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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 3151-3156 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two methods were investigated for the preparation of poly(dimethyl biphenylene) in a search for polymers combining good solubility with sufficiently high chain extension to produce a lyotropic nematic phase. The Ullmann reaction was used to condense 4,4′-diiodo-3,3′-dimethyl biphenyl and the corresponding 2,2′-dimethyl derivative with copper, and 4,4′-dibromo-2,2′-dimethyl biphenyl was polymerized using the coupling reagent, bis(1,5-cyclooctadiene)nickel(0), developed by Semmelhack. The Ullmann polymers were completely soluble in CHCl3 but only partially soluble in toluene, whereas earlier work had indicated similar polymers of higher molecular weight to be completely soluble in toluene. All the polymers produced were of low molecular weight and no evidence of the nematic phase was found by polarized light microscopy for CHCl3 solutions over the concentration range 6.8-25% by weight.
    Additional Material: 1 Tab.
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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 23 (1985), S. 1907-1916 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report a study of the conditions of the phosphorylation reaction for the preparation of aromatic polyamides using the Higashi reaction medium. For poly(p-phenylene terephthalamide) (PPD-T), the optimum conditions are: reaction temperature, 115°C; monomer concentration, C = 0.083 mol/L; and ratio of triphenyl phosphite (TPP) to monomer, 2.0. These optimum conditions produce PPD-T having ηinh = 6.2 dL/g. At temperatures of 120°C and above PPD-T precipitates from the reaction mixture, leading to lower molecular weights. At lower temperatures the reaction mixture gels, and the gel time decreases with increasing reaction temperature. However, polycondensation continues in the gel state. Monomer concentrations C = 0.10 mol/L and above produce precipitation and yield polyamides of lower molecular weight. For the preparation of poly(p-benzamide) (PBA), the optimum ratio of TPP to monomer is 0.6 for either p- aminobenzoic acid or N-4-(4′-aminobenzamido)benzoic acid. In the former case the inherent viscosity of polymer prepared at 115°C showed little dependence upon the concentration of the monomer. The highest value, ηinh = 1.8 dL/g, was obtained with C = 0.40 mol/L and a TPP/monomer ratio of 0.6. However, for the same TPP/monomer ratio, the monomer containing a preformed amide linkage, N-4-(4′-aminobenzamido)benzoic acid, gave PBA with ηinh = 4.6 dL/g when the monomer concentration is 0.33 mol/L. This is the highest value reported for PBA using the phosphorylation reaction. In A-A + B-B polycondensation, examples in which one of the monomers contained one or two preformed amide linkages produced polyamides having ηinh = 7.8 and 8.9 dL/g, respectively.
    Additional Material: 8 Ill.
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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.
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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 883-894 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In co[poly(ethylene terephthalate)-p-oxybenzoate] containing 30 mole % oxybenzoate units, the ethylene terephthate units crystallize. The copolymer melts in the temperature range 180-210°C to form a nematic phase which, at a higher temperature, transforms to an isotropic liquid. The latent heat of the first transition is 5 cal/g, and the thermodynamic melting temperature, 247°C, is essentially that expected for a random copolymer of this composition. The nematic → isotropic transition occurs at 244°C, with an enthalpy change of 3.2 cal/g (10% of the heat of fusion of poly(ethylene terephthalate)). We conclude that semiflexible polymers form a nematic phase which is rather highly disordered. The model of the nematic phase treated by Flory is modified to increase its entropy through incorporation of chain bends (which must be correlated in position and direction with those in neighboring molecules). This increases the chain extension, as measured by the fraction (1-f) of collinear chain bonds, required to form the nematic phase. For binary polymer-solvent systems, an appropriate scaling of f values leaves the phase diagram as predicted by Flory's treatment essentially unchanged.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 393-407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of statistical chain segments in the amorphous regions of a semicrystalline polymer can be characterized quantitatively by x-ray diffraction. A calculated background (which is orientation independent) must be subtracted, which requires that the intensity profile of the amorphous halo be measured on an absolute scale. Application is illustrated to samples of isotactic polystyrene which were isothermally crystallized at fixed elongation. These samples differ from those of the previous study due to the unintentional introduction of a small amount of crystallinity (0.25% to 1%) which serves as tie points in the drawing operation, giving a stronger amorphous orientation. Preferred orientation of the amorphous chain segments is rapidly depleted during the first few percent of crystallization. The crystallite orientation distribution is quite sharp, and broadens only slowly with crystallization. These results imply that, for the crystallization conditions employed, the crystallite orientation must be determined by nuclei which are formed at the earliest stages of the crystallization process.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2037-2053 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase diagram of poly(p-benzamide) (PBA) in N,N-dimethylacetamide/LiCl solutions was determined for two PBA samples having weight-average molecular weights of about 10,000. The various equilibria were studied using analytical, viscometric, and optical microscope measurements. The phase diagram at 25°C, taking as variables the concentration of polymer (Cp) and LiCl (Cs), involves several equilibria which can be summarized as follows: solid ↔ isotropic solution when 0.75 ≤ Cs ≤ 2 g/dl, solid ↔ anisotropic solution when 2 ≤ Cs ≤ 4 g/dl, isotropic solution ↔ anisotropic solution when 2 ≤ Cs ≤ 4 g/dl, and Cp 〉 6 g/dl, and dilute isotropic solution ↔ gel when Cs 〉 4 g/dl. In the Cp range in which the isotropic and anisotropic phases coexist, enrichment of the high-molecular-weight component of the polymer in the anisotropic phase becomes more marked as the volume fraction of the latter phase is decreased. The two PBA samples exhibit noticeable differences in solubility, absolute viscosity, and in their viscosity-concentration behavior. The location of the maximum in the latter dependence does not necessarily coincide with the first appearance of the anisotropic phase. In the absence of a flow field, anisotropic solutions exhibit an irreversible increase in viscosity. Inclusion of the equilibria involving the crystalline state furnishes insight into some of the common observations for extended-chain polymers. A diagram illustrates the superposition of the solubility curves for a crystalline polymer and the liquid-crystal regions. This indicates that, for the high melting crystalline polymers, the crystalline phase should be stable relative to the concentrated anisotropic phase of the wide biphasic region.
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