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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1291-1299 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photopolymerization behavior of p-phenylene diacrylic acid dimethyl ester (p-PDA Me) crystal and the thermal behavior of the resultant poly-p-PDA Me were investigated. From the kinetic study of polymerization at various temperatures a topochemical process via a stepwise mechanism was observed. Continuous change from monomer to polymer crystals was demonstrated by x-ray diffraction pattern and DSC analysis. Crystallinity of the reacting phase was maintained at an extremely high degree during the polymerization process in support of monomer crystal lattice control. Thermal study on as-polymerized poly-p-PDA Me crystal confirmed that the thermal reaction was a polymer crystal lattice-controlled depolymerization, which was followed by miscellaneous processes that involved vaporization, sublimation, and deterioration of the oligomeric or monomeric units of p-PDA Me. Thermal stability was dependent on the molecular weight. All the results are compared with those of four-center-type photopolymerization in the crystalline state.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2499-2506 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical reaction of m-phenylene diacrylic acid dimethyl ester (m-PDA Me) crystals and solutions has been studied to clarify the effects of the molecular shape on four-center type photopolymerization of diolefins. On irradiation, m-PDA Me crystals were converted into amorphous oligomers having more than two kinds of cyclobutane rings with respect to steric configuration. The characteristic oligomer formation is explained by considering a two-step mechanism: topochemical dimer formation in an ordered crystal lattice and subsequent random cycloaddition in a disordered crystal lattice. In m-PDA Me solution, reversible cyclobutane ring formation and cis-trans isomerization take place, depending on the concentration of m-PDA Me in solution and the wavelength of the irradiating light. The multiplicity of reactivity in various states has been established.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2095-2103 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5,5′-1,4-Phenylene-bis(2-cyano-2,4-pentadienoic acid) derivatives were prepared. Many of this series of compounds were found to be polymerizable in the crystalline state by irradiation with light of wavelength λ 〉 340 nm. The polymers obtained contain a benzene and a cyclobutane ring in the main chain and have a cyanoacrylate as the side chain. They are crystalline and some of them are soluble in organic solvents. Photopolymerization was found to follow a stepwise mechanism. The polymerization process is separable into an oligomerization and a subsequent polymerization by controlling the wavelength of the irradiating light; an oligomer was obtained by an irradiating light; an oligomer was obtained by an irradiating light of wavelength λ 〉 430 nm.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of temperature on the four-center type photopolymerization has been investigated for p-phenylenediacrylic acid diethyl ester over a wide temperature range including crystal transition point (56°C) and melting point (96°C) of monomer. With the elevation of temperature between -50 and 15°C, the polymerization rate in the initial stage increased and the degree of polymerization decreased monotonously, while the rate in the later stage decreased above -25°C. With irradiation at above 25°C, the monomer crystals became sticky, and the polymerization was suppressed at the stage of oligomerization with low conversion. This tendency was enhanced above the crystal transition point, giving mainly dimer in low yield. Above the melting point, only radical polymerization occurred with the aid of oxygen. The steric configuration of the products in the crystalline state was 1,3-trans with respect to the cyclobutane ring. Peaks in NMR spectra of all products were assigned to the protons involved in four compounds up to tetramer. Various results obtained have been interpreted in terms of the change, as a function of temperature, from a topochemical polymerization which proceeds under a control of the monomer lattice to a photoinitiated vinyl-type polymerization in the disordered state. It is concluded that a rigid crystal lattice is indispensable for the four-center type photopolymerization to proceed smoothly.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 397-405 
    ISSN: 0887-6266
    Keywords: mesogenic epoxy resin ; liquid crystalline thermosets ; anisotropy ; network chain orientation ; heat resistance ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The epoxy resin containing a typical mesogenic group such as biphenol was cured with catechol novolak and aromatic diamines which have neighboring active hydrogens. In the biphenol-type epoxy resin cured with catechol novolak, 4,4′ diaminodiphenylmethane, and p-phenylenediamine (PPD), the glass-rubber transition almost disappeared, and thus a very high elastic modulus was obtained in the high temperature region. It is clear that the thermal motion of the network chains is significantly suppressed in these cured systems. In addition, in the PPD-cured system, a characteristic pattern like a schlieren texture was clearly observed under the crossed polarized optical microscope. Thus we conclude that the mesogenic group contained in the epoxy molecule is oriented in the networks when the mesogenic epoxy resin is cured with phenols and diamines which have neighboring active hydrogens. On the other hand, the biphenol-type resin cured with 3,3′,5,5′-tetraethyl-4,4′-diamino diphenylmethane (TEDDM) showed a well-defined glass-rubber transition and, thus, a low rubbery modulus. In this cured system, no characteristic pattern was observed under the crossed polarized light. These results show that the large branches, such as ethyl groups on the network chains, prevent the orientation of network chains which contain the mesogenic group. © 1997 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
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  • 6
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in crystal structure during polymerization and oligomerization of 2,5-distyrylpyrazine have been investigated by x-ray crystallography. The polymer and the oligomer as obtained are three-dimensionally oriented, and the directions of the three axes of the resultant crystals coincide with those of the original crystal. The space group of the products also agrees with that of the monomer. It is concluded that the polymer and the oligomer crystals approximately duplicate the molecular arrangement in the monomer crystal. The polymerization mechanism is discussed on the basis of the crystal structures.
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 173-191 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The four-center photopolymerization of five diolefinic compounds has been investigated by x-ray crystal analysis. A common packing feature is found for the photopolymerizable crystals and all polymers are three-dimensionally oriented. Topotaxies observed are classified according to the coincidence of space group and the three crystal axes, between monomer and polymer. The polymerization mechanism is discussed on the basis of the topotaxies and it is concluded that the polymerization is lattice controlled over the whole reaction process.
    Additional Material: 15 Ill.
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  • 8
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of p-phenylenediacrylic acid diethyl ester above the transition point was determined at 70°C by x-ray diffraction. No significant differences in molecular arrangement are found between the structures of the α2 form (above the transition point) and the α1 form (at room temperature). Since the α1 form is photopolymerized, it is concluded that selective dimerization in the α2 form results not form the crystal structure of the monomer, but from the deterioration of molecular arrangement by the formation of dimer.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 737-749 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl chloride) (PVC) alone or mixed with 10 wt-% and 50 wt-% TiO2, SnO2, ZnO, and Al2O3 were pyrolyzed by using a pyrolysis gas chromatograph. Benzene, toluene, ethylbenzene, o-xylene, styrene, naphthalene, and various chlorobenzenes were identified. No hydrocarbons could be detected in pyrolysis products of any samples at 200°C. More aromatic hydrocarbons than aliphatic hydrocarbons are released from the PVC-TiO2 system and in preheated PVC. The contrary result is observed in the PVC-ZnO and PVC-SnO2 systems. Aromatics having methyl endgroups are easily released from the PVC-ZnO and PVC-SnO2 systems and at elevated pyrolysis temperature, because methylene groups are easily isolated along the chain by ZnO, SnO2 and the heating. The release of ethylbenzene o-xylene, and chlorobenzenes suggests a repeated dehydrochlorination and recombination of HCl and Cl2 to double bonds along the chain. Possible decomposition mechanisms of PVC are discussed.
    Additional Material: 11 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1381-1392 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of chlorinated polybutadienes (CPB) was investigated by using a pyrolysis gas chromatograph. CPB corresponds to poly(vinyl chloride) (PVC) constructed with head-head and tail-tail linkages of the vinyl chloride unit. Benzene, toluene, ethyl-benzene, o-xylene, styrene, vinyltoluene, chlorobenzenes, naphthalene, and methylnaphthalenes were detected in the pyrolysis products from CPB above 300°C, and no hydrocarbons could be detected at 200°C. The pyrolysis products from CPB were similar to those from PVC and new products could not be detected. Lower aliphatics, toluene, ethylbenzene, o-xylene, chlorobenzenes, and methylnaphthalenes were released more easily from pyrolysis of CPB than from PVC; amounts of benzene, styrene, and naphthalene formed were small. These results support the conclusion that recombination of chlorine atoms with the double bonds in the polyene chain takes place and that scission of the main chain may depend on the location of methylene groups isolated along the polyene chain during the thermal decomposition of PVC.
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