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MACROMOLECULES · 2023 · IF 5.5

Supertough and Biodegradable Poly(Lactic Acid) Blends with “Hard–Soft” Core–Shell Unsaturated Poly(ether-ester) through Self-Vulcanization

Rong Yang,Chaoyi Cai,Xiaochen Han,Zhifan Chen,Guozhang Gu,Chengpeng Zhang,Guoxiang Zou,Jinchun Li

The development of a biodegradable material with super toughness while preserving its biodegradability poses a significant challenge. In this study, a series of biodegradable unsaturated multiblock poly(ether-ester) poly(butylene succinate-co-fumarate)-poly(ethylene glycol) (PBSFG) was synthesized and blended with polylactic acid (PLA). The impact of fumaric acid in PBSFG on the mechanical and degradation behavior of PLA/PBSFG blends was investigated. The results revealed that fumaric acid facilitated self-vulcanization of PBSFG, thereby leading to the formation of a “hard–soft” core–shell rubber phase within PLA. The core comprised the poly(butylene succinate-co-fumarate) (PBSF) segment, while the shell consisted of the PEG chain segment. The notched impact strength and elongation at break of PLA/PBSF20G blends showed significant improvements compared with pure PLA, with values of 76.1 kJ/m2 and 303.1%, respectively. These values are 24 and 101 times higher than those of pure PLA. Furthermore, enzymatic degradation experiments were conducted on the PLA/PBSFG blends, which demonstrated that the fumaric acid content significantly accelerated the degradation rate. The degradation rate of PLA/PBSF30G even surpassed that of pure PLA. Ultimately, this work successfully yielded fully degradable and supertough PLA blends.

研究领域: 材料科学 · 生物医学工程
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Scientific Reports · 2021 ·Vol. 11 ·期 1 ·1-11 · IF 4.38

Synergistic interaction of renewable nipagin and eugenol for aromatic copoly(ether ester) materials with desired performance

Hu Keling,Sui Huachao,Zhao Dongping

Naturally occurring nipagin and eugenol were used as the collaborative starting materials for poly(ether ester) polymers. In this study, two series of nipagin and eugenol-derived copoly(ether ester)s, PHN1 1−x E1 x and PHN1 1−x E2 x (x = 0%, 5%, 10%, 15%, 20%), were prepared with renewable 1,6-hexanediol as a comonomer. The nipagin-derived component acts as the renewable surrogate of petroleum-based dimethyl terephthalate (DMT), while the eugenol-derived component acts as the cooperative property modifier of parent homopoly(ether ester) PHN1. 1,6-Hexanediol was chosen as the spacer because of its renewability, high boiling point, and short chain to enhance the glass transition temperatures ( T g s) of materials. The molecular weights and chemical structures were confirmed by gel permeation chromatograph (GPC), NMR and FTIR spectroscopies. Thermal and crystalline properties were studied by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC) and wide-angle X-ray diffraction (WXRD). The tensile assays were conducted to evaluate the mechanical properties. The results suggested that properties of this kind of poly(ether ester)s could be finely tuned by the relative content of two components for the desired applications (elastomer, rubbery) suitable for different scenarios from polyethylene glycol terephthalate (PET) and polybutylene terephthalate (PBT).

研究领域: 材料科学 · 有机化学
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Materials Science & Engineering C-Materials for Biological Applications · 2016 · IF 3.42

Synthesis and characterization of biodegradable poly(ether-ester) urethane acrylates for controlled drug release

Xuepeng Feng,Guirong Wang,Kevin Neumann,Wei Yao,Lin Ding,Songyan Li,Yang Sheng,Yan Jiang,Mark Bradley,Rong Zhang

Three polyether-ester triblock diols, with various molecular weights, were synthesized from ε-caprolactone and polyethylene glycol and used, with diisocyanates, as soft segments for the preparation of polyurethane acrylate oligomers. The polyurethane acrylates were used to generate cross-linked polyurethane films via UV initiated polymerization with and without cargo incorporation. Degradation experiment indicated that in PBS/H 2 O 2 /CoCl 2 the films degraded rapidly compared to PBS alone or with lipase. The polyurethane membrane loaded with the antibiotic tetracycline, demonstrated prolonged release over 200   h, suggesting that the polymers could be used as an implant coating for controlled drug release.

研究领域: 材料科学 · 药学 · 生物医学工程
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POLYMER · 2022 · IF 4.432

Effect of oligo(ethylene glycol) length on properties of poly(oligoethylene glycol terephthalate)s and their cyclic oligomers

Jie Huan,Jing Li,Yinjia Lan,Sheng Wang,Xiaohong Li,Xiaoming Yang,Huanjun Lu,Yingfeng Tu

We present here the effect of oligo(ethylene glycol) (OEG) segmental length on properties of cyclic oligo(oligoethylene glycol terephthalate)s (COEGTs) and their corresponding polymer counterparts, poly(oligoethylene glycol terephthalate)s (POEGTs). COEGT monomers were synthesized from terephthaloyl chloride with corresponding diethylene glycol , triethylene glycol , and tetraethylene glycol under pseudo-high-dilution conditions. As those large ring cyclic monomers are hard to be polymerized via traditional ring-opening polymerization, a cascade polycondensation-coupling ring-opening polymerization method is utilized to obtain high molecular weight POEGTs. The cascade polymerization mechanism is confirmed by the kinetics study . The structures of COEGTs and POEGTs were well characterized and their properties were studied to reveal the structure-property relationship. With the increment of OEG length in repeating units, the chain flexibility of POEGT and COEGTs is enhanced. As a result, the melting temperatures of COEGTs and glass transition temperatures of POEGTs decrease. On the other hand, the thermal degradation temperature of POEGTs and COEGTs increases due to the enhanced ether fraction and reduced ring strain. Solid-state polymer electrolytes based on POEGTs was prepared by blending with lithium bis(trifluoromethanesulfonyl)imide. The measured ionic conductivity increased with the OEG length in POEGT repeating units. Our results revealed the effect of OEG length on the structure-property relationship in cyclic oligo(ether ester)s and copoly(ether ester)s, providing a facile way to tune their properties.

研究领域: 高分子化学 · 材料科学
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JOURNAL OF BIOMATERIALS SCIENCE-POLYMER EDITION · 2017 · IF 1.9

Preparation and properties of biomedical segmented polyurethanes based on poly(ether ester) and uniform-size diurethane diisocyanates

Shengnan Yin,Yiran Xia,Qi Jia,Zhao-Sheng Hou,Na Zhang

This study describes the preparation and properties of a novel aliphatic cost-effective segmented polyurethanes (SPUs) based on poly(ether ester) (poly-(ε-caprolactone-co-l-lactide)-poly(ethylene glycol)-poly-(ε-caprolactone-co-l-lactide), PECLA) and uniform-size diurethane diisocyanates (HDI-BDO-HDI). PECLA was synthesized via bulk ring-opening polymerization with poly(ethylene glycol) (PEG) as an initiator and ε-caprolactone, l-lactide as monomers. By chain extension of PECLA diol with HDI-BDO-HDI, three SPUs with different hydrophilic segments content and hard segments content were obtained. The chemical structures of the chain extender, PECLA and SPUs were confirmed by 1H NMR, 13C NMR, FT-IR, HR-TOF-MS and GPC. The influences of PEG content and uniform-size hard segments on in vitro degradability and mechanical properties of SPU films were researched. Similar thermostability observed in TGA curves of SPU films indicated that the hard segments and PEG content had little influence on the thermostability. The formation of microsphase-separated morphologies, which were demonstrated by the results of DSC and XRD, and physical-linking (H-bonds) network structures led to better mechanical properties of SPU films (ultimate stress: 23.1–17.9 MPa; elongation at break: 840–1130%). The results of water absorption and water contact angle showed that the bulk and surface hydrophilicity were closely related with the hydrophilic PEG content in SPU backbone. And the water absorption being less than 10 wt% indicated that the SPU films had low swelling property. In vitro hydrolytic degradation studies showed that the time of the SPU films becoming fragments was 34–19 days and the degradation rate increased with the increasing content of hydrophilic segments in SPUs, indicating that the degradation rate of SPU films could be controlled by adjusting PEG content. Cytotoxicity test of film extracts were conducted using L929 cells, and the relative growth rate exceeded 90% after incubation for 24, 48 and 72 h, showing excellent cytocompatibility. The acceptable mechanical properties, controllable biodegradability and excellent cytocompatibility of the polyurethanes can make them good candidates for further biomedical applications.

研究领域: 生物医学材料 · 高分子化学 · 材料科学
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JOURNAL OF POLYMER RESEARCH · 2018 ·Vol. 25 ·期 10 ·1-11 · IF 1.434

Preparation, physicochemical properties and biocompatibility of biodegradable poly(ether-ester-urethane) and chitosan oligosaccharide composites

Zhang Na,Yin Sheng-nan,Hou Zhao-sheng,Xu Wei-wei,Zhang Jun,Xiao Ming-hui,Zhang Qi-kun

In the paper, novel composites of biodegradable poly(ether-ester-urethane) (PEEU) and water-soluble chitosan oligosaccharide (CHO) were prepared using a simple physical mixing method and their potential application as biomaterials was assessed. The PEEU and CHO were dissolved in N,N -dimethylformamide to get a homogenous solution, then the composite films were obtained by the solvent evaporation method. The composites were characterized by FT-IR, and the influence of CHO content on the physicochemical properties of the composite films, including thermal properties, surface morphologies, mechanical properties, surface and bulk hydrophilicity, and in vitro biodegradability, were researched. The thermal stability studies indicated that the composite films had lower initial decomposition temperature and higher maximum decomposition temperature than PEEU film. Only one broad endothermic peak found in DSC curves demonstrated the high compatibility of CHO with PEEU. The ultimate stress and elongation at break of composite films decreased with the increment of CHO content, and the CHO content in the composites should be controlled no more than 25  wt % in order to maintain the mechanical properties (ultimate stress: 18.5 MPa; elongation at break: 890%) to meet the requirement of implant materials. The surface morphologies of composite films were observed by cold field emission scanning electron microscope (FE-SEM), and the results indicated that the homogeneous-dispersed composites could be obtained with CHO content being less than 20  wt %. The results of water contact angle and water absorption showed that the surface and bulk hydrophilicity were closely related with the water-solubility of CHO component. In vitro degradation studies showed that the degradation rate increased with the increasing content of CHO in composites, indicating that the degradation rate of composite films could be controlled by adjusting CHO content. The surface blood compatibility of the composite films was examined by bovine serum albumin adsorption and platelet adhesion tests. It was found that composite films had improved resistance to protein adsorption and possessed excellent resistance to platelet adhesion.

CAS / MDL: 110-63-4 68-12-2
研究领域: 生物材料学 · 高分子化学 · 生物医学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Resin transfer in oil-water interface intensified by H2O2 and demulsifier for efficient water separation in tight oil

Yuxuan Tian,Yaming Qi,Hongjing Han,Xinzhan Luo,Junyao Guan,Sijia Chen,Haiying Wang,Yanguang Chen,Xuzhong Gong

Tight oil is an important unconventional oil resource, but it is difficult to separate oil and water from produced liquid and make efficient use of it. Due to the stable structure of oil–water interface caused by resin, it is difficult to achieve demulsification. In this work, a series of polyether ester demulsifierswith different degree of polymerization were designed by esterification and polymerization. In addition, hydrogen peroxide was used to regulate the structure of resin to enhance the transmission of polyether ester, and the replacement of resin was strengthened through the structural design of polyether ester. The results showed that the molecular weight and dipole moment of resin oxidized by hydrogen peroxide decreased, which was beneficial to the transfer of demulsifier. With the increase of polymerization degree, the oil solubility and surface activity of polyether ester were improved, and the replacement ability of resin was strengthened·H 2 O 2 and demulsifier were used to synergistically promote demulsification, the dehydration rate could be further increased to 99.2%, and the water content in tight oil could be reduced to 0.56%.

研究领域: 化学工程 · 石油工程
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POLYMER SCIENCE SERIES B · 2015 ·Vol. 57 ·期 4 ·313-321 · IF 0.577

Synthesis and characterizations of branched poly(butylene isophthalate)-co-poly(tetramethylene glycol)-co-poly(ethylene glycol) fibers with excellent low temperature elastic recovery

Huang Xia,Guo Ronghui,Lan Jianwu

To improve the low temperature elastic recovery and tensile properties of the traditional poly(ether-ester), a series of randomly branched poly(ether-ester)s consisting of poly(butylene isophthalate) as hard segment, poly(tetramethylene glycol) and poly(ethylene glycol) as mixed soft segment, and trimethylolpropane as trifunctional monomer were synthesized. The structure and composition of the samples were characterized by 1 H NMR and FTIR-spectroscopy. The tensile strength, elongation at break and the low temperature elastic recovery were used to characterize the mechanical properties of the synthetic polymers. The results indicate that the branched poly(ether-ester) showed an increment of mechanical and thermal properties with the increasing content of branching agent in the polymer matrix. Moreover, the low temperature elastic recovery and tensile properties of branched poly(ether-ester) were superior comparing to the traditional poly(ether-ester)s.

研究领域: 材料科学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

Synthesis and characterization of polyurethane with poly(ether-ester) diols soft segments consisted by ether and ester linkages in one repeating unit

Jinbao Xu,Wenhao Xiao,Siheng Zhang,Zhixian Dong,Caihong Lei

Development of controllable, versatile and robust degradable polyurethane (PU) is of continued attraction regarding its wide application in the field of biology and medicine. Herein, new degradable poly(ether-ester-urethane) (PEEU) with amorphous and hydrophilic poly(1,5-dioxepan-2-one) (PDXO) diols as the soft segments and 4,4-diphenylmethane diisocyanate (MDI) and butane-1,4-diols (BDO) as the hard segments was synthesized by the one-shot two -step method in a controllable manner. The degradation behavior of PEEU with various compositions in vitro was investigated by observing the changes of weight loss, molecular weight and surface morphology during the 140 days of degradation. The weight loss and degradation rate of PEEU were faster than that of PU with semi-crystallized poly( ε -caprolactone) diols as soft segments and a surface to bulk degradation process was observed by scanning electron microscopy (SEM). In addition, the weight loss decreased by increasing the hard segments composition and the weight loss was mainly from the hydrolysis of ester linkages.

研究领域: 生物材料学 · 医学材料
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CHINESE JOURNAL OF POLYMER SCIENCE · 2019 ·Vol. 37 ·期 11 ·1152-1161 · IF 2.804

Polyether-polyester and HMDI Based Polyurethanes: Effect of PLLA Content on Structure and Property

Shi Lei,Zhang Ruo-Yu,Ying Wu-Bin,Hu Han,Wang Yu-Bin,Guo Ya-Qian,Wang Wen-Qin,Tang Zhao-Bin,Zhu Jin

Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols), polytetrahydrofuran diol (PTMG diols), 4,4′-dicyclohexylmethane diisocyanate (HMDI), and 1,4-butanediol (BDO) by a two-step reaction, and the morphology and property of the resultant TPU could be adjusted by varying the PLLA contents. The soft segment was composed of PLLA and PTMG diols. By controlling the percentage of PLLA in the soft segment, the glass transition temperature and mechanical properties of the polyurethanes could be regulated. Based on the FTIR spectrum, we found that two kinds of hydrogen bonding existed individually in soft matrix and hard domain. The hydrogen bonding in soft matrix was unstable, which could be destroyed during elongation. With in situ stretching WAXS and SAXS experiments, we found that the PLLA crystal was destroyed and the PLLA domain oriented along the stretch direction. Finally, we proposed a schematic model to illustrate the microstructures of these elastomers before and after stretch.

CAS / MDL: 110-63-4 25190-06-1
研究领域: 材料科学 · 高分子化学
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Journal of Coatings Technology and Research · 2015 ·Vol. 12 ·期 3 ·525-532 · IF 1.298

Synthesis and characterization of degradable polyurethane based on poly(ether ester) polyols (PPG-2000 and ε-caprolactone/lactic acid) for marine antifouling

Yi Jie,Ren Runtao,Huang Congshu,Zhang Chuyi,Ma Yupu

Poly(ether ester) polyols consisting of polypropylene glycol-2000 (PPG-2000) and different ratios of ε-caprolactone and lactic acid (LA) had been prepared by polycondensation reactions. Degradable polyurethane (PU) films were prepared with poly (ether ester) polyols and hexamethylene diisocyanate trimer. Hydrolytic degradation experiments demonstrated that PU films could be degradable in artificial seawater. Importantly, the hydrolytic degradation of PU films in artificial seawater increased with the increase of LA content. The results also showed that the surfaces of PU films were renewed and kept active, as revealed by the scanning electron microscope micrographs of degradation PU coatings. Moreover, the copper ion release rates of PU coatings prepared with poly(ether ester) polyols reached steady state at about 35 days. The degradable polyurethanes based on poly(ether ester) polyols (PPG-2000, ε-caprolactone, and LA) could be effective and durable resins for marine antifouling.

研究领域: 材料科学 · 海洋生物学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Bio-based thermoplastic poly(ether-ester) elastomers from 2,5-thiophenedicarboxylic acid with high stiffness and elasticity

Tao Yang,Jiyang Zuo,Fei Liu,Caiqi Liu,Caohong Chen,Xiaoqin Jiang,Kangpeng Liu,Siqi Yu,Jinggang Wang,Jin Zhu

Thermoplastic elastomers (TPE), as a class of essential materials, play an important role in manufacturing, engineering, medical and military fields due to their excellent properties. However, the elastomers often underperform and suffer from the familiar trade-off between stiffness and high elasticity. In this study, thiophenedicarboxylic acid (TDCA), a class of potential bio-based aromatic monomers was used for the design and synthesis of high performance TPE. Poly(propylene thiophenedicarboxylate) (PPThF) possessing a surprising crystallization ability was proposed to use as an ideal hard segment, and a series of poly(ether-ester) copolymers were designed. Results showed that the well-defined reprocessable poly(ether-ester) elastomers demonstrated impressive ultra-high elastic modulus (>120 MPa), elasticity ( η r (1) = 55 %, and by adjusting the sequence structure, η r (1) can be further improved to as high as 73 %) and melting temperature ( T m  = 164 °C). Plus, the TDCA-based TPEEs showed excellent biocompatibility and bacteriostatic effect. This innovative work not only provides an alternative choice for the fabrication of high performance bio-based TPE, but also resolves the irreconcilable contradiction between stiffness and elasticity.

研究领域: 材料科学 · 生物医学工程
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