Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 19

1 October 2012

Volume 50, Issue 19

Pages i–iv, 3923–4154

  1. Cover Image

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    3. Articles
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      Cover Image, Volume 50, Issue 19 (pages i–ii)

      Version of Record online: 29 AUG 2012 | DOI: 10.1002/pola.26342

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      Polyaddition reactions of monomers containing a 2-oxazoline ring and a biphenyl unit represent a new efficient way for the preparation of a biphenyl unit containing poly(ester amide)s. As presented on page 3936 by Jozef Luston? , Juraj Kronek, Angela Kleinon̆, Ivica Janigová, Helena Valentová, and Jan Nedbal, the texture of crystalline and liquid crystalline (LC) phases and phase transition temperatures of monomers and polymers are determined by a polarizing optical microscope equipped with a heating stage. The cover picture shows a crystalline structure of the monomer 4,40-bis(2,-oxazolin-2-yl)biphenyl below 250 °C. For the monomer, no LC phase was observed. In spite of this, microphotographs of polymers show the existence of the mesophase with nematic texture.

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      Inside Cover, Volume 50, Issue 19 (pages iii–iv)

      Version of Record online: 29 AUG 2012 | DOI: 10.1002/pola.26343

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      A novel methacrylic monomer to design a new and attractive route in the preparation of bio-active super-paramagnetic nanoparticles (Bio-SP-HNPs) is synthesized and characterized by A. L. Medina-Castillo, J. Morales-Sanfrutos, A. Megia-Fernandez, J. F. Fernandez-Sanchez, F. Santoyo-Gonzalez, and A. Fernandez-Gutierrez on page 3944. The strategy to immobilize biomolecules on super-paramagnetic nanoparticles is based on the reactivity of vinyl sulfone groups with naturally occurring functional groups present in biomolecules (amine and thiol) under very mild conditions and without affecting their catalytic activity. The cover image shows a fluorescence microscopy picture of vinyl sulfone functionalized super-paramagnetic hybrid nanoparticles (SP-HNPs-VS) incubated with aminodansyl. It demonstrates its capacity to immobilize amino functionalized compounds through a Michael type addition reaction on its surface.

  2. Articles

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    2. Cover Image
    3. Articles
    1. Influence of alkoxy tail length on the self-organization of hairy-rod polymers based on mesogen-jacketed liquid crystalline polymers (pages 3923–3935)

      Sheng Chen, Changkai Jie, Helou Xie and Hailiang Zhang

      Version of Record online: 11 JUN 2012 | DOI: 10.1002/pola.26194

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      A series of hairy-rod polymers, poly{2,5-bis[(4-alkoxyphenyl)oxycarbonyl]styrenes} (P-OCm, m is the number of the carbons in the alkoxy groups, m = 1, 2, 4, 6, 8, 10, 12, 14, 16, and 18) were designed and successfully synthesized via free radical polymerization. The phase structures and transitions of the polymers were investigated by the combination of techniques including DSC, wide-angle X-ray diffraction, polarized optical microscopy, and rheological measurement. Combined the microphase separation (low-temperature) and the driving force of the entropy (high temperature), the P-OCm(m = 10, 12, 14, 16, and 18) can form smectic phase, re-entrant isotropic phase and columnar phases in one polymer, which was first reported in the mesogen-jacketed liquid crystalline polymers system.

    2. Synthesis and polymerization reactions of cyclic imino ethers. VI. Polymers with biphenyl structure (pages 3936–3943)

      Jozef Lustoň, Juraj Kronek, Angela Kleinová, Ivica Janigová, Helena Valentová and Jan Nedbal

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26199

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      Two different types of compounds containing a biphenyl and 2-oxazoline units were synthesized. The first type was an AB-type monomer containing a 2-oxazoline ring and hydroxyl group. The second type contains two 2-oxazoline groups and represents a monomer of AA type. Both monomers were used in thermally induced polyaddition reactions. The rod-like structure of the biphenyl unit containing polymers influenced their thermal properties and thermal stability. Both are also dependent on the length of an alkyl linker. Existence of nematic phase of polymers AA+BB type was proved by a polarizing optical microscopy.

    3. Novel synthetic route for covalent coupling of biomolecules on super-paramagnetic hybrid nanoparticles (pages 3944–3953)

      Antonio L. Medina-Castillo, Julia Morales-Sanfrutos, Alicia Megia-Fernandez, Jorge F. Fernandez-Sanchez, Francisco Santoyo-Gonzalez and Alberto Fernandez-Gutierrez

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26203

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      A novel methacrylic monomer to design a new and attractive route in the preparation of bioactive super-paramagnetic nanoparticles (Bio-SP-HNPs) was synthesized and characterized. The Bio-SP-HNPs synthesized by this new route show a relatively narrow size distribution and high magnetic susceptibility. They allow a covalent immobilization of biomolecules on their surface under very mild conditions, without affecting their catalytic activity by means of a Michael-type reaction.

    4. A phase-separable second-generation hoveyda-grubbs catalyst for ring-opening metathesis polymerization (pages 3954–3959)

      Mohammed Al-Hashimi, Chayanant Hongfa, Beena George, Hassan S. Bazzi and David E. Bergbreiter

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26206

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      This work explores the activity of polyisobutylene (PIB) supported second-generation Hoveyda-Grubbs complex 9 in a series of ring-opening metathesis polymerizations. The PIB-supported Ru complex is phase selectively soluble in the heptane phase of thermomorphic mixtures of heptane and polar solvents. The separability of these catalysts leads to lower Ru (0.5 ppm levels) contamination in the polymer products.

      Corrected by:

      Erratum: A phase-separable second-generation hoveyda-grubbs catalyst for ring-opening metathesis polymerization

      Vol. 50, Issue 24, 5211–5212, Version of Record online: 21 SEP 2012

    5. The new low-band gap polymers comprising C-, Si-, or N-bridged dithiophene and alkoxy-modified 2,1,3-benzooxadiazole units for bulk heterojunction solar cells (pages 3960–3969)

      Jian-Ming Jiang, Po-An Yang, Chia-Ming Yu, His-Kuei Lin, Kuei-Chun Huang and Kung-Hwa Wei

      Version of Record online: 5 JUL 2012 | DOI: 10.1002/pola.26216

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      A series of new crystalline, conjugated polymers—PCyTBO, PCySiTBO, and PCyNTBO—featuring alternating C-, Si-, and N-bridged dithiophene-based building blocks and BO units in their backbones were designed and synthesized. The effect of various donor segments on absorption, crystallinity, mobility, and photovoltaic properties of the polymers was investigated.

    6. Doping of polyvinylidene difluoride with cobalt nitrate: Structural, electrical, and magnetic properties (pages 3970–3975)

      Katie Fontaine, Wendy Lopez, Everett Crisman, John Derov and William B. Euler

      Version of Record online: 13 JUN 2012 | DOI: 10.1002/pola.26191

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      Addition of cobalt nitrate to PVDF induces conversion from the α-phase to the β-phase. The Co2+-doped β-phase material has electrical polarization behavior consistent with a relaxor ferroelectric.

    7. Filler effect on properties of “All-Acrylic” copolymer/clay elastomeric materials synthesized by “in situ” nitroxide mediated polymerization (pages 3976–3985)

      N. Cherifi, A. BenAboura, M. Save and L. Billon

      Version of Record online: 11 JUN 2012 | DOI: 10.1002/pola.26192

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      Gradient poly(n-butyl acrylate-grad-methyl methacrylate)/clay materials were synthesized by “in situ” Nitroxyde Mediated Polymerization in the presence of different contents of raw and modified Montmorillonite (1 to 4 wt %). The effect of the clay loading in the copolymers/Montmorillonite system was balanced by the concomitant decrease in molar masses and/or changes in molar compositions of the “all acrylic” elastomeric materials.

    8. A new access to polypyrrole-based functionalized magnetic core-shell nanoparticles (pages 3986–3995)

      Sebastian Karsten, Alexandrina Nan, Rodica Turcu and Jürgen Liebscher

      Version of Record online: 13 JUN 2012 | DOI: 10.1002/pola.26193

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      Azido-functionalized polypyrrole-magnetite core-shell nanoparticles were synthesized by surface initated oxidative polymerization of pyrroles wherein an azido group is tethered to position 3. Miniemulsion technique was applied in this field for the first time rendering this process very efficient. The starting magnetite nanoparticles were stabilized by 12-(pyrrol-1-yl)-dodecanoic acid forming remarkably stable nanofluids. The azido groups of the synthesized core-shell nanoparticles are accessible to Cu-catalyzed click-reaction with alkynes as exemplified by reaction with a biotinylated alkyne. All nanoparticles form stable dispersions and exhibit superparamagnetic behavior making them attractive for various practical applications.

    9. Benzooxadiazaole-based D–A–D co-oligomers: Synthesis and electropolymerization (pages 3996–4003)

      Palas Baran Pati, Soumyajit Das and Sanjio S. Zade

      Version of Record online: 13 JUN 2012 | DOI: 10.1002/pola.26195

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      A new series of D–A polymers were obtained by electrochemical polymerization of D–A–D type co-oligomers comprising the least explored benzo[1,2,5]oxadiazole (BDO) unit as acceptor and furan/thiophene/selenophene/EDOT as donors. All four polymers possess narrow optical band gap. The EDOT-BDO based polymer P5 film exhibited better electrochromic property compared to other three copolymers with a high contrast ratio (66%) and moderate coloration efficiency at 405 nm.

    10. Controllable ring-opening copolymerization of L-lactide and (3S)-benzyloxymethyl-(6S)-methyl-morpholine-2,5-dione initiated by a biogenic compound creatinine acetate (pages 4004–4009)

      Zibo Pang, Hong Li, Peiru He, Yuqin Wang, Hongxia Ren, Hao Wang and X.X. Zhu

      Version of Record online: 13 JUN 2012 | DOI: 10.1002/pola.26196

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      Ring-opening copolymerization of L-lactide and (3S)-benzyloxymethyl-(6S)-methyl-morpholine-2, 5-dione initiated by creatinine acetate was carried outperformed in the bulk at 130 °C. The copolymerization was well controlled as evidenced by that both the measured values of number-average molecular weight and serine (Ser) molar fraction of synthesized copolymers were close to the corresponding theoretical values; and that the higher isotacticity of synthesized copolymers and lower racemization degree of the ring-opening copolymerization. After removing O-benzyls of the copolymers, functional biodegradable copolymers of L-lactic acid and L-serine with designed molar fraction of serine, narrow molecular weight distribution, and improved hydrophilicity were finally obtained.

    11. Functionalization and patterning of reactive polymer brushes based on surface reversible addition and fragmentation chain transfer polymerization (pages 4010–4018)

      Jiyeon Choi, Philipp Schattling, Florian D. Jochum, Jeffrey Pyun, Kookheon Char and Patrick Theato

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26200

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      Reactive polymer brushes based on poly(pentafluorophenyl acrylate) were prepared using a surface reversible addition fragmentation chain transfer (S-RAFT) polymerization. A subsequent post-polymerization modification with a spiropryran moiety facilitated light responsive polymer brushes, enabling a photo-triggered change in wettability. Further the photo-degradation of the immobilized chain transfer agent was exploited for the preparation of photo-patterned reactive polymer brushes.

    12. Modification of polysaccharides via thiol-ene chemistry: A versatile route to functional biomaterials (pages 4019–4028)

      Jimmy Mergy, Audrey Fournier, Emilie Hachet and Rachel Auzély-Velty

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26201

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      A mild and rapid method for the modular functionalization of polysaccharides is presented. Several ene-functional charged and neutral polysaccharides were prepared by esterification of the hydroxyl groups with pentenoic anhydride. The derivatives were shown to undergo essentially quantitative conversions when reacted in aqueous media with thiols via thiol-ene chemistry. This coupling method, having the characteristics of a click reaction, may be advantageously used for the synthesis of functional polysaccharides for biomedical applications. Preliminary investigations demonstrated the ability to prepare cell-responsive hydrogels based on the sequential bioconjugation and crosslinking of dextran with a bioactive peptide and poly(ethylene glycol)-dithiol, respectively.

    13. Synthesis of polybenzoxazine precursors using thiols: Simultaneous thiol–ene and ring-opening reactions (pages 4029–4036)

      Zeynep Beyazkilic, Muhammet U. Kahveci, Binnur Aydogan, Baris Kiskan and Yusuf Yagci

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26202

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      A new class of polybenzoxazine precursors of combined molecular structure of benzoxazine in the open and ring form, thiol, and allyl groups has been developed. Thermally curable benzoxazine networks were obtained by simultaneous photoinduced thiol–ene and COLBERT ring-opening reactions. The thiol–ene reactions were initiated by photolysis of a benzoin type free radical photoinitiator, 2,2-dimethoxy-2-phenyl acetophenone (DMPA), and the competing COLBERT reaction was triggered by thiol compound, 1,2-ethanedithiol, present in the reaction mixture. The extent of reactions was evaluated by conducting experiments both under UV irradiation and in dark using model benzoxazine compounds.

    14. Photoresponsive water-dispersible polyaniline nanoparticles through template synthesis with copolymer micelle containing coumarin groups (pages 4037–4045)

      Jing Luo, Qun Zhou, Jun Sun, Jinqiang Jiang, Xin Zhou, Hongwu Zhang and Xiaoya Liu

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26204

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      A new strategy to prepare photoresponsive PANI nanoparticles through template synthesis using a photosensitive copolymer micelle containing coumarin moieties was reported. The resulting PANI nanoparticles show an interesting photoresponsive behavior in water solution, which is caused by the incorporated photosensitive coumarin moieties, as indicated by UV–vis absorption spectra, DLS analysis, and TEM characterization after irradiation with UV light.

    15. Synthesis of poly(vinyl laurate)-b-poly(vinyl stearate) diblock copolymers by cobalt-mediated radical polymerization in solution (pages 4046–4054)

      René-Ponce Nzé, Olivier Colombani and Erwan Nicol

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26205

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      Poly(vinyl laurate) (PVL) and poly(vinyl stearate) (PVS) were synthesized by means of cobalt-mediated radical polymerization. The efficiency of cobalt(II) diacetylacetonate (Co(acac)2) was demonstrated for controlling the radical polymerization of these monomers in solution. PVL-b-PVS diblock copolymers could be synthesized using two strategies: (1) Sequential addition, and (2) macroinitiator technique. The resulting materials were characterized by differential scanning calorimetry, revealing that both blocks exhibit side-chain crystallinity and phase segregate in the bulk.

    16. Novel antimicrobial polyethylene composites prepared by metallocenic in situ polymerization with TiO2-based nanoparticles (pages 4055–4062)

      Paula A. Zapata, Humberto Palza, Katherine Delgado and Franco M. Rabagliati

      Version of Record online: 5 JUL 2012 | DOI: 10.1002/pola.26207

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      The modified nanoparticles were well distributed into the PE matrix, which was evidenced in the mechanical and antimicrobial properties of the nanocomposites.

    17. Peptidic molecular brushes with enhanced chirality (pages 4063–4072)

      Wen Li, Xiuqiang Zhang, Jue Wang, Xiao Qiao, Kun Liu and Afang Zhang

      Version of Record online: 21 JUN 2012 | DOI: 10.1002/pola.26208

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      Brush-like polymers with monodispersed oligolysine side chains were efficiently synthesized and their secondary structures were analyzed. This molecular brush architecture affords the short peptide side chains a constrained environment to adopt enhanced chirality in solutions at various temperatures because of the reinforced interactions between the proximately packed peptide chains.

    18. A styryl tipno-based nitroxide as efficient mediator for the synthesis of multiblock polystyrenes and well-grafted polymers (pages 4073–4084)

      Pauline Souchal, Thomas Roels, Patrick Hémery and Lucien Marx

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/pola.26209

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      A styryl TIPNO-based nitroxide was prepared in good overall yield. When included in a molecular alkoxyamine, it efficiently mediates the polymerization of styrene and n-butyl acrylate to yield branched polystyrenes and poly(n-butyl acrylate) with a controlled growth of branches. When incorporated in a linear polymer by its self-condensation by manganese coupling, it controls the polymerization of styrene to give multiblock polystyrenes and provides a good control of the synthesis of the polystyrene blocks.

    19. RAFT polymerization of vinyl methacrylate and subsequent conjugation via enzymatic thiol-ene chemistry (pages 4085–4093)

      Firdaus Yhaya, Arlingga Sutinah, Andrew M. Gregory, Mingtao Liang and Martina H. Stenzel

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/pola.26210

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      Poly(vinyl methacrylate) was postmodified with thiols using Candida antartica lipase B. The reaction led to complete functionalization with various small thiols with the sole formation of the anti-Markovnikoff product.

    20. Revisit to the photocrosslinking behavior of PVA-SbQ as a water-soluble photopolymer with anomalously low contents of quaterized stilbazol side chains (pages 4094–4102)

      Kunihiro Ichimura, Shuji Iwata, Shin'ya Mochizuki, Mamoru Ohmi and Daisaku Adachi

      Version of Record online: 5 JUL 2012 | DOI: 10.1002/pola.26211

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      Higher order derivative spectra of films of poly(vinyl alcohol)s tethering stilbazolium side chains revealed the generation of a hypsochromic band at 328 nm (H-band), which disappeared rapidly and selectively under UV irradiation within exposure doses of 10 mJ cm−2. Photoinduced insolubilization of the films were attained at exposure doses of 2–3 mJ cm−2, leading to the conclusion that high photosensitivity comes from the photodimerization of H-aggregate as a ground state dimer.

    21. Producing bimodal molecular weight distribution polymers through facile one-pot/one-step RAFT polymerization (pages 4103–4109)

      Hongjuan Jiang, Lifen Zhang, Jian Qin, Wei Zhang, Zhenping Cheng and Xiulin Zhu

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/pola.26212

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      Bimodal MWD polymers were successfully synthesized using a pair of mono/difunctional trithiocarbonate RAFT agents 1 and 2 via one-pot RAFT polymerization. The system showed excellent controllability and “living” characteristics to both higher and lower molecular weight fractions, providing an efficient and facile way to producing bimodal MWD polymers with both controlled MW and MWD in the molecular level.

    22. Synthesis and characterization of graphene-containing thermoresponsive nanocomposite hydrogels of poly(N-vinylcaprolactam) prepared by frontal polymerization (pages 4110–4118)

      Roberta Sanna, Davide Sanna, Valeria Alzari, Daniele Nuvoli, Sergio Scognamillo, Massimo Piccinini, Massimo Lazzari, Emilia Gioffredi, Giulio Malucelli and Alberto Mariani

      Version of Record online: 5 JUL 2012 | DOI: 10.1002/pola.26215

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      A very simple and effective method for obtaining poly(N-vinylcaprolactam) hydrogels containing high concentration of defect-free graphene was developed. Graphene was obtained by direct graphite sonication in the self-same liquid monomer, and the so-obtained dispersion was directly frontally polymerized, thus avoiding any chemical manipulation and graphene recovery in the solid state. The corresponding nanocomposite materials were fully characterized.

    23. Anthradithiophene–thiophene copolymers with broad UV–vis absorption for organic solar cells and field-effect transistors (pages 4119–4126)

      Hoyoul Kong, Sung Heum Park, Nam Sung Cho, Shinuk Cho and Hong-Ku Shim

      Version of Record online: 26 JUN 2012 | DOI: 10.1002/pola.26217

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      New thiophene-based copolymers containing TIPS-anthra[2,3-b:7,6-b′']dithiophene (TIPS-ADT) showed very broad UV absorption spectra covering the spectral range from 300 to 750 nm. The devices fabricated using TIPS-ADT and thiophene copolymers demonstrated a promising field-effect hole mobility of 5.7 × 10−4 cm2/V s and a power conversion efficiency of 1.30%.

    24. Polycyanurate networks from anethole dimers: Synthesis and characterization (pages 4127–4136)

      Matthew C. Davis, Andrew J. Guenthner, Thomas J. Groshens, Josiah T. Reams and Joseph M. Mabry

      Version of Record online: 29 JUN 2012 | DOI: 10.1002/pola.26218

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      The natural product trans-anethole, which is a common flavor and fragrance raw material isolated on large scale from star anise, is converted into two new dicyanate esters. These dicyanates undergo polymerization to heat-resistant polycyanurate networks. Thermal analysis shows these biobased polycyanurate thermosets are equal to or better than that obtained from commercial cyanate esters derived from petrochemical feedstock.

    25. Precise synthesis of end-functionalized thermosensitive poly(vinyl ether)s by living cationic polymerization (pages 4137–4144)

      Hiroaki Shimomoto, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 29 JUN 2012 | DOI: 10.1002/pola.26219

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      A series of poly(2-methoxyethyl vinyl ether)s with narrow molecular weight distributions and with perfectly defined end groups of varying hydrophobicities was successfully synthesized by base-assisting living cationic polymerization. The cloud points were largely affected by polarity of the end groups (as well as mid groups), molecular weight, and polymer concentration.

    26. Straightforward preparation of polymers based on oligodimethylsiloxane and alkylamine (pages 4145–4154)

      Ludovic Leymarie, Jérôme Dupuy, Estelle Villegas, Philippe Chaumont, Nathalie Sintes-Zydowicz and Etienne Fleury

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26220

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      Novel oligodimethylsiloxane-based polymers with alkyl side chain were synthesized in bulk by step-growth polymerization between α,ω-glycidyl ether oligodimethylsiloxanes and a monoalkylamine in the absence of catalyst and at temperatures ranging between 80 and 180 °C. In such conditions, no etherification was observed and analytical techniques: 1H NMR, MALDI-TOF, and so forth revealed that the main polymer structure was (A2B2) n type with alkyl moieties as dangling chains and attested that the reaction proceeded as a step-growth polymerization.