Phase separation in poly(butylene terephthalate)-based materials prepared by solid-state modification

Gubbels, Erik; Jasińska-Walc, Lidia; Hermida‐Merino, Daniel; Noordover, Bart A. J.; Spoelstra, Anne B.; Goossens, Jgp Han; Koning, Cor E.

doi:10.1016/j.polymer.2014.05.051

Cited by 12 publications

(17 citation statements)

References 41 publications

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“…[53] Subsequently, this diol is incorporated into the PBT backbone via solid-state (co)polymerization to form a linear copolyester in line with earlier work from our group on PBT modification in the solid state. [54][55][56][57][58][59][60] The linear polymer chain is then transformed into a network via deprotection of the benzal group to afford a linear polymer chain with pendent-free hydroxyl groups for further thermal transesterification of the linear copolyester catalyzed by the Zn(II) catalyst. If deprotection and subsequent cross-linking takes place during processing, we can combine an initial low viscosity with final vitrimer characteristics.Normally, the deprotection step to obtain the linear copolyester with pendent hydroxyl groups, as shown in Scheme 1, involves an acid-promoted deprotection of the benzal group at room temperature and an acid used often is trifluoroacetic acid (TFA).…”

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confidence: 99%

In Situ Network Formation in PBT Vitrimers via Processing‐Induced Deprotection Chemistry

Zhou

Goossens

Bergen

et al. 2018

Macromol. Rapid Commun.

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in the solid state. [38,45] In general, the terminal relaxation behavior of PBT vitrimers above the melting temperature was rarely observed at angular frequencies down to 10 −2 s −1 in the temperature range from 250 to 270 °C. [37,38,45] Considering that typical shear rates during injection molding are as high as 10 000 s −1 and the viscosity of PBT vitrimers can be up to 10 7 Pa s at 250 °C, these PBT vitrimers cannot be processed like neat PBT during the short residence times typical for extrusion and injection molding. [52] Here, we propose a controllable way to process PBT vitrimers (based on transesterification exchange reactions) via controlling the network formation with the help of protection-deprotection chemistry. In this way, we can overcome the relatively long relaxation times and high viscosities associated with PBT vitrimers and maintain the high production rates of final parts by injection molding as for neat PBT. The strategy is schematically shown in Scheme 1: pentaerythritol is first converted into 5,5-bis(hydroxymethyl)-2-phenyl-1,3-dioxane (BPO, melting point 135-137 °C) via benzaldehyde protection chemistry. [53] Subsequently, this diol is incorporated into the PBT backbone via solid-state (co)polymerization to form a linear copolyester in line with earlier work from our group on PBT modification in the solid state. [54][55][56][57][58][59][60] The linear polymer chain is then transformed into a network via deprotection of the benzal group to afford a linear polymer chain with pendent-free hydroxyl groups for further thermal transesterification of the linear copolyester catalyzed by the Zn(II) catalyst. If deprotection and subsequent cross-linking takes place during processing, we can combine an initial low viscosity with final vitrimer characteristics.Normally, the deprotection step to obtain the linear copolyester with pendent hydroxyl groups, as shown in Scheme 1, involves an acid-promoted deprotection of the benzal group at room temperature and an acid used often is trifluoroacetic acid (TFA). [53] Accidentally we discovered that compression molding of the linear copolyester with benzal protection groups resulted in a cross-linked material with vitrimer characteristics, even without deprotection with TFA. This observation is in contrast to results previously reported by Collard et al., [53] who obtained thermoset materials after incorporation of BPO into PBT and poly(ethylene terephthalate) (PET) and repeated subsequent cycling to 300 °C in differential scanning calorimetry (DSC). Driven by this intriguing result and its practical relevance, we investigated the in situ network formation in more Vitrimers Although the network dynamics and mechanical properties of poly(butylene terephthalate) vitrimers can to some extent be controlled via chemical and physical approaches, it remains a challenge to be able to process PBT vitrimers with the same processing conditions via, for example, injection molding as neat PBT. Here, it is shown that the use of protected pentaerythritol as a latent cross...

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confidence: 99%

In Situ Network Formation in PBT Vitrimers via Processing‐Induced Deprotection Chemistry

Zhou

Goossens

Bergen

et al. 2018

Macromol. Rapid Commun.

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“…On one hand, the presence of the characteristic signals of isosorbide from 74, 81, 87, and 92 ppm proves the incorporation of the diol. The ester functions appear at 165 ppm . On the other hand, the five signals detected at 125, 129, 132, 143, and 148 ppm may be interpreted as a result of the a, b, c, d, and e carbon types as presented in Figure , due to the endo and exo positions of isosorbide hydroxyl group.…”

Section: Resultsmentioning

confidence: 94%

“…The ester functions appear at 165 ppm. [ 27 ] On the other hand, the fi ve signals detected at 125, 129, 132, 143, and 148 ppm may be interpreted as a result of the a, b, c, d, and e carbon types as presented in Figure 5 , due to the endo and exo positions of isosorbide hydroxyl group. The resulting three stereoisomers may explain the splitting of the signals as observed.…”

Section: Nmr Studymentioning

confidence: 99%

Biosourced Cyclic and Multicyclic Polyesters Based on 1,4:3,6-Dianhydrohexitols: Application to Metal Ions Uptake in Aqueous Media

Bennour¹,

Fildier

Chatti

et al. 2015

Macromol. Chem. Phys.

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Authors want to thank all INRAP staff for analysis and helpful discussion. M. Mezni is acknowledged for NMR experiments, R. Jebali and N. Chaabane for ICP analysis.International audienceIsosorbide and isomannide are polycondensed in solution with trimesoyl chloride at a concentration of 0.06 mol L-1 for the synthesis of cyclic and multicyclic polyesters. The feed ratio diol/trimesoyl chloride is varied from 1.0/1.0 to 1.6/1.0. As all obtained polyesters prove insoluble, innovative solvent-free matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI ToF MS) is performed for their characterization. The influence of the stereochemistry is shown to be of great importance for the cyclization trend. Both isosorbide and isomannide lead mainly to cyclic and multicyclic structures at a feed ratio of 1.0/1.0 and 1.1/1.0. Isomannide gives higher fractions of multicyclic structures. The products are characterized by complementary techniques such as C-13 cross polarization magic angle spinning nuclear magnetic resonance (C-13 CP-MAS NMR) and differential scanning calorimetry measurements. Application as a cryptands for the uptake of metal ions in aqueous media is followed by inductively coupled plasma atomic emission spectroscopy (ICP AES) analysis and reveal efficient toward large range of metals with tunable selectivity depending on the starting diol

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“…In comparison, the melting point of compound can be reduced before curing and polyimides exhibit excellent thermal stability after cured by the addition of reactive diluents. Moreover, many efforts have been paid to develop new materials with desirable performance by blending various polymers . Rao et al synthesized a star‐shaped, phenylethynyl‐terminated aryl ether compound (Tri‐PE‐PAEK) and used as a reactive diluent for phenylethynyl‐terminated imide oligomer PETI‐5 which has the molecular weight of 5000 g/mol .…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, many efforts have been paid to develop new materials with desirable performance by blending various polymers. [24][25][26][27] Rao et al synthesized a starshaped, phenylethynyl-terminated aryl ether compound (Tri-PE-PAEK) and used as a reactive diluent for phenylethynylterminated imide oligomer PETI-5 which has the molecular weight of 5000 g/mol. [28] Tri-PE-PAEK as a modifier not only reduces the viscosity of PETI-5 and the temperature of the minimum viscosity but also increases the tensile properties of cured polymer without sacrificing thermal stability.…”

Section: Introductionmentioning

confidence: 99%

Development of novel cardo-containing phenylethynyl-terminated polyimide with high thermal properties

Wang

et al. 2016

Polym. Adv. Technol.

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A phenylethynyl‐terminated reactive diluent [Card‐4‐phenylethynylphthalic anhydride (PEPA)], which contained fluorenyl cardo structures, was successfully synthesized and used as a modifier for flexible phenylethynyl‐terminated imide oligomer (PEI‐PEPA). The chemical structure, crosslink characterization, molecular weights, and thermal properties of the products were characterized. The imide systems with addition of 10, 20, 30, and 40 wt% Card‐PEPA to PEI‐PEPA (PEI‐PEPA‐Card) and their cured resin systems were prepared. The thermal curing behaviors of imide systems at different heating rates were analyzed by using differential scanning calorimetry. Thermal properties such as glass transition temperature (Tg) and char yield at 800°C of the resultant resin systems were studied by differential scanning calorimetry, dynamic mechanical analysis, and thermogravimetric analysis. The rheological properties were also investigated using a dynamic rheometry. These properties were found to be outstanding compared with pure PEI‐PEPA. The uncured imide systems exhibited lower Tg and lower isothermal viscosity with addition of Card‐PEPA. Furthermore, the Tg and char yield of the cured resin systems increased with addition of Card‐PEPA. The cured resin systems containing 40 wt% Card‐PEPA exhibited the highest Tg of 359°C and char yield at 800°C of 66.5%. Copyright © 2016 John Wiley & Sons, Ltd.

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Phase separation in poly(butylene terephthalate)-based materials prepared by solid-state modification

Cited by 12 publications

References 41 publications

In Situ Network Formation in PBT Vitrimers via Processing‐Induced Deprotection Chemistry

In Situ Network Formation in PBT Vitrimers via Processing‐Induced Deprotection Chemistry

Biosourced Cyclic and Multicyclic Polyesters Based on 1,4:3,6-Dianhydrohexitols: Application to Metal Ions Uptake in Aqueous Media

Development of novel cardo-containing phenylethynyl-terminated polyimide with high thermal properties

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