The effects of stereoregularity on the pressure-volume-temperature and related properties of poly(methyl methacrylate)

Quach, Anh; Wilson, Phillip S.; Simha, Robert

doi:10.1080/00222347408204553

Cited by 40 publications

(12 citation statements)

References 21 publications

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“…There is no evidence from dilatmetric data [8,9] for a Tpp in these polymers. This conclusion is verified by inspection of the specific volume-T plots of Bywater and Toporowski [125], as well a s from computer analysis of their tabulated data [124].…”

Section: S O T a C T I C A N D S Y N D I O T A C T I C P M M Amentioning

confidence: 79%

“…Following Olabisi and Simha [12], C' = 0.4343~ = 0.0894. b and c are the conventional parameters i n the Tait equation [6,7,9,12,19]. By s e r i e s expansion of In (1 f x), where x = P/b is in the range of 0 to 1, we arrive at which is correct to 2-1/2% at x = 0.5 with third-order terms, 6% with second-order terms, and 21% with the first term.…”

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 96%

“…T P P is 110°C at P = 1, dTQp/dP is 70 K/kbar. F o r all polymers studied thus far, dT /dP increases linearly with the expansion coefficient for free volume, A a , and hence as T b undergoes a major increase at T [6,9,12] and g' g P g'…”

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 99%

“…Simha et al [19] Tpp increases linearly from 142 for isotactic to 174°C for syndiotactic, while T /T decreases from 1.28 t o 1.11; the g intensity is greatest f o r isotactic, next for syndiotactic, and with a broad minimum around 20-40% syndiotactic [184]. and Simha [9] on isotactic PMMA by the method of Eq. (19).…”

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 99%

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Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers

Boyer

1980

Journal of Macromolecular Science, Part B

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A B S T R A C TThe liquid state behavior of the following atactic polymers has been reviewed: the alkyl and cycloalkyl methacrylates; polyisobutylene; polybutadiene, its random copolymers with styrene and acrylonitrile, and S-B diblocks; polystyrene; and the poly-cuolefins C3, C5, and C Just as T manifests itself through time-dependent (relaxational) and thermodynamic (transition) effects, so also does a T > T transition (relaxation) found generally in the range of 1.1 t o 1.3 T but mostly near 1 . 2 T This is designated as TQQ, a liquidl-liquid transition. T a~ is found, usually by a variety of dynamic, thermodynamic, and probe methods, in all of the above classes of polymers plus iso-PMMA, which also has a weak T < T o r T relaxation. With increasing syndiotactic content, PMMA's reveal strengthening T and T processes. Relaxation maps plotting log frequency-T TQQ. tion enthalpy about half that at T when both are observed some 50-100°K above their very low frequency values. Probe methods 6' g g g g' 2 g P P QQ-1 a r e presented for PBD and PIB, showing both T and g The latter exhibits non-Arrhenius behavior with an activag 461 Copyright 0 198 1 by Marcel Dekker, Inc. Downloaded by [Tulane University] at 09:04 05 January 2015 462 BOYER such as IR, "C-NMR, ESR with spin probes, depolarization of fluorescence, and thermally stimulated current seem unusually well suited to studies of the liquid state. The earliest concept of a TPL is that of Ueberreiter in 1943; the earliest experimental evidence is the torsion pendulum data of Schmieder and Wolf on PIB in 1953 and PMMA in 1957. TLP is inherently weak comparedto T and its strength is polymer specific, being relatively strong in PIB, weak in PBD. TLp is compared with the "slow process"of F e r r y and co-workers, ascribed t o slippage of dangling entanglements. TPQ occurs also below the entanglement molecular weightMc.Modern statistical methods such a s regression analysis are used to analyze T > T data for the presence o r absence of weak transitions, especially V-T and C -T data. The possibility of artifacts in some methods makes it imperative to search for T P p by many alternate methods, It is shown that isothermal V -P plots are more revelatory of TLL than a r e isobaric V-T plots. The use of Wood's variation of the Tait equation relating bulk modulus and pressure is useful in some cases for locating liquid state relaxations. Preliminary estimates of d(TQP)/dP, presented for PnBMA, P(cyclohexy1 MA) and a-PS, a r e in the range of 50-70 K/kbar, i.e. , 2-3 times the well known values for dT dP. A phase dualism hypothesis by Frenkel and Baranov suggests that TPL represents competition between segment-segment (liquid-like) behavior and the tendency of the macromolecule t o act as a gas at high temperature, Melt elasticity measurements on PS reveals a molecular weight dependent transition which appears to be TPQ ,The enthalpy of activation decreases by a factor of two from below to above TPp. The term "thermodynamic" in the title signifies use of quasi-equilibrium typ...

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Section: S O T a C T I C A N D S Y N D I O T A C T I C P M M Amentioning

confidence: 79%

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 96%

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 99%

Section: P H a S E D U A L I S M I N T E R P R E T A T I O N O F T L Lmentioning

confidence: 99%

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Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers

Boyer

1980

Journal of Macromolecular Science, Part B

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“…Utilizing a nonlinear least squares method, 14 we fit the experimental PVT data of 18 polymer melts and a blend melt, 15 i-poly(methyl methacrylate) (i-PMMA) 16 and PVME 17 with the equation of state to get the values of P Ã , V Ã 0 and T Ã after some trial and error. In Tables I and II, we show the final results of S 2 (the fitting goodness to P), P Ã , V Ã 0 , T Ã , 0 (linear length of CGP at 0 K), c and .…”

Section: Resultsmentioning

confidence: 99%

Application of a New Cell Model for the Equation of State to 20 Polymer Melts and a Blend Melt

Murakami¹

2005

Polym J

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ABSTRACT:In a previous publication, we reported a new cell model for the equation of state of polymer melts. The equation contains external degrees of freedom explicitly as a function of molecular weight of repeating unit. In this paper, we apply the theory to 20 polymer melts and a blend melt. The linear lengths of the coarse-grained particle (CGP) of several polymers coincide with those obtained by scattering experiments. In addition, we estimated the characteristic quantity T Ã of the equation of state per repeating unit using van der Waals constants and the critical temperature of the repeating unit or monomer. The values, T Ã , agreed with those from our result per repeating unit. This result suggests the quantitative validity of our theory. We strongly suggest that our theory must be related to the conformer model by Matsuoka and the helical wormlike chain model by Yamakawa, because T Ã must be dependent on the chemical structure and stiffness of the polymers.

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Appendix B: Robert Simha Publications

2010

Polymer Physics

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The effects of stereoregularity on the pressure-volume-temperature and related properties of poly(methyl methacrylate)

Cited by 40 publications

References 21 publications

Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers

Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers

Application of a New Cell Model for the Equation of State to 20 Polymer Melts and a Blend Melt

Appendix B: Robert Simha Publications

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The effects of stereoregularity on the pressure-volume-temperature and related properties of poly(methyl methacrylate)

Cited by 40 publications

References 21 publications

Dynamics and thermodynamics of the liquid state (T < Tg) of amorphous polymers

Dynamics and thermodynamics of the liquid state (T < Tg) of amorphous polymers

Application of a New Cell Model for the Equation of State to 20 Polymer Melts and a Blend Melt

Appendix B: Robert Simha Publications

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Product

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Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers

Dynamics and thermodynamics of the liquid state (T < T_g) of amorphous polymers