Journal of Polymer Science Part A: Polymer Chemistry

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

15 April 2001

Volume 39, Issue 8

Pages 1149–1267

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    1. Synthesis of fully lower-rim, carbonate-bridged calix[8]arenes and their curing behavior (pages 1149–1155)

      Takuo Sugioka and Allan S. Hay

      Article first published online: 23 FEB 2001 | DOI: 10.1002/pola.1091

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      Novel fully lower-rim, carbonate-bridged calix[8]arene derivatives were successfully synthesized in high yield by the condensation of p-alkyl substituted calix[8]arenes with triphosgene. The conformational features of the derivatives were examined by 1H NMR analysis. Thermosetting formulations were prepared from a mixture of bisphenol A polycarbonate with calix[8]arene carbonate derivatives using sodium benzoate as a catalyst. Their crosslinking behaviors were studied using differential thermal/thermogravimetric analysis. No glass-transition temperatures were observed after annealing at 280–300 °C.

    2. Synthesis and characterization of new organosoluble polyamides derived from bis[4-(4-carboxyphenoxy) phenyl]diphenylmethane (pages 1156–1161)

      Der-Jang Liaw, Been-Yang Liaw, Chao-Min Yang, Pei-Nan Hsu and Chieh-Ying Hwang

      Article first published online: 26 FEB 2001 | DOI: 10.1002/pola.1092

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      A series of novel polyamides were prepared by the direct polycondensation of bis[4-(4-carboxyphenoxy)phenyl]diphenylmethane (BCAPD) and various aromatic diamines. All the polymers films had a tensile strength and a tensile modulus greater than 80 MPa and 2.0 GPa, respectively. These polyamides had glass-transition temperatures between 249 and 274 °C, and their temperatures at a 10% weight loss were 477–538 and 483–540 °C in nitrogen and air atmospheres, respectively.

    3. Synthesis and electrooptic properties of side-chain methacrylate polymers containing a new azophenylbenzoxazole chromophore (pages 1162–1168)

      T. Beltrani, M. Bösch, R. Centore, S. Concilio, P. Günter and A. Sirigu

      Article first published online: 26 FEB 2001 | DOI: 10.1002/pola.1093

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      The synthesis and characterization of four methacrylate copolymers obtained by radical addition polymerization of methylmethacrylate and a new methacrylate azophenylbenzoxazole chromophore in percentage of 10, 30, 50, and 70% is reported. The electrooptic coefficient r33 of polymer films has been measured using the reflection technique. The measured values fall in the range of 1.7–3.7 pm/V (laser incident wavelength of 1.552 μm), depending on the percentage of chromophore in the polymer.

    4. Synthesis of photoreactive calixarene derivatives containing pendant cyclic ether groups (pages 1169–1179)

      Tadatomi Nishikubo, Atsushi Kameyama and Kousuke Tsutsui

      Article first published online: 27 FEB 2001 | DOI: 10.1002/pola.1094

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      Photoreactive calixarene derivatives containing pendant oxetane groups were synthesized by the reaction of C-methylcalix[4]resorcinarene (CRA), p-methylcalix[6]arene (MCA), and p-tert-butylcalix[8]arene (BCA) with (3-methyloxetan-3-yl)methyl 4-toluenesulfonate and (3-ethyloxetan-3-yl)methyl 4-toluenesulfonate. Calixarene derivatives containing oxirane groups were also prepared by the reaction of CRA, MCA, and BCA with epibromohydrin. The photochemical reaction of the obtained calixarene derivatives was examined with certain photoacid generators in the film state, and it was found that the reaction proceeded to give insoluble gel products.

    5. Highly isotactic polymethacrylates through radical polymerization of methacrylate esters of some ortho-bridged triaryl carbinols (pages 1180–1186)

      Athina Hatziyiannakou and Cleanthis Froussios

      Article first published online: 26 FEB 2001 | DOI: 10.1002/pola.1095

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      Several aromatic alcohol methacrylates were prepared, and the structure of their polymers obtained under radical polymerization conditions was examined by NMR spectroscopy to relate alcohol structure to polymer stereoregularity. High isotacticity was determined for the resulting polymer in all three occasions of alcohols that comprised of a central six-membered ring of the 9,10-dihydroanthracene type in their structure.

    6. Phenothiazine photosensitizers for onium salt photoinitiated cationic polymerization (pages 1187–1197)

      Zaza Gomurashvili and James V. Crivello

      Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1096

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      Phenothiazine compounds bearing a wide range of different substituents are excellent photosensitizers for a wide variety of onium salt cationic photoinitiators. Photosensitization takes place by an electron-transfer process in which the phenothiazine is oxidized and the onium salt is reduced.

  2. Rapid Communication

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      Benzyl potassium: An efficient one-pot initiator for the synthesis of block co- and terpolymers of ethylenoxide (pages 1198–1202)

      Nikos Ekizoglou and Nikos Hadjichristidis

      Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1097

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      This study shows that benzyl potassium is an efficient initiator for the polymerization of ethylenoxide. Well-defined diblock copolymers and triblock terpolymer of ethylenoxide have been synthesized using this initiator.

  3. Articles

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    4. Articles
    1. Synthesis and characterization of nitroglycerin-functionalized polystyrene (pages 1203–1215)

      S. Raja and R. Dhamodharan

      Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1098

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      The synthesis and characterization of nitroglycerin-functionalized polystyrene (NGPS) from polystyrene by the polymer-modification route were examined. Thus, NGPS was prepared by the following sequence of reactions: (1) Friedel–Crafts oxomalonation, (2) reduction, and (3) nitration. It was also demonstrated that synthesized NGPS undergoes thermal degradation with inhibition and burns smoothly in the presence of ammonium nitrate.

    2. Design of polyethers, thioethers, and amines with pendent iron moieties (pages 1216–1231)

      A. S. Abd-El-Aziz, E. K. Todd and G. Z. Ma

      Article first published online: 1 MAR 2001 | DOI: 10.1002/pola.1099

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      Polyaromatic ethers, thioethers, and amines complexed to cationic cyclopentadienyliron moieties were prepared via nucleophilic aromatic substitution reactions of dichloroarene complexes with various O-, S-, and N-containing dinucleophiles. A thermogravimetric analysis of the organoiron polymers showed two weight-loss steps at about 200 and 500 °C, representing the loss of the metallic moieties and polymer degradation, respectively. The solubility of the metallated materials was enhanced as a result of π coordination of the cyclopentadienyliron groups to the polymer backbones.

    3. Alkoxyamine-mediated “living” radical polymerization: MS investigation of the early stages of styrene polymerization initiated by cumyl-TEISO (pages 1232–1241)

      Salvacion P. Cresidio, Fawaz Aldabbagh, W. Ken Busfield, Ian D. Jenkins, San H. Thang, Clovia Zayas-Holdsworth and Per B. Zetterlund

      Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1100

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      This typical ion-current spectrum (SIR mode) from the high-performance liquid chromatographic/mass spectrometric analyses of the attempted nitroxide-mediated living polymerization of styrene at 60 °C shows the presence of oligomers 18 after 6 h reaction time. Although the concentration of oligomers steadily increases with reaction time, their distribution stays constant. This conclusively shows that up to eight styrene units can add to the initiating cumyl radicals before nitroxide trapping. Once trapped, the styryl radicals undergo no further addition at this temperature. Normal living polymerization is observed in this system at 110 °C.

    4. Synthesis and structure of wholly aromatic liquid–crystalline polyesters containing meta- and ortholinkages (pages 1242–1248)

      Chaobin He, Zhihua Lu, Lun Zhao and Tai-Shung Chung

      Article first published online: 2 MAR 2001 | DOI: 10.1002/pola.1101

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      A polarized light microscopy image of a wholly aromatic rigid-chain liquid–crystalline polymer containing 50% of meta- and orthokink linkages. The existence of liquid crystallinity in the polymers may be attributed to the adoption of cis conformation in kink units because the energy penalty for doing so can be compensated by the formation of the liquid–crystalline phase.

    5. MALDI-TOF-MS analysis of living cationic polymerization of vinyl ethers. II. Living nature of growing end and side reactions (pages 1249–1257)

      Hiroshi Katayama, Masami Kamigaito and Mitsuo Sawamoto

      Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1102

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      Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was utilized for the analysis of poly(isobutyl vinyl ether) obtained with the HCl–vinyl ether adduct/SnCl4/n-Bu4NCl initiating system in CH2Cl2 at −78 and −15 °C. It revealed that the system induced living cationic polymerization to form only one series of polymers with defined terminal groups. The growing end keeps its lifetime for an extended period even after the depletion of monomer. In contrast, the polymers obtained at a higher temperature, −15 °C, contained minor series of polymers originated from adventitious water. However, polymers with unsaturated C[DOUBLE BOND]C end groups cannot be detected, which means the absence of β-proton elimination.

    6. MALDI-TOF-MS analysis of living cationic polymerization of vinyl ethers. III. Polymerization with SnCl4 and TiCl4 in the absence of additives (pages 1258–1267)

      Hiroshi Katayama, Masami Kamigaito and Mitsuo Sawamoto

      Article first published online: 2 MAR 2001 | DOI: 10.1002/pola.1103

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      The cationic polymerization of isobutyl vinyl ether was carried out with the HCl–vinyl ether adduct as well as strong Lewis acids such as SnCl4 and TiCl4 without additives. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis revealed that the system induced living polymerization in CH2Cl2 at −78 °C under the conditions where the Lewis acid concentration was extremely low. However, side reactions occurred at either a higher concentration of SnCl4 or at −15 °C. This was more pronounced with SnCl4 than with TiCl4, which was due to a stronger Lewis acidity of SnCl4 as suggested by NMR analysis of the model reactions.

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