Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 17

1 September 2004

Volume 42, Issue 17

Pages 4101–4477

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      Novel fluorinated polymers by radical polyaddition: Inspiration and progress (pages 4101–4125)

      Tadashi Narita

      Version of Record online: 16 JUL 2004 | DOI: 10.1002/pola.20273

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      The story of the outset and the growth of radical polyaddition of bisperfluoroisopropenyl derivatives [CF2[DOUBLE BOND]C(CFmath image)[BOND]R[BOND]C(CF3)[DOUBLE BOND] CF2] with several organic compounds possessing carbon–hydrogen bonds is described. The reaction afforded novel fluorinated polymers bearing such organic segments in polymer main chains as 1,4-dioxane, diethyl ether, dimethoxyethane, 18-crown-6, triethylamine, glutaraldehyde, and alkanes which have never been supposed as direct starting compounds for preparation of polymers.

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    1. New polyamidation through the activation of amino groups with phenyl dichlorophosphite in pyridine (pages 4126–4131)

      Fukuji Higashi, Shuhji Yokote and Tatsuzo Murakawa

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20231

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      A new polyamidation with phenyl dichlorophosphite in pyridine/N-methyl-2-pyrrolidone was demonstrated. The reaction proceeded through the activation of two molar equivalents of amino groups instead of the activation of carboxyl groups in the usual polycondensation, yielding polyamides of high molecular weights from p-aminobenzoic acid and from aromatic dicarboxylic acids and aromatic diamines.

    2. Atom transfer radical polymerization of methyl methacrylate at ambient temperature using soluble Cu(I) complex catalysts formed with mixed ligands of multidentate amines and halide ions (pages 4132–4142)

      Dhruba P. Chatterjee, Uma Chatterjee and Broja M. Mandal

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20182

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      Atom transfer radical polymerization of methyl methacrylate was successfully performed at ambient temperature using soluble cuprous halide complex catalysts formed with mixed ligands of multidentate amines and halide ions. The living nature of the polymers was proved by the synthesis of the diblock copolymer poly(methyl methacrylate-b-ethyl methacrylate).

    3. Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1-(3-trifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines (pages 4143–4152)

      S. Y. Yang, Z. Y. Ge, D. X. Yin, J. G. Liu, Y. F. Li and L. Fan

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20252

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      A series of fluorinated polyimides were prepared from a novel fluorinated aromatic dianhydride 4,4′-[2,2,2-trifluoro-1(3-trifluoromethylphenyl)ethylidene]diphthalic anhydride (TFDA) and aromatic diamines, i.e., p-phenylenediamine (p-PDA), 4,4′-oxydianiline (ODA), 1,4-bis(4-aminophenoxy)benzene (p-APB), 1,3-bis(4-aminophenoxy)benzene (m-APB), 4-(4-aminophenoxy)-3-trifluoromethylphenylamine (3FODA), and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (6FAPB), by polycondensation procedure. The fluorinated polyimides have good solubility both in strong polar organic solvents and low boiling point organic solvents. The polyimide films exhibited high thermal stability associated with good mechanical properties. It was also found that the polyimide films showed good dielectric properties, which markedly affected the fluorine content in the polymer backbones

    4. Mixed iridium(III) and ruthenium(II) polypyridyl complexes containing poly(ε-caprolactone)-bipyridine macroligands (pages 4153–4160)

      Veronica Marin, Elisabeth Holder, Richard Hoogenboom and Ulrich S. Schubert

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20185

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      Coordination of iridium(III) and ruthenium(II) polypyridyl precursor complexes onto a polycaprolactone-containing bipyridine ligand yielded two metal-containing polymers that displayed interesting photophysical and electrochemical properties.

    5. Kinetic analysis of the mechanolysis of polymethylmethacrylate in the course of vibratory ball milling at various mechanical energy (pages 4161–4167)

      Shin-ichi Kondo, Yasushi Sasai, Shouichi Hosaka, Takaaki Ishikawa and Masayuki Kuzuya

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20245

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      Mechanolysis of poly(methylmethacrylate) (PMMA) at various mechanical energies was carried out. Kinetic analysis of mechanoradical concentrations indicated that the actual amounts of mechanoradicals produced were larger than observed. It is suggested that a large number of reactions occurred in mechanolysis. Thus, it is hoped that improvement in polymer properties can be achieved by mechanochemical reaction of a polymer with a monomer or other polymer.

    6. Nitroxide-mediated free-radical copolymerization of styrene with butyl acrylate (pages 4168–4176)

      Rocio Cuervo-Rodriguez, Vanesa Bordegé, Maria Carmen Fernández-Monreal, Marta Fernández-García and Enrique L. Madruga

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/pola.20183

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      Nitroxide-mediated controlled free-radical copolymerization of styrene and butyl acrylate were studied. Polymerization was performed in bulk at 120 °C in the presence of an acyclic β-phosphonylated nitroxide (N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN)). A bicomponent initiating system was chosen, a radical initiator, 2,2-azobisisobutyronitrile (AIBN), in conjunction with added nitroxide. This copolymerization system exhibited a living/controlled character. Monomer reactivity ratios were determined, and the Mayo–Lewis terminal model provided excellent predictions for the variation in composition over the entire conversion range. The kinetic analysis of this system indicated that the apparent propagation rate coefficient is independent of monomer feed composition, and no limiting conversion was observed, in contrast with the free-radical copolymerization of styrene and n-butyl methacrylate mediated by 1-phenyl-1-(2′,2′,6′,6′-tetramethyl-1′-piperidinyl-oxy)ethane (PETEMPO).

    7. Block copolymers of styrene and n-alkyl methacrylates with long alkyl groups. Micellization behavior in selective solvents (pages 4177–4188)

      Marinos Pitsikalis, Ekaterini Siakali-Kioulafa and Nikos Hadjichristidis

      Version of Record online: 20 JUL 2004 | DOI: 10.1002/pola.20258

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      Well-defined block copolymers of styrene and decyl methacrylate, (SDMA) were prepared by anionic polymerization high vacuum techniques. Their micellization properties were studied in two different solvents, methyl acetate (MAc), selective for the polystyrene (PS) block, and dodecane, selective for the poly(decyl methacrylate) (PDMA) block. The results were compared with those obtained, in the same solvents, from block copolymers of styrene and stearyl methacrylate (SSMA). The experimental results were discussed considering the steric hindrance effect and the ability of the long alkyl groups of the polymethacrylate, MA blocks to crystallize.

    8. Resorcinarene-based ATRP initiators for star polymers (pages 4189–4201)

      Satu Strandman, Minna Luostarinen, Satu Niemelä, Kari Rissanen and Heikki Tenhu

      Version of Record online: 22 JUL 2004 | DOI: 10.1002/pola.20257

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      Two novel multifunctional initiators for atom transfer radical polymerization (ATRP) were synthesized by derivatization of tetraethylresorcinarene. The derivatization induced a change in the conformation of the resorcinarene ring, which was confirmed by NMR spectroscopy. The initiators were used in ATRP of tert-butyl acrylate and methyl methacrylate, giving star polymers with controlled molar masses and low polydispersities. Instead of expected star polymers with eight arms, polymers with four arms were obtained. Conformational studies on the initiators by ROESY NMR and molecular modeling suggest that of eight initiator functional groups on tetraethylresorcinarene, four are located too close to each other to be able to initiate the chain growth. Star-like poly(tert-butyl acrylate) macroinitiators were further used in the block copolymerization of methyl methacrylate.

    9. Incorporation of a new alkenyl-based nonionic surfmer into acrylic latexes (pages 4202–4211)

      Esteban Aramendia, María J. Barandiaran, José C. De La Cal, Jo Grade, Trevor Blease and José M. Asua

      Version of Record online: 23 JUL 2004 | DOI: 10.1002/pola.20259

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      The mechanisms by which a new nonionic alkenyl-based surfmer (Maxemul 5011™) was involved in acrylic emulsion polymerization were investigated. No proof of homopolymerization or of chain transfer to surfmer was obtained under the conditions studied. It was found that the surfmer reacted mainly by copolymerization with the monomers in the outer shell of the polymer particles.

    10. Graft polymerization of polysilsesquioxane containing chloromethylphenyl groups by atom transfer radical polymerization (pages 4212–4221)

      Toshio Sugizaki, Mikihiro Kashio, Atsuko Kimura, Shin-ichi Yamamoto and Osamu Moriya

      Version of Record online: 22 JUL 2004 | DOI: 10.1002/pola.20285

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      Polysilsesquioxane with phenyl and chloromethylphenyl groups (PCPSQ) was used for graft polymerization with several methacrylate monomers in the presence of copper(I) bromide and (−)-sparteine. Atom transfer radical polymerization yielded graft hybrid polymers efficiently, and no gelation was observed. The process was also applied to the preparation of graft block copolymers on PCPSQ.

    11. Synthesis of large, high-solid-content latexes by miniemulsion polymerization (pages 4222–4227)

      Marcelo Do Amaral and José M. Asua

      Version of Record online: 22 JUL 2004 | DOI: 10.1002/pola.20287

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      This work shows the feasibility of using the miniemulsion polymerization technique for the preparation of high-solid-content latices with large particle sizes and narrowly distributed particle size distributions. Monomer miniemulsions were prepared with a high-pressure homogenizer, and droplet sizes of 200–700 nm were obtained. With fixed operational conditions of the homogenizer, the type of stabilizer was the key parameter determining the droplet size. The particle size of the latex obtained by miniemulsion polymerization indicated that the particles were mainly formed by droplet nucleation.

    12. Novel miktofunctional initiator for the preparation of an ABC-type miktoarm star polymer via a combination of controlled polymerization techniques (pages 4228–4236)

      U. Tunca, Z. Ozyurek, T. Erdogan and G. Hizal

      Version of Record online: 22 JUL 2004 | DOI: 10.1002/pola.20284

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      A miktofunctional initiator, 2-(2-bromo-2-methyl-propionyloxymethyl)-3-hydroxy-2-methyl-propionic acid 2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yl oxy)-ethyl ester (5), was used to prepare an ABC-type miktoarm star polymer via a combination of ring-opening polymerization (ROP), stable free-radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). The resultant miktoarm star polymer contained poly(ϵ-caprolactone), polystyrene, and poly(tert-butyl acrylate) arms.

    13. Syntheses of bisazo-containing polymethacrylates using atom transfer radical polymerization and the photoalignment behavior (pages 4237–4247)

      Ming Jin, Qing Xin Yang, Ran Lu, Ting Hua Xu and Ying Ying Zhao

      Version of Record online: 22 JUL 2004 | DOI: 10.1002/pola.20277

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      Three photoresponsive polymethacrylates containing different bisazo chromophores on the side chains were synthesized by atom transfer radical polymerization and their photoinduced birefringence behaviors were studied. These polymers showed similar Mn, Mw, Tg and UV–vis spectra and different trans-cis isomerization rates under irradiation of laser and different contents of the cis-isomers at the photostationary state. Different isomerization rate led to different growth process of birefringence, and the higher the cis content, the larger the saturated value of birefringence.

    14. Synthesis of homopolymers and multiblock copolymers by the living ring-opening metathesis polymerization of norbornenes containing acetyl-protected carbohydrates with well-defined ruthenium and molybdenum initiators (pages 4248–4265)

      Yoshitaka Miyamoto, Michiya Fujiki and Kotohiro Nomura

      Version of Record online: 23 JUL 2004 | DOI: 10.1002/pola.20286

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      Ring-opening metathesis polymerizations of norbornenes containing acetyl-protected glucose [2,3,4,6-tetra-O-acetyl-glucos-1-O-yl 5-norbornene-2-carboxylate (1)] and maltose [2,3,6,2′,3′,4′,6′-hepta-O-acetyl-maltos-1-O-yl 5-norbornene-2-carboxylate (2)] by Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OtBu)2 (A), Ru(CHPh)(Cl)2(PCy3)2 (B; Cy = cyclohexyl), and Ru(CHPh)(Cl)2(IMesH2)(PCy3) (C; IMesH2 = 1,3-dimesityl-4,5-dihydromidazol-2-ylidene) were explored, and polymerizations by both A and B proceeded in a living fashion with high initiation efficiency. First-order relationships between the propagation rates and the monomer concentrations were observed, and the estimated rate constants at 25 °C increased in the following order: A > C > B.

    15. Initiation of free-radical polymerization by peroxypivalates studied by electrospray ionization mass spectrometry (pages 4266–4275)

      Michael Buback, Holm Frauendorf and Philipp Vana

      Version of Record online: 23 JUL 2004 | DOI: 10.1002/pola.20264

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      Initiation by various peroxypivalates of the radical polymerization of methyl methacrylate in toluene solution has been studied via polymer end-group analysis using electrospray ionization mass spectrometry (ESI-MS). Conclusive peak assignments allowed for measuring the type and concentration of the fragments that actually initiate macromolecular growth after thermal decomposition of these peroxypivalates.

    16. Role of cyclic dithiocarbonate as a promoter in the reaction of epoxide and imine in the presence of water (pages 4276–4283)

      Kentarou Suzuki, Hisakazu Horii, Yuko Sugita, Fumio Sanda and Takeshi Endo

      Version of Record online: 27 JUL 2004 | DOI: 10.1002/pola.20246

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      The reaction of epoxide and amine released from imine was promoted by five-membered cyclic dithiocarbonate (DTC) in one-component epoxy resin with imine as a latent initiator. At first, DTC reacted with the amine, which hydrolyzed from imine, to convert into a thiol-containing thiourethane. The thiol group interacted with the epoxide by hydrogen bonding to enhance the reactivity with the amine.

    17. Narrowly dispersed micrometer-sized composite spheres based on diazonium–polystyrene (pages 4284–4288)

      Zhaohui Yang, Hailin Cong and Weixiao Cao

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20256

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      Diazonium group–substituted polystyrene (PS–Nmath image) micrometer-sized spheres with a narrow distribution were prepared from highly crosslinked polystyrene particles. The composite spheres formed with the micro-PS–Nmath image sphere as core and submicro copolymer colloids composed of styrene (S), methyl methacrylate (MMA), and acrylic acid (AA) or SiO2 nanoparticles as shell were then prepared via columbic interaction. The ionic linkages between the core and shell convert to covalent bonds by the thermal treatment process. As a result, the composite spheres become very stable toward polar solvents as well as toward ultrasonic treatment.

    18. Enzyme immobilization to ultra-fine cellulose fibers via amphiphilic polyethylene glycol spacers (pages 4289–4299)

      Yuhong Wang and You-Lo Hsieh

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20271

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      Porous support containing ultra-fine cellulose fibers with an average diameter of 500 nm was chemically modified to immobolize enzyme proteins.A lipase enzyme (E.C. was successfully covalently bound to surfaces of cellulose fibers via a two-step process including activation of cellulose and subsequent coupling of enzymes. The fiber-bound lipase possessed much improved stability upon the exposure to organic solvents, that is, cyclohexane and toluene, as well as higher retention of catalytic activity at elevated temperatures up to 80 °C.

    19. Synthesis and characterization of electrically conducting poly(o-/m-toluidine-co-o-/m-aminoacetophenone) copolymers (pages 4300–4310)

      P. Savitha and D. N. Sathyanarayana

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20208

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      Poly(o-/m-toluidine-co-o-/m-aminoacetophenone) copolymers are synthesized with various compositions of monomers using the emulsion and inverse emulsion methods. The copolymers possess the features of high conductivity and good solubility. The high conductivity of the copolymers may be partially due to their more crystalline nature as deduced from the X-ray diffraction patterns. The influence of the polymerization conditions is investigated. Results are interpreted on the basis of the effect of the [BOND]COCH3 substituent on the polymer chain.

    20. Synthesis, characterization, and degradation of poly(anhydride-co-amide)s and their blends with polylactide (pages 4311–4317)

      Zhi-Qin Zhang, Xin-Mei Su, Han-Ping He and Fan-Qi Qu

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20274

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      Novel polyanhydrides [poly(N,N′-bis (L-alanine) sebacoylamide) (PBSAM)] containing amide groups in the main chains were prepared from natural amino acid and sebacic acid (SA) and characterized by IR, 1H NMR, gel permeation chromatography, and differential scanning calorimetry. PSA, copolymers [P(1,6-bis(P-carboxyphenoxy) hexane (CPH)-BSAM)] and [P(CPH-SA)], blends of P(CPH-BSAM) and P(CPH-SA) with polylactide (PLA) (number-average molecular weight = 2.90 × 105) were also prepared. Then differential scanning calorimetry was used to study their thermal properties. In the end, the hydrolytic degradation was evaluated in 0.1 M phosphate buffer pH 7.4 at 37 °C. The results indicate that the existence of amide, aromatic, and ester bonds in the main chain of polymers slows down the degradation rate, and the tendency becomes clearer with the increasing amount of them. Therefore, these materials will be used for drug delivery and nerve regeneration.

    21. Synthesis and chirooptical properties of optically active poly(ester imide)s based on axially asymmetric 1,1′-binaphthyls (pages 4318–4326)

      Naiheng Song, Wei Qi, Xuepeng Qiu, Lianxun Gao and Mengxian Ding

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20297

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      A series of optically active poly(ester imide)s (PEsI's) has been synthesized by the polycondensation reactions of new axially asymmetric dianhydrides, that is, (R)-2,2′-bis(3,4-dicarboxybenzoyloxy)-1,1′-binaphthyl dianhydride and (S)-2,2′-bis(3,4-dicarboxybenzoyloxy)-1,1′-binaphthyl dianhydride, and various diamines with aromatic, semiaromatic, and aliphatic structures. The polymers have inherent viscosities of 0.45–0.70 dL/g, very good solubility in common organic solvents, glass-transition temperatures of 124–290 °C, and good thermal stability. Wide-angle X-ray crystallography of these polymers shows no crystal diffraction. In comparison with model compounds, an enhanced optical rotatory power has been observed for the repeat unit of optically active PEsI's based on aromatic diamines, and it has been attributed to a collaborative asymmetric perturbation of chiral 1,1′-binaphthyls along the rigid backbones.

    22. Direct synthesis of linear low-density polyethylene of ethylene/1-hexene from ethylene with a tandem catalytic system in a single reactor (pages 4327–4336)

      Fahad Alobaidi, Zhibin Ye and Shiping Zhu

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20288

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      A tandem catalyst system consisting of an ethylene trimerization catalyst, (η5-C5H4CMe2C6H5)TiCl3 (1), and a copolymerization metallocene catalyst, [(η5-C5Me4)SiMe2(tBuN)]TiCl2 (2) or rac-Me2Si(2-MeBenz[e]Ind)2ZrCl2(3) was used to synthesize a series of ethylene-1-hexene copolymers with ethylene as the sole monomer. It has been demonstrated that, by simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylene samples with melting temperature ranging from 60 °C to 128 °C, crystallinity from 5.4% to 53%, and hexene percentage from 0.3 to 14.2 can be efficiently produced. The figure shows the effect of 1 amount on the polymer melting behavior.

    23. Amphiphilic membranes crosslinked and reinforced by POSS (pages 4337–4352)

      Irada S. Isayeva and Joseph P. Kennedy

      Version of Record online: 26 JUL 2004 | DOI: 10.1002/pola.20262

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      The synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments co-crosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane-POSS) cages are described. The materials were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The octasilane-POSS was found to function simultaneously as crosslinker and reinforcing agent.

    24. Synthesis and characterization of polyurethane–urea nanoparticles containing methylenedi-p-phenyl diisocyanate and isophorone diisocyanate (pages 4353–4369)

      In Woo Cheong, Hyun Chul Kong, Jeong Ho An and Jung Hyun Kim

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20298

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      4,4′-methylenedi-p-phenyl diisocyanate (MDI) was successfully introduced into the synthesis of isophorone diisocyanate (IPDI)-based polyurethane–urea nanoparticles, which was achieved by stepwise prepolymer mixing process. The effects of MDI content on the hard–hard segment interaction and consequent crystallinity change of soft segment, i.e., polytetramethylene adipate (PTMA) glycol, was studied and interpreted from the viewpoint of chemical structure of the two diisocyanates.

    25. Konjac glucomannan-graft-acrylic acid hydrogels containing azo crosslinker for colon-specific delivery (pages 4370–4378)

      Zhi-Lan Liu, Han Hu and Ren-Xi Zhuo

      Version of Record online: 27 JUL 2004 | DOI: 10.1002/pola.20272

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      This article presents the synthesis and characterization of novel hydrogel systems designed for colon-targeting drug delivery. The hydrogels were composed of konjac glucomannan (KGM), copolymerized with acrylic acid (AA) and crosslinked by the aromatic azo agent bis(methacryloylamino)-azobenzene (BMAAB). The dependence of swelling ration on the pH and specific biodegradability under β-glycosidase indicate that obtained hydrogels are potential for colon-targeting drug delivery.

    26. Synthesis and ring-opening polymerization of new monoalkyl-substituted lactides (pages 4379–4391)

      Thomas Trimaille, Michael Möller and Robert Gurny

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20251

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      In a two-step one-pot synthesis new monoalkyl-substituted lactides were prepared and polymerized by controlled ring-opening polymerization (ROP) with Sn(Oct)2, Sn(OTf)2, and DMAP, respectively. Good control of molecular weight and narrow polydispersities were achieved for these new functionalized poly(lactides), which are interesting as biocompatible and biodegradable materials for medical applications.

    27. Click chemistry in materials synthesis. 1. Adhesive polymers from copper-catalyzed azide-alkyne cycloaddition (pages 4392–4403)

      David D. Díaz, Sreenivas Punna, Philipp Holzer, Andrew K. McPherson, K. Barry Sharpless, Valery V. Fokin and M. G. Finn

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20330

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      A sticky situation is observed when polyvalent azides and alkynes are assembled into crosslinked polymer networks by copper-catalyzed 1,3-dipolar cycloaddition. The condensation polymerization is efficiently promoted by Cu ions either leached from the metal surface or added to the monomer mixture, and strong interactions with metal surfaces are provided by the multiple triazole binding elements produced.

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    1. Significant effect of hydrogen-bonding interaction on syndiotactic-specificity in radical polymerization of N-isopropylacrylamide (pages 4404–4408)

      Tomohiro Hirano, Hitomi Miki, Makiko Seno and Tsuneyuki Sato

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20315

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      Radical polymerization of N-isopropylacrylamide (NIPAAm) was investigated in toluene at 0 °C in the presence of Lewis base. It was found that O-coordinating Lewis base enhanced syndiotactic-specificity of NIPAAm polymerization and, in particular, the syndiotactic diad reached up to 63% in the presence of twofold amount of hexamethylphosphoramide (HMPA). This is the first example of a direct synthesis of a syndiotactic-rich poly(NIPAAm) by a radical polymerization. The NMR analysis revealed that the 1:1 complex formation of NIPAAm and HMPA through a hydrogen-bonding interaction is the key of the syndiotactic-specific radical polymerization. The mechanism for the present polymerization system was discussed.

  4. Articles

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    1. Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions (pages 4409–4416)

      Vishal Sipani, Ann Kirsch and Alec B. Scranton

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20209

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      The effective propagation rate constant (kp; averaged over all the propagating active centers) was characterized for solvent-free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the kp value as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions followed by a monotonic increase above a threshold value of conversion. The profiles for the kp were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased.

    2. Samarium enolate on crosslinked polystyrene beads. III. Anionic initiator for well-defined synthesis of poly(hydroxyethyl methacrylate) on solid support (pages 4417–4423)

      Masayoshi Tanaka, Atsushi Sudo and Takeshi Endo

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/pola.20210

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      A solid-supported samarium enolate successfully was able to initiate the polymerization of 2-(trimethylsilyloxy)ethyl methacrylate through in a living anionic fashion. The silyl group in the side chain of the formed polymer was readily removed by a weak acid to afford the corresponding well-defined poly(hydroxyethyl methacrylate). The hydroxyl group of the immobilized polymer could be utilized as an initiator for acid promoted ring opening polymerization of lactone to give the corresponding graft copolymer.

    3. Synthesis and photopolymerization of novel multifunctional vinyl esters (pages 4424–4436)

      Tai Y. Lee, W. Kaung, E. Sonny Jönsson, K. Lowery, C. A. Guymon and C. E. Hoyle

      Version of Record online: 29 JUL 2004 | DOI: 10.1002/pola.20181

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      Multifunctional vinyl ester monomers were synthesized via an amine catalyzed Michael addition of thiols to vinyl acrylate. The vinyl ester monomers contain thioether linkages, which are effective in reducing oxygen inhibition of the free-radical homopolymerization and copolymerization processes with acrylates. The vinyl ester monomer not only enhances the polymerization rates of multifunctional acrylates, it also acts as a plasticizer leading to much higher acrylate conversions than obtained in the absence of the vinyl ester.

    4. Kinetic study of the crosslinking reaction of 1,2-polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate (pages 4437–4447)

      Kohji Masaki, Shin-ichi Ohkawara, Tomohiro Hirano, Makiko Seno and Tsuneyuki Sato

      Version of Record online: 29 JUL 2004 | DOI: 10.1002/pola.20250

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      The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy. The initial disappearance rate (R0) of the pendant vinyl groups of 1,2-PB was expressed by R0 = k[DCPO]0.8[vinyl group]−0.2 (120 °C). The unusual rate equation was explained in terms of polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The vinyl group of 1,2-PB showed a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with vinyl acetate (VAc), suggesting that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain.

    5. Segmented block copolymers of poly(ethylene glycol) and poly(ethylene terephthalate) (pages 4448–4457)

      B. García-Gaitán, M. Del P. Pérez-González, A. Martínez-Richa, G. Luna-Bárcenas and S. M. Nuño-Donlucas

      Version of Record online: 30 JUL 2004 | DOI: 10.1002/pola.20301

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      A new series of segmented copolymers were synthesized from poly(ethylene terephthalate) (PET) oligomers and poly(ethylene glycol) (PEG) by a two-step solution polymerization reaction. PET oligomers were obtained by a glycolysis depolimerization. Structural features were characterized by infrared and nuclear magnetic resonance spectroscopies. A single glass-transition temperature was detected for all the synthesized segmented copolymers. The molar masses of the copolymers were determined by GPC.

    6. Metallo-supramolecular block copolymer micelles: Improved preparation and characterization (pages 4458–4465)

      Gottfried Mayer, Vitali Vogel, Bas G. G. Lohmeijer, Jean-François Gohy, Jacomina A. Van Den Broek, Winfried Haase, Ulrich S. Schubert and Dieter Schubert

      Version of Record online: 30 JUL 2004 | DOI: 10.1002/pola.20263

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      An improved method for the preparation of metallo-supramolecular micelles that makes use of a syringe pump for the controlled addition of water is described. This approach yields a very homogeneous distribution of micellar size as analyzed by analytical ultracentrifugation.

    7. Influence of ortho-substituents on the synthesis and properties of poly(phenylacetylene)s (pages 4466–4477)

      Martin G. Mayershofer, Martin Wagner, Udo Anders and Oskar Nuyken

      Version of Record online: 30 JUL 2004 | DOI: 10.1002/pola.20265

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      A series of poly(phenylacetylene)s bearing increasingly sterically demanding ortho-substituents in their phenyl rings were prepared via polymerization initiated either by Mo[N-2,6-i-Pr2C6H3)(CHCMe2Ph)[OCMe(CF3)2]2 or by the quaternary system MoOCl4n-Bu4Sn–EtOH–quinuclidine (1:1:2:1). Depending on the steric demands of the ortho-substituents of the monomer and the initiating system employed, the synthesis of soluble, deeply colored poly(phenylacetylene)s was achieved in moderate to high yields. The size of the ortho-substituents decisively influenced not only the polymerizability of the monomer with the initiator used, but also the maximum effective conjugation length of the polymers as well as their solution stability.