallyl‐di‐9‐fluorenylsilane (DAFS), 9,9‐diallylfluorene (DAF), and 9‐allylfluorene (AF), were investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged zirconocene catalysts, especially a syndioselective catalyst, showed a higher reactivity for all the comonomers than the nonbridged catalysts. DAFS was mainly incorporated into the polymer chain via cyclization insertion, whereas DAF was copolymerized via both 1,2‐ and cyclization insertions. Cyclization selectivity, ratio of cyclized insertion unit, of DAF in the copolymerization with propylene was higher than that in the copolymerization with ethylene. Copolymerization with AF yielded low‐molecular weight copolymer because of frequent chain transfer reaction. Optical properties of the propylene based‐copolymers were investigated by UV‐vis and photoluminescence spectroscopy, and absorption‐ and emission‐derived from fluorenyl groups were detected in the copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3542–3552, 2010
Synthesis and characterization of epoxy functionalized cooligomers based on chlorotrifluoroethylene and allyl glycidyl ether
Authors: Santhosh Kumar K. S. , Ameduri Bruno 
Published: July 2010

AbstractThe synthesis of functionalized fluorocooligomers based on chlorotrifluoroethylene (CTFE) and allyl glycidyl ether (AGE) under radical copolymerization is presented. The compositions of comonomers in the cooligomers were determined by three different analyses viz: from 1H and 19F NMR spectroscopy by using 1,3‐bis(trifluoromethyl) benzene as the external standard, epoxy equivalent weight value, and elemental analyses. The compositions determined by three methods were matching reasonably well and showed that the resulting poly(CTFE‐co‐AGE) cooligomers exhibit a tendency for alternation. The distribution of the monomers in the cooligomers was proposed based on the assessment of the reactivity ratios, ri, of both comonomers. These values were determined from the kinetics of radical copolymerization of CTFE with AGE from Fineman‐Ross, Kelen‐Tudos, and extended Kelen‐Tudos methods which led to the assessment of the average reactivity ratios as: rCTFE = 0.20 ± 0.03 and rAGE = 0.15 ± 0.08 at 74 °C. The lower Mn values substantiated the formation of cooligomers rather than copolymers. The formation of cooligomers was attributed to the chain transfer to AGE (by hydrogen abstraction from AGE) from the allylic transfer. The poly(CTFE‐co‐AGE) cooligomers were soluble in most of the common organic polar solvents. An optimization of cooligomer yields was investigated by using ethyl vinyl ether as a third comonomer and from different initiators. The thermal stabilities of the cooligomers, obtained by thermal gravimetric analysis, showed a 5% weight loss at temperatures over 225 °C under air. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3587–3595, 2010
Facile synthesis of polyaniline hemispheres in diethyl ether/ice mixture solvent and growth mechanism study
Authors: Ma Hui‐yan , Li Yun‐wu , Cao Fei , Gao Yu , Gong Jian , Deng Yu‐lin 
Published: July 2010

AbstractBy using the new methodology of synthesis of container structure, we demonstrate the ability to control an improved ice‐templating method to synthesis of polyaniline (PANI) in the form of hemisphere. The influence of the synthetic parameters, such as the concentration of doping‐acid, oxidant, and aniline on the morphologies of PANI structures, has been investigated. It is determined that the doping acid and the second solvent added (such as diethyl ether absolute) have great positive influence on the formation of product's micro‐morphology. The structure and morphology of PANI hemispheres are characterized by Fourier transform infrared (FT‐IR) spectra, X‐ray diffraction (XRD) patterns, energy‐dispersive X‐ray analysis (EDX), optical microscope images, and scanning electron microscope images (SEM). The formation mechanism of hemispheres in this article is well suggested. PANI hemispheres have super performance in sensitivity, time response to NH3 compared with traditional polymerization at room temperature. This work extends the field of functional materials with complex container structure and offers a new green route to synthesis of hemispherical container structure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3596–3603, 2010
Reducibly degradable hydrogels of PNIPAM and PDMAEMA: Synthesis, stimulus‐response and drug release
Authors: Zhang Bo‐yu , He Wei‐Dong , Li Li‐ying , Sun Xiao‐li , Li Wen‐tao , Zhang Ke‐ren 
Published: July 2010

AbstractReducibly degradable hydrogels of poly(N‐isopropylacrylamide) (PNIPAM) and poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) were synthesized by the combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and click chemistry. The alkyne‐pending copolymer of PNIPAM or PDMAEMA was obtained through RAFT copolymerization of propargyl acrylate with NIPAM or DMAEMA. Bis‐2‐azidyl‐isobutyrylamide of cystamine (AIBCy) was used as the crosslinking reagent to prepare reducibly degradable hydrogels by click chemistry. The hydrogels exhibited temperature or pH stimulus‐responsive behavior in water, with rapid response, high swelling ratio, and reproducible swelling/shrinkage cycles. The loading and release of ceftriaxone sodium proved the feasibility of the hydrogels as the stimulus‐responsive drug delivery system. Furthermore, the presence of disulfide linkage in AIBCy favored the degradation of hydrogels in the reductive environment. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3604–3612, 2010
Ring opening polymerization of lactide promoted by alcoholyzed heteroscorpionate aluminum complexes
Authors: Silvestri Antonella , Grisi Fabia , Milione Stefano 
Published: July 2010

AbstractThe alcoholysis of the heteroscorpionate methyl aluminum complex (bpzmp)AlMe2 (1) (bpzmp = 2,4‐di‐tert‐butyl‐6‐(bis‐(3,5‐dimethylpyrazol‐1‐yl)methyl)phenoxo), promoted both by phenol and isopropanol, has been investigated. The reaction of 1 with phenol afforded the dimeric mono(phenoxo) derivative 2, whereas the alcoholysis of 1 with the less acidic isopropanol involved the coordinated heteroscorpionate ligand and led to the tetrahedral complex 3 in which the aluminum atom is surrounded by one κ2‐N,O− coordinated bpzmp ligand and one η1‐O− coordinated ppzmp ligand (ppzmp = 2,4‐di‐tert‐butyl‐6‐(i‐propoxy‐(3,5‐dimethylpyrazol‐1‐yl)methyl)phenoxo). Complexes 1–3 have been tested in the ring opening polymerization (ROP) of L‐lactide. The dimeric mono(phenoxo) derivative 2 was inactive in the ROP of L‐lactide. Quite surprisingly, complex 3 was found to be active in ROP of L‐ and rac‐lactide, showing a good molar‐mass control. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3632–3639, 2010
Specific recognition of syndiotactic poly(methacrylic acid) in porous isotactic poly(methyl methacrylate) thin films based on the effects of stereoregularity, temperature, and solvent
Authors: Kamei Daisuke , Ajiro Hiroharu , Akashi Mitsuru 
Published: July 2010

AbstractThe effects of stereoregularity, temperature, and solvent on the specific recognition of syndiotactic (st)‐poly(methacrylic acid) (PMAA) in macromolecularly porous isotactic (it)‐poly(methyl methacrylate) films were investigated to give important insights into the regularity and stability of nanospaces in the it‐PMMA films as well as template polymerization. The porous it‐PMMA films were fabricated on quartz crystal microbalance (QCM) substrates via the layer‐by‐layer (LbL) assembly of it‐PMMA/st‐PMAA, plus the st‐PMAA extraction from the assembly. QCM analysis and infrared spectroscopy revealed the first case of stereocomplex formation using st‐PMAA with lower stereoregularity (rr = 73%) in the LbL films, while st‐PMAA obtained with conventional free radical polymerization (rr = 62%) was barely incorporated into the porous it‐PMMA films. The maximum st‐PMAA incorporation increased from 25 to 40 °C, but there were almost no difference between 40 and 55 °C, indicating that the it‐PMMA crystallization would also be accelerated with increasing temperature. The studies on st‐PMAA incorporation with various complexing solvents revealed that the host it‐PMMA in the porous films could only form the original stereocomplex with 2/1 unit‐molar stoichiometry (st‐PMAA/it‐PMMA) in acetonitrile/water or ethanol/water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3651–3657, 2010
Synthesis, characterization, electrochromic properties, and electrochromic device application of a novel star polymer consisting of thiophene end‐capped poly(ε‐caprolactone) arms emanating from a hexafunctional cyclotriphosphazene core
Authors: Gorur Mesut , Yilmaz Faruk , Kilic Adem , Demirci Ali , Ozdemir Yusuf , Kosemen Arif , Eren San Sait 
Published: July 2010

AbstractHexa‐armed and thiophene (Thi) end‐capped poly(ε‐caprolactone) star polymer (N3P3‐(PCL‐Thi)6), containing cyclotriphosphazene core, was prepared in a four‐step reaction sequence. Ring‐opening polymerization (ROP) and “click chemistry” techniques were employed in the first and final steps, respectively. Hexa‐armed PCL star polymer (N3P3‐(PCL‐OH)6) was successfully synthesized via ROP of ε‐caprolactone (ε‐CL) by using hekzakis(p‐(hydroxymethyl)phenoxy) cyclotriphosphazene as the multisite initiator and tin(II) 2‐ethylhexanoate (Sn(Oct2)) as the catalyst in bulk at 115 °C. Further modifications of the N3P3‐(PCL‐OH)6 were accomplished by derivatization of the hydroxyl‐functional chain ends. The obtained N3P3‐(PCL‐OH)6 was then reacted with 2‐bromo‐2‐methylpropanoyl bromide, and this led to a star polymer with bromide end groups, N3P3‐(PCL‐Br)6. In the third step, N3P3‐(PCL‐Br)6 was azidified with sodium azide (NaN3) in DMF affording N3P3‐(PCL‐N3)6. Conversion of the azide chain end groups into Thi was quantitatively accomplished via the “click reaction” between N3P3‐(PCL‐N3)6 and prop‐2‐yn‐1‐yl 3‐thienyl acetate in the final step. Subsequently, the star polymer with six Thi chain ends (N3P3‐(PCL‐Thi)6) was employed in electrochemical copolymerization with both pyrrole and Thi. Electrochromic properties and electrochromic device application of N3P3‐(PCL‐Thi)6/PThi were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3668–3682, 2010
Real‐time SAXS and WAXS study of the multiple melting behavior of poly(ε‐caprolactone)
Authors: Yang I‐Kuan , Liu Chia Yun 
Published: July 2010

AbstractThe multiple melting behavior of poly(ε‐caprolactone) (PCL) was investigated by real‐time small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) measurements coupling with differential scanning calorimetry (DSC). Semicrystalline specimens prepared by a continuous cooling process showed lengthening of the Bragg period during the progress of double melting. A model of variable thickness of lamella was proposed to fit to the SAXS patterns and revealed that both the crystalline lamella and the amorphous layer contributed to the increase in Bragg period while the later dominated the contribution. The model of variable thickness although satisfied the SAXS data was unable to compromise the data from other probing tools. A modification of the model proposed that each lamella piling up to construct the stacks in the crystallites was itself nonuniform in thickness. The modification with the parallel occurrence of the mechanism of surface melting and crystallization successfully compromised the observations from SAXS, DSC, and optical microscopy and provided a new perspective for the explanation to lengthening of the Bragg period related to multiple melting behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1777–1785, 2010
Study of layered silicate clays as synergistic nucleating agent for polypropylene
Authors: Preschilla Nisha , Rasheed A. S. Abdul , Sahadevan Swayajith , Biswas Amit , Bellare Jayesh R. , Shyamroy Subarna 
Published: July 2010

AbstractEffect of very small quantities of organically modified layered silicate clay on the nucleation of polypropylene (PP), as an additive at ppm levels dosage was investigated, in combination with two of the most commercially exploited organic nucleating agents, one of which is a cyclic aromatic phosphinate salt and the other is bis(3,4‐dimethylbenzylidene) sorbitol, each representing a separate class of nucleating molecules by itself. Substitution of a considerable fraction of either of these organic nucleating agents with organically modified inorganic nanoclay was seen to result in a unique synergy between the two in nucleating PP. Polarized light microscopy studies of these synergistic formulations with organoclay to nucleating agent ratios of 1:1 and 1:3 totaling 0.2 weight percent in PP showed significant reduction in spherulite size from that of non‐nucleated PP, and compared with the samples containing exclusive organic nucleating agent at similar loading. Differential scanning calorimetric studies provided evidence and insight into such synergistic behavior. Crystallization and supercooling temperatures for the synergistic formulations were comparable for those formulations containing only organic nucleating agents, indicating comparable nucleation efficiency, whereas organoclay alone, although showing some extent of nucleation, was clearly poorer in efficiency. Wide and small angle X‐ray scattering studies further explained these observations. An increase in the gamma polytype fraction was seen in samples that contained both organoclay and nucleating agent, pointing to the role of organoclay as a gamma nucleator. Organoclay was found to be completely exfoliated in these synergistic formulations and was seen as well‐dispersed, single platelets in the PP matrix. A hybrid network consisting of exfoliated organoclay platelets and organic nucleating agent molecules was proposed, which is more stable and stiffer than the network formed by nucleating agent alone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1786–1794, 2010