Morphology and Molecular Miscibility of Segmented Copoly(ether ester)s with Improved Elastic Properties As Studied by Solid State NMR

Gabriëlse, Wouter; Guldener, Viola Van; Schmalz, Holger; Abetz, Volker; Lange, Ronald F. M.

doi:10.1021/ma020029i

Cited by 12 publications

(11 citation statements)

References 17 publications

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“…These results will be presented elsewhere. 30 Mechanical Characterization. TEM and SFM investigations show that in the PEB containing copolyesters the hard phase is dispersed within a matrix of the soft phase.…”

Section: Resultsmentioning

confidence: 99%

Morphology, Surface Structure, and Elastic Properties of PBT-Based Copolyesters with PEO-b-PEB-b-PEO Triblock Copolymer Soft Segments

et al. 2002

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The elasticity of commonly known poly(butylene terephthalate)-poly(tetramethylene oxide) (PBT-PTMO)-based copoly(ether ester)s is increased by replacement of PTMO soft segments with poly-(ethylene oxide)-block-poly(ethylene-stat-butylene)-block-poly(ethylene oxide) (PEO-b-PEB-b-PEO) triblock copolymer soft segments containing a nonpolar middle block based on hydrogenated polybutadiene (PEB). The incorporation of this strongly incompatible PEB block resulted in the aimed increased phase separation between the PBT hard blocks and the soft segment phase, leading to a disperse PBT phase and hence to an increased elasticity. Dynamic shear experiments in combination with small-angle X-ray scattering revealed that crystallization of the PBT hard segments occurs from a microphase-separated melt. The resulting dispersed PBT hard phase in these materials is shown using transmission electron microscopy (TEM) and scanning force microscopy (SFM), whereas the increased elasticity is demonstrated using mechanical characterization. Hysteresis measurements reveal that the plastic deformation after recovery from 100% strain is only 1-6% (depending on composition) for the new PEB-containing copolyesters compared to 33% for a PBT-PTMO-based copoly(ether ester). The combination of results obtained with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) points toward a complex morphology for the PEB-containing copolyesters. Five different phases exist: a crystalline pure PBT phase, pure amorphous PEB, and PBT phases and a PEO-rich phase besides an amorphous mixed PEO/PBT phase.

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Section: Resultsmentioning

confidence: 99%

Morphology, Surface Structure, and Elastic Properties of PBT-Based Copolyesters with PEO-b-PEB-b-PEO Triblock Copolymer Soft Segments

et al. 2002

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“…Methylene oxide hydrogen (peak f at δ 3.85) and methylene hydrogen (peak e at δ 1.87) were compared to aromatic hydrogen (peak a at δ 8.21) to determine the percentage of ether segment in the final products. Methylene oxide hydrogen (peak d at δ 4.62) at polymer backbone and methylene oxide hydrogen (peak d * at δ 4.07) at an independent polyether were used to calculate ether segment contents in copolymers listed in Table . , In summary, the catalytic activity of the three catalysts for the synthesis of the PEEs with high-molecular weight and excellent comprehensive performance through the direct polycondensation of TPA, BDO, and PTMG ranks in an increasing order: …”

Section: Resultsmentioning

confidence: 99%

“…31,33 Worth mentioning is that the magnitude of maximum relaxation in the tan δ curve reflects the relative amount of amorphous materials in the copolymers. 26 As the hard segment content in the PEEs increased, its peak position shifted to higher temperature and the peak intensity decreased. The weak peaks at 100−160 °C on tan δ curves may be attributed to the relaxation and reorientation of the carboxyl groups in the amorphous phases.…”

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 96%

“…Methylene oxide hydrogen (peak d at δ 4.62) at polymer backbone and methylene oxide hydrogen (peak d* at δ 4.07) at an independent polyether were used to calculate ether segment contents in copolymers listed in Table 1. 26,27 In summary, the catalytic activity of the three catalysts for the synthesis of the PEEs with high-molecular weight and excellent comprehensive performance through the direct polycondensation of TPA, BDO, and PTMG ranks in an increasing order: Unreactive PTMG. Previous studies on the PEEs synthesized by transesterification among DMT, BDO, and PTMG demonstrated that less ether segments remained on the PEE backbone than feed ones.…”

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 99%

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Scalable Synthesis of Poly(ester-co-ether) Elastomers via Direct Catalytic Esterification of Terephthalic Acid with Highly Active Zr–Mg Catalyst

Song

Huang

et al. 2018

ACS Sustainable Chem. Eng.

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The poly(ester-co-ether)s (PEEs) comprising poly(butylene terephthalate) and poly(tetramethylene glycol) (PTMG) segments were cost-efficiently synthesized by direct esterification of terephthalic acid (TPA) and 1,4-butandiol (BDO)/PTMG with M n of 1000 in one feeding step by a unique nontoxic Zr−Mg catalyst that is designed and synthesized in our laboratory, avoiding undesirable eco-hazardous cocatalyst and byproducts that must be produced when terephthaloyl chloride (TPC) and dimethyl terephthalate (DMT) were chosen. The structure of the Zr− Mg catalyst and PEEs was systematically analyzed by high-resolution 1 H NMR, ATR-FTIR spectroscopies, and X-ray diffraction. The size-exclusion chromatography suggested that the weight-average molecular weight of the PEEs reaches up to 60 600 g/mol. In particular, the ether-segment retention, molecular weight, melt processability, and mechanical properties of the PEEs are significantly higher by Zr−Mg catalyst than by Ti−Mg and traditional tetrabutyl titanate (TBT) catalysts. DSC and DMA analyses revealed that the PEE copolymers obtained by the Zr− Mg catalyst have random segment distribution, glass transition temperature down to −34 °C, and good elasticity and strong toughness at ambient temperature. TBT is an efficient catalyst for the polycondensation between TPC/BDO or DMT/BDO prepolymers and PTMG for synthesizing excellent PEEs, unfortunately accompanying with the usage of toxic and expensive bases and the formation of hazardous HCl or methanol byproducts. This study confirmed that TBT is not powerful enough to achieve high-molecular-weight and thus tough PEEs via the environ-benign direct polycondensation among TPA, BDO, and PTMG anymore, while the Zr−Mg catalyst developed here is active enough to catalyze the direct polycondensation without compromise or toxic discharge. Furthermore, the TPA-based PEE elastomers demonstrate potential to replace current eco-unsafe elastomers like rubbers, polyurethane, polyolefin, and TPC-/DMT-based PEEs.

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“…This is attributed to strain‐induced crystallization of soft segments, which becomes more important with increasing PTMO content or its length. The literature shows that it is an irreversible process . As a matter of fact, the PTMO crystallites remain present even after the stress is released …”

Section: Resultsmentioning

confidence: 99%

Effects of co‐hard segments on the microstructure and properties thermoplastic poly(ether ester) elastomers

Hao

Zhang

et al. 2016

J of Applied Polymer Sci

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A thermoplastic poly(ether ester) elastomer (TPEE) is composed of polyester hard segments and polyether soft segments. Polyester and polyether segments are often homopolymer segments. This work aims at incorporating poly(butylene phthalate (PBP) as co-hard segments in the hard segments of poly(butylene terephthalate) (PBT)-b-poly(tetramethylene oxide) (PTMO) thermoplastic elastomer, and investigating structures and properties of the resulting materials, denoted as (PBT-co-PBP)-b-PTMO. (PBT-co-PBP)-b-PTMO was synthesized from dimethyl terephthalate (DMT), dimethyl phthalate (DMP), PTMO (M n 5 1000 g/mol), and 1,4-butanediol (BDO). The crystallinity of (PBT-co-PBP)-b-PTMO first decreased and then increased with increasing PBP content from 5% to 10% due to a decrease in the average sequence length of the PBT hard segments. Its elongation at break was increased by 200-350%. When the mass fractions of PBT and PBP were 42% and 8%, respectively, the (PBT-co-PBP)-b-PTMO showed the best performance in terms of permanent deformation, strength, and hardness whose values were 30%, 25 MPa, and 37 D, respectively. All the synthesized copolymers had good thermal stability with a decomposition temperature of 4008C or so. V C 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43337.

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Morphology and Molecular Miscibility of Segmented Copoly(ether ester)s with Improved Elastic Properties As Studied by Solid State NMR

Cited by 12 publications

References 17 publications

Morphology, Surface Structure, and Elastic Properties of PBT-Based Copolyesters with PEO-b-PEB-b-PEO Triblock Copolymer Soft Segments

Morphology, Surface Structure, and Elastic Properties of PBT-Based Copolyesters with PEO-b-PEB-b-PEO Triblock Copolymer Soft Segments

Scalable Synthesis of Poly(ester-co-ether) Elastomers via Direct Catalytic Esterification of Terephthalic Acid with Highly Active Zr–Mg Catalyst

Effects of co‐hard segments on the microstructure and properties thermoplastic poly(ether ester) elastomers

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