Isomorphic behavior of random copolymers: thermodynamic analysis of cocrystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Kamiya, Noriho; Sakurai, Minoru; Inoue, Yoshio; Chûjô, Riichirǒ

doi:10.1021/ma00013a023

Cited by 81 publications

(73 citation statements)

References 6 publications

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“…At low 3HV compositions, cocrystallization would mean inclusion into a relatively defect-free lattice, which appears to be less favourable. The NMR results presented here are similar in a general sense to previous solid state NMR studies on P(3HB-co-3HV) cocrystallization (10,11). Both previous studies, which were based on lineshape deconvolution, also reported significant inclusion of 3HV in the PHB-type lattice.…”

Section: Nmr Analysissupporting

confidence: 89%

“…In the present NMR study, which we feel is based on fewer assumptions than the two previous studies, we calculate a higher degree of cocrystallization. For example, Kamiya et al (10) saw no 3HV incorporation until the 3HV content was above 18 mol%.…”

Section: Nmr Analysismentioning

confidence: 99%

“…There is increasing evidence, however, that the cocrystallization of both comonomers is not uniform, and that there is selective partitioning of comonomers between crystalline and amorphous phases (4,(9)(10)(11). Partitioning must alter the dynamics of crystallization, with ramifications such as altering the number of defects in the crystalline phase, and changing the crystalline domain sizes.…”

Section: Introductionmentioning

confidence: 99%

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Cocrystallization in random copolymers of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) and its effect on crystalline morphology

Orts¹,

VanderHart²,

Bluhm³

et al. 1995

Can. J. Chem.

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Small-angle X-ray scattering (SAXS) and solid state CPMAS I3c NMR were used to describe the crystalline morphology of a series of bacterially produced poly((3-hydroxybutyrate-co-P-hydroxyvalerate) copolymers containing random distributions of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV). Modeling of SAXS results showed that the morphology of this isodimorphic system is better described by two phases, crystalline and amorphous, having defects within each domain. This is in contrast to a model with a large interfacial region between phases. For the 3HV composition range 0-27 mol%, the polymer crystallizes in a poly(P-hydr0xybutyrate)-type crystalline lattice. Solid state NMR results showed that there is significant incorporation of the 3HV minor component into the poly(P-hydroxybutyrate) crystalline phase over this composition range. The ratio of the 3HV content in the crystalline phase relative to the overall 3HV content is not linear, but increases with increasing 3HV. For the 21 and 27% 3HV samples, the 3HV content in the crystalline phase is as much as 213 of the overall 3HV content. Inclusion of 3HV is correlated to an increase in crystalline disorder (as measured by SAXS), implying that it is easier to accommodate the bulkier 3HV comonomer into a crystalline region that already contains defects.Key words: bacterial polyesters, poly(3-hydroxyalkanates), small-angle X-ray scattering, solid state NMR, cocrystallization.RCsumC : On a utilisC la diffraction des rayons X B de petits angles (SAXS) et la RMN du 13c CPMAS B 1'Ctat solide pour dCcrire la morphologie cristalline d'une sCrie de copolymkres poly(P-hydroxybutyrate-co-phydroxyvalCrate) produits par une voie bactCrienne et contenant des distributions au hasard de 3-hydroxybutyrate (3HB) et de 3-hydroxyvalCrate (3HV). Un modelage des resultats SAXS a montrC que la meilleure f a~o n de dCcrire la morphologie de ce systkme isodimorphique est B l'aide de deux phases, l'une cristalline et l'autre amorphe, ayant des dkfauts dans chaque domaine. Pour une composition de 3HV allant de 0 i 27 mol%, le polymkre cristallise dans une rCseau cristallin du type poly(P-hydroxybutyrate). Les rCsultats de la RMN B l'etat solide ont montrC que, sur cette plage decomposition, il se produit une incorporation importante du composant mineur du 3HV dans la phase cristalline du poly(P-hydroxybutyrate). Le rapport de la quantitC de 3HV contenue dans la phase cristalline par rapport B la quantitC totale de 3HV n'est pas linCaire; il augmente avec une augmentation du 3HV. Pour les Cchantillons contenant 21 et 27% de 3HV, la quantitC de 3HV contenue dans la phase cristalline reprksente pratiquement les 213 de la quantitC totale de 3HV. I1 existe une corrClation entre l'inclusion du 3HV et l'augmentation du dCsordre cristallin (tel que mesurC par SAXS); ceci implique qu'il est plus facile d'accommoder le gros comonombre 3HV dans une region cristalline qui contient dCjB des dCfauts.

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Section: Nmr Analysissupporting

confidence: 89%

Section: Nmr Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cocrystallization in random copolymers of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) and its effect on crystalline morphology

Orts¹,

VanderHart²,

Bluhm³

et al. 1995

Can. J. Chem.

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“…Sanchez and Eby 3,4 put forward an equation of melting-point depression that takes care of the defect entering into the crystals. Recently, Kamiya et al 9 proposed a theory of copolymer crystallization in which the comonomer units produce the cocrystals. According to their theory, the equation of the melting-point depression of a copolymer containing single type of defect structure can be expressed as follows: …”

Section: Discussionmentioning

confidence: 99%

An equilibrium study on the distribution of structural defects between the lamellar and amorphous portions of poly(vinylidene fluoride) and (vinylidene fluoride-tetra fluoro ethylene) copolymer crystals

Dikshit¹,

Nandi²

2000

J. Polym. Sci. B Polym. Phys.

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“…Kamiya et al 4) developed a thermodynamic model for the bulk Gibbs energy, which gives the defect Gibbs energy e of HB-HV and HV-HV diads in the HB crystal based on the well-known model of Sanchez and Eby 5) , and obtained values for e of 5.1 and 7.7 kJ/mol, respectively. A concentration dependence of these values was surmised.…”

Section: Introductionmentioning

confidence: 99%

On the isomorphism of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) random copolymers

Wendling¹,

Suter²

1999

Macromol. Theory Simul.

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SUMMARY:The defect Gibbs energy of hydroxyvalerate comonomer inclusions into the crystals made up by random copolymers of poly(b-hydroxybutyrate-co-b-hydroxyvalerate) (PHB/HV) is calculated by means of the thermodynamic integration approach. The result obtained for a single inclusion is in excellent agreement with those obtained by fitting experimental melting temperature and cocrystal composition data. Lattice model calculations that cover the whole range of copolymer composition were carried out based on calculations of double inclusion, which revealed a decrease of the average defect Gibbs energy in adjacent defects. On decomposing the Gibbs energy, it is found that the configurational entropy contributes the dominant part of the defect Gibbs energy.

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Isomorphic behavior of random copolymers: thermodynamic analysis of cocrystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Cited by 81 publications

References 6 publications

Cocrystallization in random copolymers of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) and its effect on crystalline morphology

Cocrystallization in random copolymers of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) and its effect on crystalline morphology

An equilibrium study on the distribution of structural defects between the lamellar and amorphous portions of poly(vinylidene fluoride) and (vinylidene fluoride-tetra fluoro ethylene) copolymer crystals

On the isomorphism of poly(β-hydroxybutyrate-co-β-hydroxyvalerate) random copolymers

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