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1.
J. R. Schneider Willman I. R. Peat 《Journal of polymer science. Part A, Polymer chemistry》1987,25(3):857-872
13C-NMR has been used to analyze the microstructures of a series of experimental chlorinated ethylene–vinyl acetate copolymers (15–56% CI). Previously established line assignments for EVA copolymers and substituent effect parameters for chlorine have enabled us to tentatively assign partial structures up to five carbon atoms in length. The 13C-NMR analyses of a commercial vinyl chloride–vinyl acetate copolymer, a commercial vinyl chloride–vinyl acetate–ethylene terpolymer, and a commercial chlorinated polyethylene support the structural assignments. Data obtained for the experimental resins indicate that the acetate groups influence the way in which chlorine is added to the polymer chain. furthermore, the data indicate the acetate groups undergo little, if any, chlorination. 相似文献
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Biphenylene as a crosslinking unit in polyaromatic ether–ketone and ether–ketone–sulfone resins. XVI
Raymond J. Swedo C. S. Marvel 《Journal of polymer science. Part A, Polymer chemistry》1979,17(9):2815-2824
Biphenylene units have been incorporated into polyaromatic ether–ketone and polyaromatic ether–ketone–sulfone resins as useful crosslinking sites. Crosslinking is achieved by heating the resins to 300–400°C. The keto polymers are soluble only in sulfuric acid before curing, but the sulfone polymers are soluble also in some aprotic solvents. Molded “I beams” of the cured keto polymer are stronger than those of the sulfone polymer. Both classes of polymer are quite thermally stable. Curing can be hastened by catalyzing with rhodium compounds. 相似文献
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We have established time–temperature transformation and continuous-heating transformation diagrams for poly(ether–ether–ketone) (PEEK) and PEEK/poly(ether–imide) (PEI) blends, in order to analyze the effects of relaxation control on crystallization. Similar diagrams are widely used in the field of thermosetting resins. Upon crystallization, the glass transition temperature (Tg) of PEEK and PEEK/PEI blends is found to increase significantly. In the case of PEEK, the shift of the α-relaxation is due to the progressive constraining of amorphous regions by nearby crystals. This phenomenon results in the isothermal vitrification of PEEK during its latest crystallization stages for crystallization temperatures near the initial Tg of PEEK. However, vitrification/devitrification effects are found to be of minor importance for anisothermal crystallization, above 0.1°C/min heating rate. In the case of PEEK/PEI blends, amorphous regions are progressively enriched in PEI upon PEEK crystallization. This promotes a shift of the α-relaxation of these regions to higher temperatures, with a consequent vitrification of the material when crystallized below the Tg of PEI. The data obtained for the blends in anisothermal regimes allow one to detect a region in the (temperature/heating rate) plane where crystallization proceeds in the continuously close proximity of the glass transition (dynamic vitrification). These experimental findings are in agreement with simple simulations based on a modified Avrami model coupled with the Fox equation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 919–930, 1998 相似文献
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Polyesteramide 6NT6–polytetramethylene ether glycol (PTMEG) copolymers, precipitated from dilute solution, have been studied by small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with variation of the PTMEG content. A comparison of the structural characteristics of these materials has been made with those of the 6NT6 homopolymer. Chain folding is assumed as the crystallization mechanism for the low-PTMEG-content copolymers, with possible inclusion of polyether segments within the 6NT6 crystal lattice. WAXS data support the view of a weakening of the 6NT6 crystalline packing in the equatorial planes as the reason for broadening of the diffraction peaks, for changes in their relative intensities, and for the increase in the equatorial interplanar distances in the high-PTMEG-content samples. The annealing behavior has also been investigated. 相似文献
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D. B. Bailey P. M. Henrichs 《Journal of polymer science. Part A, Polymer chemistry》1978,16(12):3185-3199
The DMSO solution copolymerization of acrylonitrile and vinylidene chloride can be adequately described by the terminal-unit copolymerization model. The sequence distribution measured by 13C-NMR is in excellent agreement with the theoretically calculated diad, triad, and pentad distributions. The variation of glass transition temperatures with copolymer composition is explained by sequence distribution. 相似文献
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Takeshi Ogawa C. S. Marvel 《Journal of polymer science. Part A, Polymer chemistry》1985,23(4):1231-1241
Polyaromatic ether–ketones and polyaromatic ether–keto–sulfones were sulfonated by suspending the polymer powders in dichloroethane containing liquid sulfur tiroxide and trialkyl phosphate at room temperature. It was found that more than one sulfonic group can be introduced per each repeating unit of the polymers without degradation. The sulfonated polymers were soluble in various organic solvents, and solubility and mechanical properties depended on the initial molecular weight of polymers as well as the degrees of sulfonation. Strong films can be cast from their dimethylformamide solutions. 相似文献
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In the second part of this general study, the carbon fiber–PEEK interfacial shear strength is measured by means of a fragmentation test on single-fiber composites. Different thermal treatments (continuous cooling from the melt, isothermal treatments and long melting temperature time) are applied to these model composites prior to testing. The results are systematically compared with the previously determined reversible work of adhesion between carbon fiber and PEEK. It is shown that physical interactions at the interface determine, to a large extent, the magnitude of the interfacial shear strength between both materials. However, it appears that the magnitude of the stress transfer from the matrix to the fiber is affected either by the existence of an interfacial layer or by a preferential orientation of the polymer chains near the fiber surface. The results obtained on systems that have been subjected to isothermal treatments (isothermal crystallization of PEEK) seem to confirm the existence of a transcrystalline interphase, the properties of which are dependent upon the crystallization rate of the matrix and the interfacial adhesion energy. 相似文献
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Christian Pichot Marie-France Llauro Quang-Tho Pham 《Journal of polymer science. Part A, Polymer chemistry》1981,19(10):2619-2633
The compositions and sequence distributions of vinyl acetate–butyl acrylate copolymers obtained with batch and semicontinuous emulsion polymerizations have been studied by 1H and 13C NMR. The batch process gives heterogeneous copolymers while with the semicontinuous one the sequence distribution is statistical. These differences in sequence distributions have been related to the physical properties of the copolymers. 相似文献
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John K. Borchardt E. Dwyann Dalrymple 《Journal of polymer science. Part A, Polymer chemistry》1982,20(7):1745-1764
A multiple-correlation analysis program was used to generate equations relating the Alfrey–Price Q and e values of vinyl monomers to the 13C-NMR absorption frequencies of the α- and β-carbon atoms of the monomers. Separate equations for the calculation of Q and e values of styrenes, chlorinated olefins, acrylates, methacrylates, vinyl ethers, and esters, nitrogen containing monomers, allyl compounds, and miscellaneous olefins were developed. The correlation coefficients of most of these equations were greater than 0.99 and permit accurate calculation of the Q and e values. The Q and e values so calculated may then be used to obtain estimates of the reactivity ratios in copolymerizations prior to actually performing the experiments. Attempts to develop a single Q value equation and a single e value equation for 63 vinyl monomers of the above classes resulted in relations having correlation coefficients of 0.63 and 0.81, respectively, too low to permit sufficiently accurate calculation of the Q and e values. 相似文献
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Robert J. Gambogi D. L. Cho H. Yasuda Frank D. Blum 《Journal of polymer science. Part A, Polymer chemistry》1991,29(12):1801-1805
Plasma polymerized hydrocarbons made from ethane and methane were produced under different reactor conditions and probed by solid-state carbon-13 nuclear magnetic resonance (13C-NMR) with cross-polarization and magic-angle sample spinning. NMR experiments provided structural information about the plasma polymers. The conditions of low power, high hydrocarbon gas flow rate, and no added hydrogen gas appeared to give the highest amount of nonprotonated sp3 hybridized carbons in the films for the reactor design used. The use of methane or ethane as reactor gas did not affect plasma polymer structure significantly. 相似文献
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《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1983,39(8):713-715
The proton-decoupled 13C FT—NMR spectra of para-, meta- and ortho-cresyl benzoates have been recorded and the observed signals have been assigned following the substituent additivity rule. The important features of diagnostic value of these spectra are discussed. 相似文献
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The aim of this general study is to determine the physicochemical characteristics and mechanical properties of carbon fiber–PEEK interfaces. In the first part, the dispersive component of the surface energy and the electron acceptor–donor (acid–base) characteristics of PEEK polymer and different types of untreated and surface-treated carbon fibers are determined by means of inverse gas–solid chromatography at infinite dilution. It appears, in particular, that the acid–base surface properties of PEEK and, consequently, the orientation of macromolecules near the surface, depend on the processing of this polymer. Moreover, according to previous work, an estimation of the adhesion energy, corresponding to physical interactions (London and acid–base interactions) at carbon fiber–PEEK interfaces is proposed. Whatever the surface characteristics of PEEK, the highest level of carbon fiber–PEEK adhesion is achieved in systems involving oxidized or sized carbon fibers. 相似文献
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J. V. Prasad 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):2033-2036
Commercial block copolymers of propylene with ethylene (PEBC) are multiphase systems comprising block and random copolymers as well as small amounts of homopolymers. At present, no satisfactory method exists for characterizing the “blocky” structure of these copolymers. This article aims to fulfill this need. Accordingly, the block and random copolymers of propylene with ethylene have been investigated using 13C CP/MAS NMR with high-power dipolar decoupling. Comparisons have been made between the spectra of block and random copolymers and it is shown possible to distinguish between them by means of an additional signal, appearing at 32.5δ, in block copolymers (attributable to block junctions). © 1992 John Wiley & Sons, Inc. 相似文献
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Rong‐Ming Ho Ping‐Yen Hseih Ching‐Cheng Yang Jiang‐Jen Lin 《Journal of Polymer Science.Polymer Physics》2001,39(20):2469-2480
A series of low‐ether‐content polyether–polyester block copolymers with amide linkages were synthesized. Their crystallization kinetics and mechanisms were investigated. The crystallization kinetics were analyzed via Avrami treatment; an average value of 1.8 for the Avrami index was thus obtained. Athermal nucleation was evidenced by observations of a linear boundary between impinged spherulites under polarized light microscopy and transmission electron microscopy. The development of spherulitic morphology with a hedgehog texture was attributed to the mechanism of lamellar branching. On the basis of the morphological observations and Avrami analysis, a crystallization mechanism through a heterogeneous nucleation process with homogeneous lamellar branching was proposed. No regime transition was found for polyether–polyesters in the examined temperature ranges, and the crystallization was identified as regime I kinetics on the basis of a Lauritzen Z test. The copolymerization of poly(ether amide)s with polyesters led to a significant suppression of the crystallization rate of polyester crystals. The suppression was explained as the result of a dilution effect in nucleation combined with an increasing nucleation barrier. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2469–2480, 2001 相似文献
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J. C. J. F. Tacx G. P. M. Van Der Velden A. L. German 《Journal of polymer science. Part A, Polymer chemistry》1988,26(5):1439-1456
The compositions and sequence distributions of homogeneous styrene (S)–ethyl methacrylate (E) copolymers, obtained by low conversion solution polymerization have been studied by 1H- and 13C-NMR. A new set of peak triad assignments was proposed for the δ 2.1–4.2 ppm region in the 1H-NMR spectrum, whereby the reactivity ratios of rS = 0.59 and rE = 0.50 were used to establish this new assignment. The EEE and SSS blocks, present in these copolymers, have a high degree of syndiotacticity (σEE = 0.23, σSS = 0.39), whereas the ESE units are exhibiting a slight tendency toward isotacticity (σES = 0.66). 相似文献
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M. Periyasamy Warren T. Ford Frank J. McEnroe 《Journal of polymer science. Part A, Polymer chemistry》1989,27(7):2357-2366
p-Divinylbenzene (DVB) 13C-labeled at the methine carbon of the vinyl group was copolymerized in suspension with styrene at 70, 70–95, and 135–155°C using 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The number of unreacted vinyl groups in each copolymer was determined by 13C CP–MAS NMR analysis of solid samples, direct polarization 13C-NMR analysis of CDCl3-swollen gels, and bromination. Results from the three methods agree methods agree qualitatively. Even the 1% DVB-crosslinked networks contained 40% unreacted DVB-vinyl groups when prepared by high conversion polymerization at 70°C and 16% unreacted DVB-vinyl groups when polymerization was finished at 95°C. The analyses were also applied to some commercial crosslinked polystyrenes. Every sample examined contained pendent vinyl groups 相似文献