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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The history of rigid chain polymers (i.e., polymers that show mesogenic behavior either in the melt or in solution) is traced from its beginnings to the present. Some correlations between certain mesogenic structures and the physical properties of the corresponding polymers are drawn, particularly as they relate to fibers and to a lesser degree to films and molding resins. Some factors relating to the processing of rod-like polymers from thermotropic melts and from lyotropic solutions are dealt with, and some end use applications for rigid chain polymers are given.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 79-84 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,4′-Diaminobenzanilide (DAB) was reacted with diacids via the Yamazaki phosphorylation reaction to yield simple polyamides and random copolyamides. The use of DAB was found to promote polycondensation because DAB contains a preformed amide linkage which minimizes the amounts of by-products formed. It also maximizes polymer solubility since the monomer is unsymmetrical. The order of the inherent viscosity values of the polymers obtained from DAB by reaction with different diacids, isophthalic 〉 aliphatic 〉 terephthalic, was found to parallel polymer solubility in the reaction medium. The inherent viscosity of the polyamide based on terephthalic acid, DAB-T, was increased greatly by copolymerization, isophthalic acid being more effective than an aliphatic diacid in this regard. None of the polymers formed a thermotropic nematic phase, but the copolymer having an equimolar ratio of terephthalic and adipic acid formed anisotropic solutions in 100% sulfuric acid at polymer concentrations exceeding 40%. Strong films were cast from such solutions.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 4045-4047 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3241-3249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-molecular-weight polyamides containing p-benzamide units can be obtained by polycondensation of monomers having preformed amide linkages in N-methylpyrrolidone with added CaCl2 and LiCl in the presence of pyridine and triphenylphosphite (the conditions used by Higashi et al.). For example, the polyterephthalamide of 4,4′-diaminobenzanilide having ηinh = 5.4 was obtained. Similarly, polycondensation of p-phenylenediamine with N,N′-bis(p-carboxyhenyl)terephalamide produced a polymer having ηinh = 5.15. These results constitute the first demonstration that the phosphorylation reaction can be used to prepare rodlike polymers containing p-benzamide units of molecular weights adequate for commercial-quality fibers. Polymerization of p-aminobenzoic acid using either Yamazaki or Higashi conditions does not lead to a polyamide having a high inherent viscosity. Block copolyamides having rigid and semiflexible blocks were prepared by using both Yamazaki and Higashi conditions. Block copolymers composed of p- and m-benzamide units, and having ηinh = 3.0-3.1, were synthesized by using a rigid prepolymer obtained by applying the Yamazaki reaction to a monomer containing a preformed amide linkage, 4-N-(4′-aminobenzamido)-benzoic acid. Use of monomers having preformed amide linkages with Higashi conditions afforded block copolymers having inherent viscosities of up to 4.75.
    Additional Material: 4 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 373-381 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel extension of the Yamazaki reaction is used to prepare block copolymers having rigid blocks of poly-(p-benzamide) (PBA) and semiflexible blocks of polyamide-hydrazide. A PBA prepolymer having M ≅ 10,000 was synthesized by the usual Yamazaki reaction using triphenylphosphite. As previously reported, higher-molecular-weight PBA could be obtained using 4-N-(4′-aminobenzamido)benzoic acid containing a preformed amide linkage. Addition of p-aminobenzhydrazide and terephthalic acid then led to formation of the polyamide-hydrazide blocks using as the active reactant the diphenylphosphite formed as a by-product in the first polymerization. Evidence that a block copolymer is produced includes an increase in inherent viscosity during the second step, differences in the solubility of the copolymer compared to the homopolymers, and comparison of the phase diagram of the block copolymer in N-methylpyrrolidone having 4% added LiCl with those of a random copolymer, and of mixtures of the two homopolymers. The critical concentration required to form a nematic phase in solutions of the block copolymers is correlated with the length (or axial ratio) of the rigid block, and with its proportion in the copolymer.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2837-2841 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 20 (1982), S. 109-115 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1851-1872 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-molecular-weight 4′-acetoxyphenyl-4-acetoxyoinnamate, as well as several polyesters synthesized from this monomer and aliphatic dibasic acids, exhibit thermotropic nematic phases. DSC heating curves for all of the polymers exhibit multiple transitions. The amount of crystallinity of these polymers at room temperature is small and the degree of order along the chain axis in the crystalline phase is poor. For the lower homologues the nematic phase exists over a broad temperature range of approximately 100°C. The polyester from chiral (+)-3-methyl adipate forms a thermotropic cholesteric phase. Both the diacetoxy monomer and azelate polymers of low molecular weight adopt the homeotropic texture on glass slides, but with increasing molecular weight the planar texture becomes preferred. Investigation of the effects of electric fields in the conduction regime upon the nematic phase of the diacetoxy monomer revealed that Williams domains are formed only with difficulty. In most cases, a stationary pattern appeared instead. At higher voltage the dynamic scattering mode (DSM) was obtained, and above this a field-induced transition to the isotropic phase. The azelate polyesters exhibited Williams domains and the DSM in the conduction regime. The formation time for Williams domains was fairly short for polymers having ηinh 〈 0.44 dL/g, but increased to 80 min when ηinh = 0.68 dL/g. The DSM was only observed for polymers having ηinh 〈 0.61 dL/g. For these polymers the critical frequency separating the conduction and dielectric regimes exhibits a stronger temperature dependence than that of low-molecular-weight nematogens. A new instability pattern is reported for the azelate polyesters in the dielectric regime.
    Additional Material: 21 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1119-1131 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A homologous series of polyesters was prepared from 4,4′-dihydroxybiphenyl and dibasic acids having 5-12 methylene units. The mesophases formed at elevated temperatures were studied by differential scanning calorimetry and polarized light microscopy. This family exhibits an unusual odd-even effect when the transition temperatures are plotted as a function of the number of methylene units in the dibasic acid. Not only do the points for odd and even members fall on different curves, but the odd members exhibit a nematic phase over a very short temperature interval, while the even members form a highly ordered smectic phase. For both the odd and even series, the transition temperatures are significantly depressed when the inherent viscosity falls below 0.2 dL/g. The largest depression occurs for the crystal melting transition, so that polymers of low ηinh show anisotropic and biphasic regions over wider temperature ranges. A copolymer formed from an equimolar mixture of sebacic and chiral (+)-3-methyl adipic acid forms a cholesteric phase. Evidently copolymerization destabilizes the smectic phase which would have been expected. The results are discussed in terms of existing theory.
    Additional Material: 8 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 863-875 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The persistence length of poly(terephthaloyl p-amino benzhydrazide) (X-500) in dimethyl sulfoxide (DMSO) has been determined from intrinsic viscosities measured for several whole-polymer samples. An approximate correction is applied for excluded volume effects, and these corrected values are fitted using the viscosity treatments of Yamakawa and Fujii and of Eizner and Ptitsyn. Both give for the persistence length of X-500 values in the range 30-35 Å. Revised treatment of our previous light scattering data for the same polymer yields 49 Å for the persistence length. Thus the chain extension of X-500 falls between those of para-linked polyamides and those of typical freely coiling macromolecules. Phase diagram studies indicate the solubility of X-500 in DMSO decreases with rising temperature, and can be increased by the addition of LiCl. No anisotropic phase is found in DMSO at the highest volume fraction of polymer, v2 = 0.19, which can be obtained with 4 g/dl LiCl. The critical concentration of X-500 needed for the appearance of the anisotropic phase depends upon solvent since Morgan reported an anisotropic phase for this polymer in 100% H2SO4 when v2 ≈ 0.13.
    Additional Material: 5 Ill.
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