Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 6

15 March 2004

Volume 42, Issue 6

Pages 1293–1536

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      Dendritic aromatic polyamides and polyimides (pages 1293–1309)

      Mitsutoshi Jikei and Masa-aki Kakimoto

      Version of Record online: 23 JAN 2004 | DOI: 10.1002/pola.20018

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      The syntheses and properties of dendritic and hyperbranched aromatic polyamides and polyimides are reviewed. In addition to conventional stepwise reactions for dendrimer synthesis, an orthogonal/double-stage convergent approach and dendrimer syntheses with unprotected building blocks are described as new synthetic strategies for dendritic polyamides. Hyperbranched polyamides and polyimides composed of various repeating units are presented. Besides the self-polycondensation of AB2-type monomers, new polymerization systems with AB4, AB8, A2 + B3, and A2 + BB′2 monomers have been developed for hyperbranched polyamides and polyimides. The copolymerization of AB2 and AB monomers is discussed separately with respect to the effects of branching units on the properties.

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    1. Chemically functionalized clay vinyl ester nanocomposites: Effect of processing parameters (pages 1310–1321)

      D. Yebassa, S. Balakrishnan, E. Feresenbet, D. Raghavan, P. R. Start and S. D. Hudson

      Version of Record online: 23 JAN 2004 | DOI: 10.1002/pola.11073

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      We chose the reactive surfactant approach in formulating vinyl ester–montmorillonite clay nanocomposites. The reactive onium salt (ω-undecylenyl amine hydrochloride) was synthesized from ω-undecylenyl alcohol through a series of synthetic conversions. Nonreactive onium salt (undecyl amine hydrochloride) was made from undecyl amine. The relative amounts of exfoliated, intercalated, and as-treated clay and the size of the clay particle aggregates depended significantly on the composition of clay and the processing conditions. As observed, the progressive absence of X-ray diffraction peaks clearly demonstrated that it is the combination of partially reactive clay and mixing conditions that promotes layer separation and achieves a greater degree of exfoliation.

    2. Synthesis and properties of photoalignable aromatic polyesters containing phenylenediacrylate units in their backbones and n-alkyl moieties in their side groups (pages 1322–1334)

      Seung Woo Lee and Moonhor Ree

      Version of Record online: 23 JAN 2004 | DOI: 10.1002/pola.11059

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      A series of new photoreactive aromatic polyesters was synthesized; all these polyesters have high molecular weight, and good solubility and film formation ability. The polymers are thermally stable up to 357 °c. In films, the polymer chains undergo preferential photoalignment on irradiation with linearly polarized ultraviolet light. The photoaligned films induce liquid crystal alignments that range from homogeneous to homeotropic along the chain orientation direction, depending on the length of the n-alkyl side groups. The excellent properties of the polyesters make them promising candidate materials for use as LC alignment layers in advanced liquid crystal display devices.

    3. All hydrocarbon main-chain thermotropic liquid crystalline polymers, poly(1,1′-biphenylene-4,4′-alkenediyl)s, prepared by the ADMET method and their hydrogenated polymers, poly(1,1′-biphenylene-4,4′-alkanediyl)s (pages 1335–1349)

      Sung-Hoon Joo and Jung-Il Jin

      Version of Record online: 23 JAN 2004 | DOI: 10.1002/pola.11061

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      A series of poly(4,4′-biphenylenealkenylene)s and copolymers were prepared by the acyclic diene metathesis (ADMET) polymerization of 4,4′bis(alkeylene)-1,1′-biphenyls. Unsaturated polymers thus prepared were then hydrogenated to produce the corresponding saturated polymers. All the polymers were found to be thermotropic and to form solid-like smectic phases in melt. We observed that one of the phenylene units of the biphenyl structure could selectively be hydrogenated at an elevated temperature.

    4. Facile synthetic route to polymerizable hindered amine light stabilizers for transition-metal-catalyzed olefin copolymerization (pages 1350–1355)

      M. Auer, R. Nicolas, A. Vesterinen, H. Luttikhedde and C.-E. Wilén

      Version of Record online: 26 JAN 2004 | DOI: 10.1002/pola.11082

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      A simple route was developed for the direct synthesis of a 2,2,6,6-tetramethylpiperidine-functionalized α-olefin light stabilizer. The hindered amine light stabilizer monomer was successfully randomly copolymerized with ethene via metallocene catalysis, as shown in the 13C NMR spectrum of the synthesized copolymer.

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    1. Synthesis and characterization of novel biodegradable amphiphilic graft polymers based on aliphatic polycarbonate (pages 1356–1361)

      Tao Peng, Si-Xue Cheng and Ren-Xi Zhuo

      Version of Record online: 26 JAN 2004 | DOI: 10.1002/pola.11067

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      A series of biodegradable amphiphilic graft polymers were successfully synthesized by grafting poly(2,2-dimethyltrimethylene carbonate) sequences onto a water-soluble polymer poly-α,β-[N-(2-hydroxyethyl)-L-aspartamide] (PHEA) backbone. We established the feasibility of preparing these novel graft polymers by the ring-opening polymerization initiated by the macroinitiator PHEA bearing hydroxyl groups without adding any catalyst. The successful grafting of poly(2,2-dimethyltrimethylene carbonate) sequences onto the PHEA backbone was verified by combined size exclusion chromatography and multi-angle laser light scattering analysis. The chemical structures of graft polymers were characterized by Fourier transform infrared and 1H NMR. By controlling the feed ratio of the monomer to the macroinitiator, graft polymers with different hydrophilicities can be easily obtained.

    2. Utility of atom transfer radical polymerization for the preparation of poly(methyl methacrylate) beads in an aqueous suspension (pages 1362–1366)

      Niyazi Bicak, Mustafa Gazi, Umit Tunca and Inan Kucukkaya

      Version of Record online: 26 JAN 2004 | DOI: 10.1002/pola.11093

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      The copper-mediated atom transfer radical polymerization of methyl methacrylate proceeds with first-order kinetics and controlled chain growth to yield nearly spherical bead polymers (300–600 μm) in aqueous suspensions when hexylated triethylenetetramine and poly(vinyl pyrrolidone) are used as the ligand and stabilizer, respectively.

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    1. Effect of the synthetic method and support porosity on the structure and performance of silica-supported CuBr/pyridylmethanimine atom transfer radical polymerization catalysts. I. Catalyst preparation and characterization (pages 1367–1383)

      Joseph V. Nguyen and Christopher W. Jones

      Version of Record online: 27 JAN 2004 | DOI: 10.1002/pola.20001

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      Silica-supported CuBr/pyridylmethanimine (PMI) complexes that facilitate the atom transfer radical polymerization of methyl methacrylate are prepared and characterized. Four different synthetic routes including multistep grafting, two-step grafting, one-pot, and preassembled complex methods are evaluated on three different silica supports [SBA-15 (48 and 100 Å pores) and Cab-O-Sil EH5]. The resulting solids are characterized by a battery of techniques. The combination of elemental analysis and spectroscopic results indicate that a variety of different surface species likely exist for most catalysts, including copper species that are both mono and bis-coordinated by PMI ligands as well as PMI-free CuBr species interacting with the silica surface.

    2. Effect of the synthetic method and support porosity on the structure and performance of silica-supported CuBr/pyridylmethanimine atom transfer radical polymerization catalysts. II. Polymerization of methyl methacrylate (pages 1384–1399)

      Joseph V. Nguyen and Christopher W. Jones

      Version of Record online: 28 JAN 2004 | DOI: 10.1002/pola.20008

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      A systematic study of the effect of synthesis method and catalyst structure on the atom transfer radical polymerization (ATRP) performance of CuBr/pyridylmethanimine complexes supported on silica is described. Four different synthetic routes, including multistep-grafting, two-step-grafting, one-pot, and preassembled-complex methods are evaluated on three different silica supports [SBA15 (48 and 100-Å pores) and Cab-O-Sil EH5]. The resulting solids are utilized for ATRP of methyl methacrylate. Nonporous Cab-O-Sil was the most effective support because of its small particle size, lack of porosity, and relative solubility in the reaction media. The catalysts could be effectively recycled, with improved controlled character.

    3. Synthesis of spherical and hemispherical sugar-containing poly(ornithine) dendrimers (pages 1400–1414)

      Huricha Baigude, Kaname Katsuraya, Kohsaku Okuyama, Kenichi Hatanaka, Emi Ikeda, Naokazu Shibata and Toshiyuki Uryu

      Version of Record online: 28 JAN 2004 | DOI: 10.1002/pola.11031

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      A series of sugar-containing poly(ornithine) dendrimers for possible antigen delivery and related applications is synthesized by combining maltose or lactose to the surface of poly(ornithine) dendrimer G3 through reductive amination. The structure and the degree of substitution of poly(ornithine) dendrimers with different peripheral amino groups are investigated by NMR and mass spectrometry.

    4. Synthesis and cationic photopolymerization of new silicon-containing oxetane monomers (pages 1415–1420)

      M. Sangermano, R. Bongiovanni, G. Malucelli, A. Priola, J Olbrych, A. Harden and N. Rehnberg

      Version of Record online: 28 JAN 2004 | DOI: 10.1002/pola.20005

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      The cationic photopolymerization of oxetane-based systems containing silicon monomers was investigated. New silicon-containing oxetane monomers were synthesized for this purpose. The surface properties of UV-cured films were greatly modified, depending on the silicon monomer structure and concentration.

    5. Influence of interfaces on the rates of crosslinking in poly(dimethyl siloxane) coatings (pages 1421–1431)

      T. R. E. Simpson, Z. Tabatabaian, C. Jeynes, B. Parbhoo and J. L. Keddie

      Version of Record online: 28 JAN 2004 | DOI: 10.1002/pola.20006

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      The reaction rate of a silyl (SiH) crosslinker in coatings of poly(dimethyl siloxane) (PDMS) has been found to vary with the type of substrate. The reaction rate in a 2.5-μm-thick coating on a PDMS substrate, determined with a new method of infrared ellipsometry, is 16 times greater than in the same coating on the native oxide on silicon. Intermediate rates are found on polystyrene and on poly(ethylene terephthalate) substrates. The polar contribution to the surface energy is greater in those substrates with lower rates of reaction. We propose that the polar surfaces more strongly attract the Pt catalyst and form complexes that inhibit the SiH reaction rate.

    6. Synthesis and properties of novel sulfonated polyimides from 2,2′-bis(4-aminophenoxy)biphenyl-5,5′-disulfonic acid (pages 1432–1440)

      Xiaoxia Guo, Jianhua Fang, Kazuhiro Tanaka, Hidetoshi Kita and Ken-ichi Okamoto

      Version of Record online: 28 JAN 2004 | DOI: 10.1002/pola.11063

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      Novel sulfonated polyimides were prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 2,2′-bis(4-aminophenoxy)biphenyl-5,5′-disulfonic acid (oBAPBDS),and common nonsulfonated diamines. Their solubility behaviors, proton conductivity, water uptake, and membrane stability toward water were investigated. Membranes with reasonably high proton conductivity and excellent water stability were successfully developed.

    7. Implementing the reversible addition–fragmentation chain transfer process in PREDICI (pages 1441–1448)

      Michael Wulkow, Markus Busch, Thomas P. Davis and Christopher Barner-Kowollik

      Version of Record online: 2 FEB 2004 | DOI: 10.1002/pola.11089

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      There is currently a highly controversial debate about the nature of the reversible addition–fragmentation chain transfer (RAFT) mechanism. In this debate, kinetic computer modeling is frequently used as a powerful tool to correlate experimental data with theoretical models to deduce the rate coefficients that govern the process. This communication discusses the mathematical and mechanistic implementation of the RAFT process in the PREDICI program package and elucidates the well-founded mathematical basis of the approach.

    8. Low-temperature route to thermoplastic polyamide elastomers (pages 1449–1460)

      Gouher Rabani, Georgina M. Rosair and Arno Kraft

      Version of Record online: 2 FEB 2004 | DOI: 10.1002/pola.11098

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      Thermoplastic polyamide elastomers were obtained by polymerization of aminobenzoyl-substituted telechelics derived from poly(tetrahydrofuran)-diols with several diacid dichlorides (terephthaloyl dichloride, 4,4′-biphenyldicarbonyl dichloride, or 2,6-naphthalenedicarbonyl dichloride) and chlorotrimethylsilane in N,N-dimethylacetamide at 0–20 °C. The as-prepared polymers had melting temperatures above 190 °C and exhibited elastic properties at room temperature, as evidenced by dynamic mechanical analysis and stress-strain measurements. The polymer with 2,6-naphthalenedicarboxamide hard segments had the widest rubbery plateau within the series, the highest extension at break, and good recovery properties.

    9. Functionalization of polyethylene/silane copolymers in posttreatment reactions (pages 1461–1467)

      S. Lipponen and J. Seppälä

      Version of Record online: 2 FEB 2004 | DOI: 10.1002/pola.11064

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      We have performed a route to produce highly reactive halo- and alcoxysilane containing polyethylene. The metallocene catalyst enables copolymerization of ethylene with phenylsilane containing comonomer after the phenylsilane groups are treated in solution to form fluoro-, chloro-, methoxy-, or ethoxysilane groups. With this method, the comonomer content in polyethylene can be adjusted in a wide area without loss of the molar mass.

    10. Radical copolymerization of 2-trifluoromethylacrylic monomers. I. Kinetics of their copolymerization with norbornenes and vinyl ethers as studied by in situ1H NMR analysis (pages 1468–1477)

      Hiroshi Ito and Dolores C. Miller

      Version of Record online: 2 FEB 2004 | DOI: 10.1002/pola.20004

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      2-Trifluoromethylacrylic monomers have been found to undergo radical co- and terpolymerization with norbornene derivatives and vinyl ethers under normal conditions, although none of the monomers homopolymerized, through detailed in situ analysis of the kinetics by 1H NMR. This NMR technique is particularly useful for investigating terpolymerization kinetics as shown for methyl 2-trifluoromethylacrylate (MTFMA), maleic anhydride (MA), and norbornene (NB). The copolymers typically contain 60–70 mol % trifluoromethylacrylic units. This novel radical copolymerization provides the foundation for the preparation of chemical-amplification resist resins for emerging 157-nm lithography.

    11. Radical copolymerization of 2-trifluoromethylacrylic monomers. II. Kinetics, monomer reactivities, and penultimate effect in their copolymerization with norbornenes and vinyl ethers (pages 1478–1505)

      Hiroshi Ito, Masaki Okazaki and Dolores C. Miller

      Version of Record online: 3 FEB 2004 | DOI: 10.1002/pola.20003

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      The radical copolymerization of 2-trifluoromethylacrylic acid and t-butyl 2-trifluoromethylacrylate (TBTFMA) with norbornenes (NBs) and vinyl ethers with 2,2′-azobisisobutyronitrile was studied in detail through the analysis of the kinetics in situ with 1H NMR and through the determination of the monomer reactivity ratios. The terminal model failed to explain the copolymerization behavior, and the penultimate model exhibited an excellent fit with all the experimental data. The simulations based on the penultimate model reactivity ratios and the in situ kinetic data showed a very satisfying agreement.

    12. Radical copolymerization of 2-trifluoromethylacrylic monomers. III. Kinetics and monomer reactivities in the copolymerization of t-butyl 2-trifluoromethylacrylate and methacrylate with styrene bearing hexafluoroisopropanol (pages 1506–1527)

      Hiroshi Ito, Masaki Okazaki and Dolores C. Miller

      Version of Record online: 3 FEB 2004 | DOI: 10.1002/pola.20002

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      The radical copolymerization of t-butyl 2-trifluoromethylacrylate (TBTFMA) and styrene bearing hexafluoroisopropanol [4-(1,1,1,3,3,3- hexafluoro-2-hydroxypropyl)styrene (STHFA)] provided an interesting polymer for use in the formulation of 157-nm chemical amplification resists. The copolymerization was studied in detail in comparison with t-butyl methacrylate (TBMA) through the analysis of the kinetics in situ with 1H NMR and through the determination of the monomer reactivity ratios. The TBTFMA–STHFA copolymerization was described by the penultimate model better than by the terminal model, whereas the latter was adequate for the TBMA–STHFA system. The copolymerizations were simulated on the basis of the reactivity ratios, and the results were compared with the in situ kinetic data. As the conversion dependence of the feed composition shown to the right indicates, the two sets of the data showed very good agreement.

    13. Synthesis of polyesters by the polyaddition of bis(oxetane)s with active di(ester)s (pages 1528–1536)

      Hiroto Kudo, Tomohiko Kurakata, Masaki Sasaki and Tadatomi Nishikubo

      Version of Record online: 3 FEB 2004 | DOI: 10.1002/pola.11057

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      The polyaddition of bis(oxetane)s with active diesters using quaternary onium salts is classified as a new synthetic method for the polyesters. The reaction of bis(oxetanes) (4,4′-BEOBP, 1,4-BEOMB, 1,2-BEOMB, 4,4′-BEOMB, TM-BEOBP) with active diesters (PTTP, PTIF, NPTP, NPIP) was carried out in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in NMP for 24 h, affording corresponding polyesters with Mn's in the range of 220–18,200 in 41–98% yields. The obtained polymers could be soluble in common organic solvents and had high terhmal stabilities.

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