Interchain exchange and interdiffusion in blends of poly(ethylene terephthalate) and poly(ethylene naphthalate)

Krentsel, L. B.; Makarova, V. V.; Kudryavtsev, Yaroslav V.; Govorun, E. N.; Litmanovich, A. D.; Маркова, Г. Д.; Васнев, В. А.; Куличихин, В. Г.

doi:10.1134/s0965545x09110091

Cited by 8 publications

(3 citation statements)

References 17 publications

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“…The contribution of COOH end groups was also found negligible in these studies. Krentsel et al reported the same rate constants for a melt of commercial PET and PEN ( M η ≈ 10 4 ) containing residual catalyst and that of catalyst-free synthesized PET and PEN ( M η ≈ 10 3 ), the greater amount of reactive end groups compensating the absence of catalyst in the latter case.…”

Section: Introductionmentioning

confidence: 79%

Kinetics and Mechanisms of Poly(poly(ethylene terephthalate)-co-poly(ε-caprolactone)) Catalyzed Randomization: Influence of End Groups

et al. 2010

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Hydroxy-ester interchanges were found to be the predominant reactions involved in poly-(ethylene terephthalate)-poly(ε-caprolactone) copolyester randomization. Even for high molar-mass copolyesters having low hydroxyl end group concentration, kinetic studies show that ester-ester interchanges play a minor role. Reaction rate was almost proportional to hydroxyl end groups concentration. The randomization kinetics was studied by 1 H NMR on copolyesters obtained in situ by reacting a series of poly(ethylene terephthalate)s of various molar masses and end groups with ε-caprolactone, in the molten state and in the presence of Ti(OBu) 4 catalyst. A mechanism involving parallel catalyzed second-order hydroxy-ester and ester-ester interchanges is proposed for the randomization step and perfectly fits experimental data. This study clearly shows that the nature and concentration of hydroxyl end groups must be carefully controlled for reliable synthesis of copolyesters by homopolyester melt blending.

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Section: Introductionmentioning

confidence: 79%

Kinetics and Mechanisms of Poly(poly(ethylene terephthalate)-co-poly(ε-caprolactone)) Catalyzed Randomization: Influence of End Groups

et al. 2010

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“…Therefore, study on improving the processing properties and solubility of poly(aryl ether)s through structural modification is one of the research hotspots. Structure changes have focused on the introduction of semi flexible groups (such as sulfone, sulfur ether, methylene substituents) to improve the solubility and rigid groups (such as naphthalene [12][13][14], aromatic heterocyclic, anthracene) to enhance the thermal stabilities, and the incorporation of pendant alkyl or phenyl groups on to the poly(aryl ether) in the backbone of the polymeric chain [15][16][17][18][19]. Our group has synthesized and characterized poly(aryl ether)s with pendant -naphthyl groups [20].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Preliminary Properties of Novel Poly(aryl ether)s Containingβ-Naphthalene Pendant Group

Wang

Tao

Xiang

et al. 2014

Journal of Chemistry

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Two novel poly(aryl ether)s containingβ-naphthalene pendant group were synthesized and the structures of these polymers were confirmed by1HNMR spectroscopy. The polymers exhibited good thermal stabilities with highTgof 256°C and 274°C, respectively. The polymers are soluble in common organic solvents, such as DMAc, DMSO, CH2Cl2, and CHCl3, and can be electrospun into microfiber (1–5 µm) with lots of nanopores (<100 nm) from CHCl3solution. These fibers showed high hydrophobicity, and the contact angle of fibers is above 120°.

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“…Segmental exchange reactions (reshuffling) are common phenomena in ionic and covalent ring opening polymerization of heterocyclic monomers, which often preclude synthesis of (co)polymers with required strictly defined properties. Although there are several reaction routes leading to segmental exchange, the processes involving active chain ends are the most important 1–6. These processes are realized by the attack of an active center of polymerization (or of a specific type of chain end, which is active in segmental exchange processes) on a monomeric unit in another chain and subsequent chain scission of the attacked macromolecule with the simultaneous merging of the attacking chain with one part of the cleaved chain (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Kinetic Monte Carlo Studies on the Importance of the Reaction Scheme in Segmental Exchange of Copolymer Chains

Szymański

Sosnowski

2012

Macro Theory & Simulations

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Kinetic Monte Carlo studies (confirmed by integration of the corresponding differential equations) are used to demonstrate the fundamental differences between the two most often accepted schemes of segmental exchange. Modeling of reshuffling systems, originally composed of homopolymers of various $\overline {DP} _{{\rm n}} $, various mass distributions, and different compositions, is carried out until the equilibrium copolymers are obtained. It is shown that one of the schemes leads always to a random microstructure (Bernoulli statistics) whereas modeling of the other one indicates possibility of formation of all achievable distributions of comonomer units (from multiblock to nearly alternate). The concepts of the degrees of randomness and reshuffling are discussed and new definitions are proposed.

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Interchain exchange and interdiffusion in blends of poly(ethylene terephthalate) and poly(ethylene naphthalate)

Cited by 8 publications

References 17 publications

Kinetics and Mechanisms of Poly(poly(ethylene terephthalate)-co-poly(ε-caprolactone)) Catalyzed Randomization: Influence of End Groups

Kinetics and Mechanisms of Poly(poly(ethylene terephthalate)-co-poly(ε-caprolactone)) Catalyzed Randomization: Influence of End Groups

Synthesis and Preliminary Properties of Novel Poly(aryl ether)s Containingβ-Naphthalene Pendant Group

Kinetic Monte Carlo Studies on the Importance of the Reaction Scheme in Segmental Exchange of Copolymer Chains

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