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POLYMER DEGRADATION AND STABILITY · 2022 · IF 5.204

Super-tough and flame-retardant poly(lactic acid) materials using a phosphorus-containing malic acid-based copolyester by reactive blending

Rong Yang,Guozhang Gu,Chen Tang,Zhicheng Miao,Hongwei Cao,Guoxiang Zou,Jinchun Li

It is a great challenge to simultaneously prepare flame-retardant and super-tough poly(lactic acid) (PLA) materials. Herein, we reported a facile approach that PLA reactively blends with phosphorus-containing copolyester. In this paper, a quinary aliphatic copolyester (PPE) containing phosphorus and pendent hydroxyl group was synthesized with sebacic acid, dimethyl malate, diethyl phosphite, 1,6-hexanediol, and 1,3-propanediol by polycondensation. Then, flame-retardant and super-tough PLA materials (PLA/PPEU) can be achieved by reactively blending with PPE and hexamethylene diisocyanate. The results showed that the toughness of PLA was significantly enhanced. The maximum notched impact strength is 75.3 kJ/m 2 indicated a super toughness performance. Meanwhile, the flame retardance of the PLA was improved obviously. The limited oxygen index (LOI) of PLA increased from 20 to 26%. Moreover, the PLA blends can pass the UL-94 V-0 rating. In addition, both the total heat release and total smoke production of PLA were decreased. The resultant super-tough and flame-retardant PLA materials could be widely applied in electrical and electronic equipment.

研究领域: 材料科学 · 聚合物化学
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ACS Applied Polymer Materials · 2024 · IF 4.4

Strong and Reusable Biobased Multiblock Copolyester Adhesives

Hongsheng Wang,Shishuai Gao,Yitong Xie,Xiaoyu Shi,Chenhuan Lai,Daihui Zhang,Chunpeng Wang,Fuxiang Chu

The development of sustainable and recyclable adhesives simultaneously requiring high strength and ductility is challengeable. Herein, we synthesized furan ring-containing copolyesters as sustainable, strong, and tough adhesives. FTIR and 1H NMR analyses confirmed the successful synthesis of copolyesters. Furthermore, structures and physiochemical properties of copolyesters were easily tunable by varying the feeding ratio of comonomers. The obtained copolyesters exhibited several interesting features as adhesives, which synergistically resulted in superior adhesion behavior, including high adhesion strength (12.60 MPa), satisfactory toughness (work of debonding = 2623 N m–1), wide temperature adaptability (adhesion strength = 8.23 MPa at −70 °C and 3.83 MPa at 100 °C), and excellent solvent resistance (9.27 MPa of adhesion strength in N,N-dimethylformamide after 24 h). The present work significantly advances and provides perspectives on the design of strong and tough sustainable adhesives.

CAS / MDL: 25190-06-1
研究领域: 材料科学 · 绿色化学
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2022 ·Vol. 33 ·期 7 ·2265-2275 · IF 3.348

Synthesis of bio-based polyesters with crystallization properties comparable to poly(butylene terephthalate)

Xuan Fei,Yingkang Zhu,Jinggang Wang,Zhen Jia,Xiaoqing Liu

To enhance the crystallization of poly(butylene 2,5-furandicarboxylate) (PBF) thus substitute its petroleum-based analogue poly(butylene terephthalate) (PBT), a series of high molecular weight poly(butylene-co-1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PBCF) copolyesters with low contents (0–19 mol%) of 1,4-butanediol (BDO) are synthesized from 2,5-furandicarboxylic acid (FDCA), 1,4-cyclohexanedimethylene (CHDM) and BDO. Their chemical structures and compositions are confirmed by nuclear magnetic resonance ( 1 H NMR and 13 C NMR). Their number average molecular weights are from 20,500 to 36,100 g/mol with the polydispersity index ( Ð ) of 1.67–1.99. The thermal stability and crystallization behaviors are investigated by thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC). Results show that PBCFs demonstrate comparable crystallization rate to PBT as the crystallization half time is from 18 to 29 s and the melting enthalpy is 34.1–41.4 J/g as well as the higher melting temperature of 238–263°C than 225°C for PBT. In addition, PBCFs exhibit excellent mechanical properties of tensile modulus between 1220 and 1510 MPa. These investigations suggest that a moderate amount CF unit can improve the melting temperature and enhance the originally weak crystallizability of furan-based polyesters. Generally, PBCFs can be the engineering plastic with satisfied thermal and mechanical performance.

研究领域: 材料科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Semi-aromatic copolyesters with high strength and fire safety via hydrogen bonds and π-π stacking

Yan-Peng Ni,Qi-Tian Li,Lin Chen,Wan-Shou Wu,Zi-Hao Qin,Yi Zhang,Li Chen,Xiu-Li Wang,Yu-Zhong Wang

Currently, it is still a huge challenge to prepare flame-retardant polymeric materials with excellent fire safety, high strength, good durability and processability. We here propose a H-bonding cross-linking strategy that can simultaneously endow polymers with excellent flame retardancy, non-dripping behavior and enhanced strength. In this work, a novel benzimidazole monomer, 2-(4-methoxycarbonyl-phenyl)-1H-benzimidazole-5-carboxylic acid methyl ester (PBM) has been designed as a H-bonding cross-linking monomer to prepare poly(ethylene terephthalate)-based copolyesters (PET- co -PBMs). Interestingly, along with the hydrogen bonding, the π-π stacking interactions from the benzimidazole groups also exist. Due to the formation of physical crosslinking network via hydrogen bonding and π-π stacking, the melt strength of copolyesters are greatly improved. Combining with char forming ability of benzimidazole, PET- co -PBMs display excellent fire safety. Moreover, PET- co -PBMs also exhibit higher glass transition temperature, higher mechanical strength and good processability. This work provides a promising strategy to design polymers with high strength, good processability, excellent flame retardance and anti-dripping performance.

研究领域: 材料科学 · 高分子化学
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E-POLYMERS · 2021 ·Vol. 21 ·期 1 ·336-345 · IF 2.025

Biodegradable thermoplastic copolyester elastomers: Methyl branched PBAmT

Wen-Bo Neng,Wen-Guang Xie,Bo Lu,Zhi-Chao Zhen,Jun-Long Zhao,Ge-Xia Wang,Jun-Hui Ji

A series of novel biodegradable copolyesters named poly(butylene 3-methyl adipate co -terephthalate) (PBA m T) were synthesized from the monomers of 3-methyl adipic acid (AA m ), 1,4-butanediol (BDO), and terephthalic acid (TPA) through a process of esterification and polycondensation. 1 H NMR analysis shows that they are random copolymers whose composition can be well controlled by the feed ratio of monomers. From the results of DSC and XRD, the introduction of methyl group successfully destroys the crystallizability of the PBA m chains, thus making it become a relative soft segment compared to PBA, while these random PBA m T copolymers constructed by soft segment PBA m and rigid segment PBT change from semi-crystalline polymers to nearly amorphous polymers as the feed ratio of A m increases. Especially, mechanical tests reveal that the copolymers show outstanding elasticity and rebound resilience with excellent strength. These thermoplastic copolyester elastomers with good performance by simply introduction of branched methyl group on polybutylene adipate terephthalate (PBAT) copolymer chains may well explore the potential application of biodegradable PBAT-based material. Graphical abstract Methyl branched PBA m T possesses excellent elasticity and shows certain degradation performance.

研究领域: 材料科学 · 高分子化学
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POLYMER · 2016 · IF 3.586

Modification of poly(ethylene 2,5-furandicarboxylate) with 1,4-cyclohexanedimethylene: Influence of composition on mechanical and barrier properties

Jinggang Wang,Xiaoqing Liu,Yajie Zhang,Fei Liu,Jin Zhu

A series of poly(ethylene- co -1,4-cyclohexanedimethylene 2,5-furandicarboxylate)s (PECFs) with different compositions were synthesized from 2,5-Furandicarboxylic acid (FDCA), 1,4-cyclohexanedimethylene (CHDM) and ethylene glycol (EG). Their chemical structures , composition and sequence distribution were determined by FT-IR, 1 H NMR and 13 C NMR. The composition of the resulted polyesters could be controlled by the feed mole ratio of CHDM to dimethyl furan-2,5-dicarboxylate (DMFD). And for all the copolyesters, the degree of randomness (R) was close to 1, indicating their randomness. Their thermal and mechanical properties were investigated by Differential Scanning Calorimeter (DSC) and tensile testing , results showed that the crystallizability, tensile modulus and strength of PECFs were decreased with the increasing content of CHDM at first (0–59%), and with the introduction of more CHDM (76–100%) units, they were increased accordingly. However the elongation at break was changed contrarily. The barrier properties study demonstrated that although the O 2 and CO 2 permeability of PEF was increased by the introduction of CHDM, PECF-32 and PECF-76 still showed excellent barrier properties, which were better or comparable to those of PEN and PEI.

研究领域: 材料科学 · 高分子化学
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MACROMOLECULES · 2025 · IF 5.2

Disulfide-Driven On-Demand Degradation of the PBAT Copolymer: Stable Comprehensive Performance, Long-Term Storage, and Redox-Induced Degradation

Chen Lin,Han Hu,Hanxu Zhu,Qingyang Luan,Zhenzhong Li,Jinggang Wang,Jin Zhu

Common biodegradable polyesters are degraded under favorable conditions, such as industrial compost. Poly(butylene adipate-co-terephthalate) (PBAT) is one of the most prospective and prevalent biodegradable polymer, while its degradation in natural environment is slow. Herein, we introduce a stimulus group with disulfide bonds to obtain a poly(butylene adipate-co-dithiodipropionate-co-terephthalate) (PBADiT) copolyester. Their melting temperature is higher than 120 °C and the thermal stability is sufficient for melt processing. They show high modulus (>110 MPa) and high toughness when ≤30% of disulfide bonds are introduced. BDi (butylene dithiodipropionate) units show slightly lower hydrolysis and enzymatic degradation ability, and PBADiT copolymers show acceptable storage stability in a damp environment. The redox response of PBADiT helps realize on-demand degradation after use. From 0.01 to 1 mol/L H2O2 solutions, the hydrolysis of PBADiT can be regulated or accelerated by 15 days of fast hydrolysis with weight loss exceeding 40%. Reductive conditions, represented by 0.2 mol/L dithiothreitol (DTT) solutions, are also an efficient stimulus source for achieving rapid breakage of PBADiT. Hence, PBADiT copolymers provide a new approach for sustainable and degradable materials with required usage time and impart the polymer with accelerated degradation in redox environments.

研究领域: 材料科学 · 环境科学 · 生物化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 ·Vol. 142 ·期 17 ·e56781 · IF 2.8

High Glass Transition PEcBT and PEPecBT Copolyesters Synthesized by Direct Esterification Route

Yanru Chen,Linbo Wu

2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) based copolyesters like poly(cyclohexane dimethylene-co-2,2,4,4-tetramethyl cyclobutylene terephthalate) (PCcBT) has high transparency, heat-resistance and safety and has been commercialized to replace bisphenol A polycarbonate in food contact applications. However, its synthesis and processing suffer from CBDO sublimation, composition deviation and relatively poor thermal stability. In order to obtain transparent heat-resistant CBDO-based copolyesters with improved synthesis robustness and thermal stability, poly(ethylene co-tetramethyl cyclobutene terephthalate (PEcBT)) copolyesters were synthesized from ethylene glycol (EG), CBDO, and terephthalic acid (TPA) via direct esterification route, and the structure–property was studied. It is found that the presence of EG effectively inhibited the sublimation of CBDO, and the resulting PEcBT copolyesters had reasonably good thermal stability so that the melt polycondensation proceeded smoothly without serious foaming. PEcBT copolyesters with intrinsic viscosity ([η]) over 0.60 dL/g were successfully synthesized at copolymer composition ( ϕ cBT ) up to 67 mol%. A quantitative relationship between T g and its influence factors is established. The copolyesters with ϕ cBT of 48–62 mol% displayed T g of 126°C–144°C, flexible tensile behavior, satisfactory tensile properties and reasonably good impact performance. Ternary PEPecBT copolyesters were also synthesized using 1,5-pentanediol as another diol comonomer to improve toughness of the materials.

CAS / MDL: 120-61-6 818-08-6
研究领域: 材料科学 · 高分子化学
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Journal of Environmental Chemical Engineering · 2021 · IF 5.909

Urea fertilizer with precisely regulable slow-release performance by complexing with random copolyester

Hong-Fang Li,Shao-Du An,Luyun Zhang,Hui Peng,Wenzhong Ma,Xiaoyu Meng,Hai-Mu Ye

Slow-release fertilizers have been widely used to promote agricultural production with less losses to the environment. However, further achievement of fertilizer with precisely regulable release performance is still full of challenges, especially for the most used nitrogen fertilizer – urea. In this study, we provide a strategy for regulating performance of slow-release urea fertilizer (SRUF) based on inclusion complexation between biodegradable copolyester and urea via simply changing chain composition. The units of butylene adipate (BA) are copolymerized into the main chains of poly(butylene succinate) (PBS) to obtain a series of random copolyesters of poly(butylene succinate- co -butylene adipate) (PBSA). The crystallizability of PBSA declines with increasing BA content, leading to the longer slow-release time for corresponding PBSA/urea inclusion complex fertilizer. The monotonous, nearly linear relationship between chain composition and the slow-release performance of SRUF has been demonstrated, revealing the great potential to design SRUF with precise slow-release time. Consequently, pot trails in the lab are employed to evaluate the promotion effect of SRUF on Brassica chinensis L.. The growth indexes of plants significantly increase with increasing BA content in PBSA chains used in SRUF of inclusion complex. The plants reach about twice of dry weight in optimized group by referring to neat urea group when the SRUF shows a release duration closely matching to the growth cycle of Brassica chinensis L.

研究领域: 农业科学 · 材料科学
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LIQUID CRYSTALS · 2019 · IF 3.078

Synthesis and properties of novel photocrosslinkable aromatic-aliphatic liquid crystal copolyesters based on poly(ethylene glycol) and cinnamic acid

Peng Wei,Yanping Wang,Yumin Xia,Yong He,Yimin Wang

Firstly, PEGn-TA monomers with carboxyl functional groups were synthesised by terephthalic acid (TA) and poly(ethylene glycol) (PEG) with molecular weight of 200, 400 and 600. Then, photocrosslinkable thermotropic liquid crystal copolyesters derived from PEGn-TA, 4,4ʹ-biphenol, 4-hydroxy-cinnamic acid and 4-hydroxy-benzoic acid were successfully obtained by Vilsmeier adduct solution polymerisation method. Influence of PEG molecular weight on thermal behaviour, liquid crystal mesophase, hydrophilicity, structure and photoactivity were investigated by various measurements. Experimental results indicated that all copolyesters showed nematic mesophase textures, relative low melting temperatures, and two glass transitions as well as better hydrophilicity were observed for those contained higher PEG molecular weight. Photocrosslinking rate was increased first and then decreased due to effect of flexible PEG moieties. The resulted copolyesters with liquid crystal behaviour, excellent hydrophilicity and photoactivity could be potentially used as biomaterial.

CAS / MDL: 92-88-6 7400-08-0
研究领域: 材料科学 · 高分子化学
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INDUSTRIAL CROPS AND PRODUCTS · 2023 · IF 5.9

Synthesis of cellulose graft cyclic anhydride and epoxide alternating copolyesters in a DBU/ DMSO/CO2 solvent system

Gu Guo,Yuanlong Guo,Hailiang Sheng,Pengcheng Liu,Lei Dai,Michael North,Lei Deng,Xiaofeng Luo,Haibo Xie

A series of cellulose grafted alternating cyclic anhydride (CA) and epoxide (EPO) copolyesters (cell- g -P(CA-alt-EPO)) have been prepared in the novel DBU/DMSO/CO 2 cellulose solvent system. The DBU acted both as a reagent for cellulose dissolution and as a catalyst for ring-opening copolymerization (ROCOP) of cellulose with EPO and CA. The structural features and thermal performances of cell- g -P(CA-alt-EPO) were characterized via MALDI-TOF, FT-IR NMR, TGA, DSC and XPS. Perfectly alternating sequence distributions and controlled molecular weights of a series of cell- g -P(CA-alt-EPO) were easily achieved by a variation of the CA or EPO. The cell- g -P(CA-alt-EPO) also had satisfactory UV-absorbing properties and cellulose grafted phthalic anhydride and glycidyltrimethylammonium chloride exhibited outstanding antibacterial behavior. Antibacterial activity against Escherichia coli and Staphylococcus aureus were 96.7% and 99.4% respectively. Thus, cell- g -P(CA-alt-EPO) with good solubility, melt processability, UV absorption and antibacterial properties have potential applications in UV-shielding and antibacterial agent fields.

研究领域: 材料科学 · 化学工程
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RSC Advances · 2017 ·Vol. 7 ·期 87 ·55418-55426 · IF 3.108

Synthesis of copolyesters with bio-based lauric diacid: structure and physico-mechanical studies

Meiling Chen,Nesren A. H. Saada,Fei Liu,Haining Na,Jin Zhu

Lauric diacid (LCDA), also known as 1,12-dodecanedioic acid, is used to develop a series of copolyesters along with 1,4-cyclohexanedicarboxylic acid (CHDA) and 1,4-butanediol (BDO). The resulting poly(butylene lauric dicarboxylate-co-butylene 1,4-cyclohexanedicarboxylate) (PBLC) is proved to be a random copolyester with three triad sequences. When the LCDA content increases from 20 to 60 mol%, Tm of the copolyester decreases from 133 to 57 °C. At the same time, the tensile modulus and strength decrease from 94 and 14 MPa to 40 and 5 MPa, respectively. Moreover, the elongation at break also drops from 640 to only 50%. However, further increasing the LCDA content to 80 mol%, the copolyester becomes amorphous with no Tm, and its tensile modulus, strength, and the elongation at break all improve significantly to 68 and 7 MPa, and over 1400%, respectively. More importantly, for the homo-polymer poly(butylene lauric dicarboxylate) (PBL), it has a relatively high Tm of 73 °C compared to that of polycaprolactone (PCL), but lower tensile modulus and strength, and significantly higher ductility, compared to those of PCL, linear low density polyethylene, and polybutylene succinate.

CAS / MDL: 556-91-2 110-63-4
研究领域: 材料科学 · 高分子化学
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