Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 June 2002

Volume 40, Issue 12

Pages 1929–2097

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    1. Atom transfer radical homo- and block copolymerization of methyl 1-bicyclobutanecarboxylate (pages 1929–1936)

      Xiao-Ping Chen, Anne Buyle Padias and H. K. Hall Jr.

      Version of Record online: 24 APR 2002 | DOI: 10.1002/pola.10274

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      A nonolefinic monomer, methyl 1-bicyclobutanecarboxylate (MBC), was successfully polymerized by the controlled/“living” atom transfer radical polymerization (ATRP) technique, resulting in a well-defined homopolymer, PMBC, with only cyclobutane ring units in the polymer chain. An AB block copolymer poly(methyl 1-bicyclobutanecarboxylate)-b-polystyrene (PMBC-b-PS), having an all-ring unit segment, was also synthesized with narrow polydispersity and designed number-average molecular weight in addition to precise end groups. The 1H NMR spectra, glass-transition temperature, and thermal stability of PMBC, PMBC-b-PS, and PS-b-PMBC were investigated. The experimental results showed that the cyclobutane rings in the two block polymers improved their thermal stability.

    2. Synthesis of end-functionalized poly(methyl methacrylate) by ruthenium-catalyzed living radical polymerization with functionalized initiators (pages 1937–1944)

      Kyung-Youl Baek, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 25 APR 2002 | DOI: 10.1002/pola.10280

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      A series of 2-bromoisobutyrates and 2-chloro-2-phenylacetates with an amide, alcohol, or amine function led to end-functionalized poly(methyl methacrylate)s (PMMAs) in the Ru(II)-catalyzed living radical polymerization. The chloride initiators with an amine additive produced well-controlled end-functionalized PMMAs (Mw/Mn ≤ 1.30). The 1H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis confirmed that the functional groups were quantitatively introduced into the α end.

    3. Effects of salts and copolymer composition on the lower critical solution temperature of poly(methyl 2-acetamidoacrylate-co-methyl methacrylate) solutions (pages 1945–1951)

      Hirokazu Okamura, Yasushi Morihara, Seizo Masuda, Keiji Minagawa, Takeshi Mori and Masami Tanaka

      Version of Record online: 25 APR 2002 | DOI: 10.1002/pola.10281

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      Poly(methyl 2-acetamidoacrylate-co-methyl methacrylate)s containing greater than 83 mol % of methyl 2-acetamidoacrylate (MAA) units are soluble in water. All water-soluble copolymers exhibit a lower critical solution temperature (LCST) in a salt solution, and copolymers with MAA contents in the region of 83–90 mol % exhibit an LCST in pure water. The LCST of copolymer solutions depends on the composition and concentration of the copolymer. In addition, some salts have a salting-out effect, and others (carbonate and phosphate) have a salting-in effect.

    4. Reactive blending of functional polysiloxanes with poly(butylene terephthalate): Clarification of reaction mechanisms and kinetics from a model compound study (pages 1952–1961)

      C. A. Fustin, M. Sclavons, V. Verhelst, V. Vermylen, S. Bebelman, P. Merlin and C. Bailly

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10283

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      The reaction mechanisms and kinetics in melt-reacted blends consisting of functional polysiloxanes and poly(butylene terephthalate) (PBT) have been clarified with a model compound study. PBT functional groups reactive toward functional siloxane oligomers at high temperatures in the presence and absence of a catalyst have been identified, and an estimate of the relative reaction kinetics has been provided. Reaction mechanisms are suggested that are compatible with the results of this study and with literature data.

    5. Influence of stereochemistry on the thermal properties of partially cycloaliphatic polyamides (pages 1962–1971)

      Bert Vanhaecht, Bart Rimez, Rudolph Willem, Monique Biesemans and Cor E. Koning

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10284

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      The effects of the partial substitution of 1,4-disubstituted cyclohexane monomers for linear aliphatic monomers in polyamides are discussed. More specifically, the relation between the stereochemistry of the cycloaliphatic residues and the thermal properties (the melting temperature and crystallization temperature) was investigated. For this purpose, two different types of copolyamides were synthesized: in polyamides 12.6, the adipic acid residues were partially replaced by cis/trans-1,4-cyclohexanedicarboxylic acid (1,4-CHDA), whereas in polyamides 4.14, the 1,4-diaminobutane residues were partially substituted by cis/trans-1,4-diaminocyclohexane (1,4-DACH). In contrast to the use of 1,4-DACH as a comonomer, 1,4-CHDA residues showed isomerization upon thermal treatment of the polyamides. This isomerization of the cycloaliphatic residues influenced the thermal properties of the copolyamides.

    6. Star poly(methyl methacrylate) with end-functionalized arm chains by ruthenium-catalyzed living radical polymerization (pages 1972–1982)

      Kyung-Youl Baek, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10279

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      Star polymers with functional groups at the free chain ends of arm polymers, that is, surface-functionalized star polymers, were synthesized by the in situ linking reaction between ethylene glycol dimethacrylate (EGDMA) and α-end-functionalized linear living poly(methyl methacrylate) (PMMA) with amide, alcohol, and amine groups in RuCl2(PPh3)3-catalyzed living radical polymerization. These star polymers were obtained in high yields (75–90%) with an initiating system consisting of α-functionalized 2-chloro-2-phenylacetate (initiator) and n-Bu3N (additive).

    7. Functional polyesters prepared by polymerization of α-allyl(valerolactone) and its copolymerization with ε-caprolactone and δ-valerolactone (pages 1983–1990)

      Bryan Parrish, Jennifer K. Quansah and Todd Emrick

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10277

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      We report the ring-opening homopolymerization of α-allyl(valerolactone), compound 2, and its copolymerization with ε-caprolactone and δ-valerolactone using stannous(II) catalysis. Although the polymerization of substituted δ-valerolactones has received little attention for the preparation of functional polyesters, we found that compound 2 may be incorporated in controllable amounts into copolymers with other lactones, or simply homopolymerized to give a highly functionalized, novel poly(valerolactone). The presence of the pendant allyl substituent had a substantial impact on the thermal properties of these materials relative to conventional polyesters prepared from lactones, and most of the polymers presented here are liquids at room temperature. Dihydroxylation of the pendant allyl groups gave polyesters with increased hydrophilicity that degraded more or less rapidly depending on their extent of functionality.

    8. Synthesis of multihydroxyl branched polyethers by cationic copolymerization of 3,3-bis(hydroxymethyl)oxetane and 3-ethyl-3-(hydroxymethyl)oxetane (pages 1991–2002)

      Yu Chen, Melania Bednarek, Przemysław Kubisa and Stanisław Penczek

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10282

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      The cationic polymerization of 3,3-bis(hydroxymethyl)oxetane with 3-ethyl-3-(hydroxymethyl)oxetane leads to soluble, multihydroxyl branched polyethers with a number-average molecular weight limited by transfer to about 103. This polymer contains primary HO[BOND] groups exclusively in [TRIPLE BOND]C[BOND]CH2[BOND] OH units. Because of the equal reactivity of both comonomers in the copolymerization, the composition of the copolymers and, therefore, the content of hydroxyl groups may be changed simply by the adjustment of the composition of the comonomer feed. The structure of the resulting multihydroxyl branched polyethers is schematically shown.

    9. Evaluation of compatibility and properties of biodegradable polyester blends (pages 2003–2014)

      Jacob John, Ramaswamy Mani and Mrinal Bhattacharya

      Version of Record online: 30 APR 2002 | DOI: 10.1002/pola.10297

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      Three different biodegradable polyesters, namely, polycaprolactone (PCL), polybutylene succinate (BIONOLLE), and a copolyester of adipic acid, terephthalic acid, and 1,4-butanediol (EASTAR) were melt-blended using a twin-screw extruder. The percentage composition of each of the aforementioned polymers was varied to obtain different blends, and the mechanical properties were evaluated. Selected blends showed significant improvement in tensile strength as compared with the individual polymers used to prepare the blend. The compatibility between the polymer phases was examined via Fourier transform infrared (FTIR) and nuclear magnetic resonace (NMR) spectroscopy as well as dynamic mechanical analysis. FTIR and NMR data confirmed the occurrence of hydrogen-bonding and ester-interchange reactions. Thermal properties and changes in crystallinity of the blends were studied with the help of Differential Scanning Calorimeter (DSC) and X-ray diffraction.

    10. Main-chain viologen polymers with triflimide counterion exhibiting lyotropic liquid-crystalline properties in polar organic solvents (pages 2015–2024)

      Pradip K. Bhowmik, Haesook Han and Ivan K. Nedeltchev

      Version of Record online: 3 MAY 2002 | DOI: 10.1002/pola.10298

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      The solution properties of three main-chain viologen polymers in polar both protic and aprotic organic solvents were studied microscopically under crossed polarizers. They exhibited lyotropic liquid-crystalline phase in methanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide.

    11. Synthesis and characterization of well-defined ABC-type triblock copolymers via atom transfer radical polymerization and stable free-radical polymerization (pages 2025–2032)

      U. Tunca, T. Erdogan and G. Hizal

      Version of Record online: 1 MAY 2002 | DOI: 10.1002/pola.10300

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      An asymmetric difunctional initiator 2-phenyl-2-[(2,2,6,6 tetramethylpiperidino)oxy] ethyl 2-bromo propanoate (1) was used for the synthesis of ABC-type methyl methacrylate (MMA)- tert-butylacrylate (tBA)-styrene (St) triblock copolymers via a combination of atom transfer radical polymerization and stable free-radical polymerization.

    12. Iron-catalyzed living radical polymerization of acrylates: Iodide-based initiating systems and block and random copolymerizations (pages 2033–2043)

      Isamu Onishi, Kyung-Youl Baek, Yuzo Kotani, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 3 MAY 2002 | DOI: 10.1002/pola.10299

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      The (CH3)2C(CO2Et)I/Fe(Cp)I(CO)2 initiating system induced living radical polymerization of methyl acrylate, n-butyl acrylate, and tert-butyl acrylate in the presence of metal alkoxides such as Al(Oi-Pr)3 and Ti(Oi-Pr)4 to give polymers with controlled molecular weights and narrow molecular weight distributions (Mw/Mn < 1.2). The initiating system also enabled the synthesis of block and random copolymers of acrylates and styrene.

    13. Effect of the tail-group length and degree of polymerization on the order parameter of side-chain liquid-crystalline polymethacrylates containing phenylbenzoate mesogenic groups (pages 2044–2048)

      E. B. Barmatov

      Version of Record online: 3 MAY 2002 | DOI: 10.1002/pola.10267

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      The effect of the tail-group length n and degree of polymerization on the order parameter S of side-chain liquid-crystalline polymethacrylates was examined with 2H NMR spectroscopy. A decrease of the order parameter S of the liquid-crystalline polymers with an increasing number of carbon atoms in the end aliphatic group was found (see figure).

    14. Star-shaped and photocrosslinked poly(1,5-dioxepan-2-one): Synthesis and characterization (pages 2049–2054)

      Maria Ryner, Alexandra Valdre and Ann-Christine Albertsson

      Version of Record online: 6 MAY 2002 | DOI: 10.1002/pola.10304

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      New star-shaped and photocrosslinked poly(1,5-dioxepan-2-one) (PDXO) has been synthesized through ring-opening polymerization initiated by SnOct2/pentaerythritol. The star-shaped PDXO was end-functionalized by acrolyol chloride to form acrylate end groups. The end-functionalized PDXO was photocrosslinked, initiated by 2,2-dimethoxy-2-phenylacetophenone. The gel content ranged from 80 to 99%, indicating a high degree of crosslinking.

    15. Controlled radical polymerization of 2-hydroxyethyl methacrylate with a hydrophilic ruthenium complex and the synthesis of amphiphilic random and block copolymers with methyl methacrylate (pages 2055–2065)

      Yusuke Fuji, Kazuya Watanabe, Kyung-Youl Baek, Tsuyoshi Ando, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 7 MAY 2002 | DOI: 10.1002/pola.10302

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      A hydrophilic ruthenium complex with ionic phosphine ligands {RuCl2[P(3-C6H4SO3Na)(C6H5)2]2} in conjunction with a halide initiator (R-X) induced controlled radical polymerization of 2-hydroxyethyl methacrylate (HEMA) in methanol under homogeneous conditions. Methyl methacrylate (MMA) can also be polymerized in living fashion with the same initiating system in methanol. Especially for such hydrophobic polymers, the water-soluble catalyst was readily removed from the polymers by simple washing with an aqueous dilute acid. This system can be applied to the direct synthesis of amphiphilic random and block copolymers of HEMA and MMA.

    16. Synthesis and characterization of new highly organosoluble poly(etherimide)s derived from 1,1-bis{4-[4-(3,4-dicarboxyphenoxy)phenyl]-4-phenylcyclohexane} dianhydride (pages 2066–2074)

      Der-Jang Liaw, Chung-Yu Hsu, Pei-Nan Hsu and Shu-Ling Lin

      Version of Record online: 7 MAY 2002 | DOI: 10.1002/pola.10264

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      From a bulky pendent bis(ether anhydride), 1,1-bis[4-(4-dicarboxyphenoxy)phenyl]-4-phenylcyclohexane dianhydride (3), a series of new poly(ether imide)s were prepared with various diamines. They had inherent viscosities of 0.50–0.73 dL g−1; GPC number-average and weight-average molecular weights of up to 57,000 and 130,000, respectively; and glass-transition temperatures at 226–255 °C. Most of the polymers could be dissolved in chloroform in as high as a 30 wt % concentration. Thermogravimetric analysis showed that all polymers were stable up to 450 °C under nitrogen. Transparent tough, and flexible films could be obtained by solution casting from dimethylacetamide solutions; they had tensile strengths of 79–103 MPa and tensile moduli 1.5–2.1 GPa.

    17. Synthesis and burst strength of water-swollen immunoisolatory tubules (pages 2075–2084)

      Irada S. Isayeva, Alan N. Gent and Joseph P. Kennedy

      Version of Record online: 7 MAY 2002 | DOI: 10.1002/pola.10303

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      A series of amphiphilic hydrogel tubules have been prepared by copolymerizing/crosslinking hydrophilic poly(dimethylacrylamide) segments with hydrophobic di-, tri-, and octamethacrylate-telechelic polyisobutylene crosslinkers, and their elastic modulus and burst strength in the water-swollen state were investigated. The burst strength of our water-swollen amphiphilic tubules is in the 0.2–0.5 MPa range, which is sufficient for implantation and immunoisolatory applications.

    18. Preparation of partially hydrolyzed oligo(vinylacetate) as polyol for polyurethane formation (pages 2085–2092)

      Jörg Zimmermann, Alexander Sunder and Rolf Mülhaupt

      Version of Record online: 7 MAY 2002 | DOI: 10.1002/pola.10275

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      Polyols based on oligo(vinylacetate) were synthesized using a convenient one-pot, two-step process. Polymerization of vinylacetate was performed in 2-propanol as chain transfer agent using di-tert-butylperoxide as free radical initiator. Saponification of the oligomers was performed using stoichiometric amounts of methanol in the presence of a basic catalyst. Well-defined oligo(vinylacetate-co-vinylalcohol) polyols with a degree of polymerization below 12 and a hydroxyfunctionality smaller than 4 were obtained. Oligo(vinylacetate-co-vinylalcohol) was employed as polyol component in polyurethane formation.

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      Living radical polymerization of methyl methacrylate catalyzed by cuprous N,N-diethyldithiocarbamate (pages 2093–2097)

      Peng Li and Kun-Yuan Qiu

      Version of Record online: 7 MAY 2002 | DOI: 10.1002/pola.10309

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      Atom transfer radical polymerization (ATRP) of MMA catalyzed by Cu(S2CNEt2) was described. Living characteristics was exhibited in both normal and reverse ATRP processes: first-order kinetics, a proportional increase of Mn with the monomer conversion and rather low Mw/Mn (<1.32). Because of the present side reactions in reverse ATRP system, the initiator efficiency is only half that of the one in the normal system. Photolabile group, diethylthiocarbamoylthiyl, end-caps the resulting PMMA chain.

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