Phosphorus-Containing Poly(ethylene terephthalate): Solid-State Polymerization and Its Sequential Distribution

Li, Liang-Jie; Duan, Rong-Tao; Zhang, Junbo; Wang, Xiuli; Chen, Li; Wang, Yu‐Zhong

doi:10.1021/ie400224z

Cited by 23 publications

(18 citation statements)

References 39 publications

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“…NMR is by far the technique of choice for the determination of the composition and chemical microstructure of PET copolyesters and terpolyesters . Regarding poly(ethylene terephthalate‐ co ‐isophthalate)s (PET x I y ), which are known to be the main PET modification used for plastic bottles, literature affords a good number of cases in which the copolyester is fully characterized .…”

Section: Copolyesters and Blendsmentioning

confidence: 99%

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Ilarduya

Muñoz‐Guerra

2014

Macro Chemistry & Physics

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The use of NMR spectroscopy in solution to investigate the chemical structure of engineering poly(alkylene terephthalate)s such as poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT) is reviewed. Chemical defects present in the polyester chain, such as oxydialkylene units, as well as accompanying side products such as cyclic oligomers generated in the polycondensation, are well detected in 1H NMR spectra. The technique is also demonstrated to be effective for identifying, and even for quantifying in certain cases, the end groups of these polyterephthalates, including those that are generated in small amounts as a consequence of thermal degradation. The application of NMR to the study of the chemical microstructure of copolyesters derived from such polyterephthalates is also reviewed for its unique ability to determine comonomeric sequence lengths and degree of randomness (R). Copolyesters synthesized by either melt polycondensation or entropically driven ring opening polymerization, in addition to those prepared by solid‐state modification or melt blending, are the object of this review.

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Section: Copolyesters and Blendsmentioning

confidence: 99%

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Ilarduya

Muñoz‐Guerra

2014

Macro Chemistry & Physics

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“…This well-known technique is extensively employed in industry as an extension of the melt polycondensation to produce high molecular weight polyesters with improved properties suitable for wide range of applications (e.g., bottles, films, and fiber production). This competitive process to conventional melt polycondensation, involving heating of the starting partially crystalline polyester at a temperature between its glass transition temperature ( T g ) and its melting point ( T m ), is used mainly for PET manufacturing to get over its relatively low molecular weight [31,32,33,34,35,36,37,38].…”

Section: Introductionmentioning

confidence: 99%

Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, II: An Efficient and Facile Method to Synthesize High Molecular Weight Polyester Appropriate for Food Packaging Applications

et al. 2018

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Abstract:The goal of this study was to synthesize, through a facile strategy, high molecular weight poly(ethylene furanoate) (PEF), which could be applicable in food packaging applications. The efficient method to generate PEF with high molecular weight consists of carrying out a first solid-state polycondensation under vacuum for 6 h reaction time at 205 • C for the resulting polymer from two-step melt polycondensation process, which is catalyzed by tetrabutyl titanate (TBT). A remelting step was thereafter applied for 15 min at 250 • C for the obtained polyester. Thus, the PEF sample was ground into powder, and was then crystallized for 6 h at 170 • C. This polyester is then submitted to a second solid-state polycondensation (SSP) carried out at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 • C, under vacuum. Ultimately, a significant increase in intrinsic viscosity is observed with only 5 h reaction time at 205 • C during the second SSP being needed to obtain very high molecular weight PEF polymer greater than 1 dL/g, which sufficient for manufacturing purposes. Intrinsic viscosity (IV), carboxyl end-group content (-COOH), and thermal properties, via differential scanning calorimetry (DSC), were measured for all resultant polyesters. Thanks to the post-polymerization process, DSC results showed that the melting temperatures of the prepared PEF samples were steadily enhanced in an obvious way as a function of reaction time and temperature increase. It was revealed, as was expected for all SSP samples, that the intrinsic viscosity and the average molecular weight of PEF polyester increased with increasing SSP time and temperature, whereas the number of carboxyl end-group concentration was decreased. A simple kinetic model was also developed and used to predict the time evolution of polyesters IV, as well as the carboxyl and hydroxyl end-groups of PEF during the SSP.

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“…To obtain high molecular weight polyesters appropriate for several applications (e.g., bottles, films, and fiber production), an extensively-used method has been industrially applied as a third-step to polyesters, which is solid-state polymerization (SSP) performed under mild conditions. This alternative technique to the conventional melt polycondensation, involving heating the polyester in temperatures just lower from its melting point and higher than its glass transition temperature, was greatly exploited in PET [20,21,22,23,24,25,26,27] to overcome its low molecular weight.…”

Section: Introductionmentioning

confidence: 99%

Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase

et al. 2017

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Abstract:In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 • C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV), end groups (-COOH), and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.

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Phosphorus-Containing Poly(ethylene terephthalate): Solid-State Polymerization and Its Sequential Distribution

Cited by 23 publications

References 39 publications

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, II: An Efficient and Facile Method to Synthesize High Molecular Weight Polyester Appropriate for Food Packaging Applications

Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase

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