Glassy poly(p-phenylene sulphide): determination of the local structure

Jones, Teresa; Mitchell, Geoffrey R.; Windle, Alan H.

doi:10.1007/bf01410689

Cited by 26 publications

(14 citation statements)

References 31 publications

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“…They indicate that the carbonate group is trans-cis and that the chain, considering virtual phenylene bonds, is essentially a planar zig-zag. There remains contention however, as to whether the planes of the phenylene groups are nearly normal to, [15,25] or at _+ 45 ~ to [22], the plane of the carbonate group, in any case it appears that for PC [15] and other phenylene polymers [16,26], the molecular profile is sufficiently corrugated to encourage a level of special short range correlations between phenyiene groups on neighbouring chains. These correlations, which are limited to a small number of chemical repeats, also include those which generate the shoulder observed in the scattering pattern of PC at s -1.8 1~-~.…”

Section: Methodsmentioning

confidence: 97%

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The effect of annealing on the local structure of glassy polycarbonate

Mitchell

Windle

1985

Colloid & Polymer Sci

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Annealing of polycarbonate glasses at temperatures below Tg leads to an increase in yield stress and a drop in the impact strength. Although such behaviour may be related to the corresponding reduction in free volume upon annealing, variations in the wide-angle X-ray scattering curves indicate some modification to the local structure. The area of an intrachain peak at s -0.7/~l-i is monitored with respect to annealing temperature and time. It is proposed that the variations may be described by an increasing level of interlocking or (nesting) between neighbouring chain segments, a process which is a natural consequence of the molecular shape of polycarbonate.

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Section: Methodsmentioning

confidence: 97%

“…This paper reports a development of the wide angle X-ray scattering (WAXS) work of Neki and Geil [5] and Saffell and Windle [8] and uses recent analyses of the local structure of polycarbonate and other phenylene based polymers [15,16].…”

Section: Introductionmentioning

confidence: 99%

The effect of annealing on the local structure of glassy polycarbonate

Mitchell

Windle

1985

Colloid & Polymer Sci

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“…16, No.4, 1984 The Local Conformation of Poly(dimethylsiloxane) would expect considerable fluctuations in the values of the bond rotation angles, and such distortions are included in the next model considered. We may easily incorporate random uncorrelated thermal-like fluctuations of the skeletal bond rotation angles into the scattering calculations, 20 • 24 and we consider here Gaussian distributions of rotation angles centered about the rotation states, trans, gauche and -gauche. Figure 4 shows the calculated si(s) curves for such models compared with the experimental data.…”

Section: Conformational Analysismentioning

confidence: 99%

The Local Conformation of Poly(dimethylsiloxane)

Mitchell

Odajima

1984

Polym J

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ABSTRACT:Wide-angle X-ray scattering (WAXS) data obtained at room temperature from bulk poly( dimethylsiloxane) is presented and compared with the scattering functions calculated for random single chains in which the skeletal bond rotation angles have been assigned according to the precepts of the rotational isomeric state (RIS) approximation. There are significant differences between experimental and calculated curves, which are not eliminated by the introduction of large thermal-like fluctuations of the bond rotation angles. It is suggested that the rotation states are delocalised in PDMS, as the scattering calculated for a chain with free rotation of the skeletal bonds provides a more satisfactory fit to the experimental data. The relevance of the RIS approach for describing the local conformation of polymer molecules is discussed and the need to sample the spatial distribution function of the chain at different scales is stressed.KEY WORDSThe characteristics of the trajectories of individual polymer molecules have been extensively studied, both theoretically and by experiment.1 In these studies the use of the rotational isomeric state (RIS) model 2 has been particularly successful in providing a framework within which a broad understanding of the configuration dependent properties of macromolecules has developed. However, recently the approximations inherent in the RIS approach have been critically examined. 3 -u Procedures have been presented which allow for the inclusion of thermal-like fluctuations in the values assigned to the skeletal bond rotations angles, 3 • 4 • 10 · 11 and more radical approaches have been considered which evaluate the chain properties taking account of all possible molecular configurations.5·9 The result of each of these studies suggests that many of the discrepancies and anomalies observed in previous studies may be accounted for by abandoning the approximations of the RIS model for a more exact treatment. A common feature of configurational studies is that the correctness of the proposed model is evaluated by comparing experimental measurements of the mean square end-to-end vector or similar large correlation distance functions with those calculated on the basis of the model. Thus while the properties measured are dependent upon longrange correlations, the input to the models, whether it be a RIS or modified model, is essentially of a short range nature, defining the interdependence of the conformational energy for skeletal bond rotations. Such interdependence is usually restricted to first and second nearest neighbour bonds. Under these circumstances it would seem more direct to attempt to determine the characteristics of the local t Present address:

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“…(1) (2) These synthetic difficulties can be overcome by the use of a soluble precursor for the target polymer. Thus, conductive polymers such as poly(p-phenylenevinylene)(22-25) and poly(p-phenylene)(26-2S) which are insoluble in common solvents, are synthesized via soluble precursors.…”

Section: "}^mentioning

confidence: 99%

Poly(sulfonium cation) for the Synthesis of High-Molecular-Weight Poly(phenylene sulfide)

Yamamoto

Tsuchida

1996

Step-Growth Polymers for High-Performance Materials

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High molecular weight poly(phenylene sulflde)(PPS), Mw > 2 x 10 5 , was synthesized via a poly(sulfonium cation) through oxidative polymerization of methyl 4-(phenylthio)phenyl sulfoxide. Polymerization proceeds in protic acid homogeneously. The poly(sulfonium cation) was soluble in common solvents such as acetonitrile, acetone, formic acid and dimethyl sulfoxide. The poly(sulfonium cation) was available as a soluble intermediate for the synthesis of high molecular weight poly(phenylene sulfide). It was feasible to convert high molecular weight poly(arylene sulfide) through the Sn 2 reaction with pyridine as a nucleophile. This polymerization is applicable to the synthesis of new block copolymers such as, poly(phenylene sulfide)-block-[poly(tetrafluoroethylene-co-per fluoro (propylvinyl ether)]}-block-poly(phenylene sulfide). The poly sulfonium cation is isolatable as a stable salt which acts as an unique polymeric reagent for the methylation of aromatic compounds having mobile hydrogen.High molecular weight poly(p-phenylene sulfide) (PPS) has received much attention as a high-performance engineering plastic due to its excellent chemical, thermal, and mechanical properties which are a result of its high crystallinity(i-6) These properties make it difficult to synthesize high molecular weight PPS. Normally, the preparation of PPS employs high-temperature and high-pressure processes in order to overcome poor solvent solubility, e.g. commercial preparations of PPS are often carried out at temperature in excess of the boiling point of NMP, and require the use of pressure vessels. To overcome these difficulties a large amount of effort has been put into the formation of high molecular weight poly(arylene sulfide) (PAS)(Eq. l)(7-75). PPS can also be obtained by other reaction mode, e.g. electrophilic reaction and

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Glassy poly(p-phenylene sulphide): determination of the local structure

Cited by 26 publications

References 31 publications

The effect of annealing on the local structure of glassy polycarbonate

The effect of annealing on the local structure of glassy polycarbonate

The Local Conformation of Poly(dimethylsiloxane)

Poly(sulfonium cation) for the Synthesis of High-Molecular-Weight Poly(phenylene sulfide)

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