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Engineering Plastics Application

Engineering Plastics Application
  • Since 1973 (Monthly)
  • ISSN:1001-3539
  • CN:37-1111/TQ
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Volume 54 期 7，2026 2026年第54卷第7期

  • Materials & Applications

    WANG Shihao, WU Lei, ZHANG Pengyao, LIU Xudong, ZHU Yan, ZHANG Yaoyao, XU Feng, JIA Shikui

    DOI：10.3969/j.issn.1001-3539.2026.07.001
    摘要：To address the inherent flammability of poly(butylene adipate-co-terephthalate)(PBAT), the development of biodegradable composites with desirable flame-retardant properties is aimed. A bio-based phosphorus-doped flame retardancy (AL-DPPC) was successfully prepared by nucleophilic substitution reactions between alkaline lignin (AL) and diphenylhypophosphonyl chloride (DPPC). AL-DPPC was then incorporated into PBAT matrix by melt blending to obtain biodegradable flame-retardant PBAT composites (PBAT/AL-DPPC). Subsequently, the effects of AL-DPPC content on the crystallization behavior, mechanical properties, thermal stability and flame retardancy of the composites were systematically investigated, and the flame-retardant mechanism was analyzed. The limiting oxygen index(LOI) results show that when AL-DPPC loadings are 5 wt% and 7 wt%, the LOI values of PBAT/AL-DPPC composites are increased from 20.1% (neat PBAT) to 28.5% and 29.5%, respectively. Cone calorimeter tests indicate that for 7 wt% of AL-DPPC modified PBAT composite, its peak heat release rate and total heat release are decreased by 33.5% and 15.7%, respectively, compared to neat PBAT, while the fire performance index is increased by 44.4%, indicating a significantly reduced fire risk. Crystallization test results reveals that the crystallinity of PBAT composites first increase and then decrease with increasing AL-DPPC content. Observations of the residual char morphology shows that after combustion, PBAT composites formed a denser char layer than neat PBAT, effectively enhancing the flame retardancy of the material. In summary, AL-DPPC can endow PBAT with excellent flame retardancy at a low addition level, providing an effective route for the preparation of high-performance flame-retardant PBAT.  
    关键词：poly(butylene adipate-co-terephthalate);alkaline lignin;diphenylphosphinic chloride;crystallization;flame retardancy   
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    更新时间：2026-08-06

    DANG Haichun, LI Xiurong, LI Jiaxuan, SONG Hongxia, CUI Xuannan, ZHANG Yuhang, XU Lijun, DONG Jiacheng, LIU Bingxiao

    DOI：10.3969/j.issn.1001-3539.2026.07.002
    摘要：Aiming at the critical issues of hydrophobic modification layer detachment and hydrophobicity attenuation in hydrophobic polyurethane sponges(PUS), hydrophobic calcium carbonate (CaCO3) with different morphologies was introduced into PUS and treated with acid etching to prepare hydrophobic porous skeleton PUS, endowing it with excellent oil-water separation performance. Firstly, hydrophobic CaCO3 with diverse morphologies was controllably synthesized by regulating the content of magnesium chloride and using cetyltrimethylammonium bromide as a hydrophobic modifier. Secondly, hydrophobic PUS was prepared by incorporating the synthesized hydrophobic CaCO3 via a one-step free foaming method. Finally, acid etching was conducted on PUS/CaCO3 hydrophobic sponges to construct micro-nano porous structures on both the surface and interior of PUS skeleton, thus obtaining structurally stable hydrophobic porous skeleton PUS. The incorporation of hydrophobic CaCO3 effectively enhanced the hydrophobicity of PUS, while the morphology of CaCO3 exerted a significant influence on the oil absorption performance of the composite sponges. Specifically, PUS modified with rod-shaped CaCO3 (PUS/RCC) exhibited higher adsorption efficiency for engine oil and edible oil. For PUS after acid etching(EPUS/RCC), its oil absorption capacities for edible oil, engine oil and carbon tetrachloride used to simulate heavy oil reached 29.9, 29.5, 55.5 g/g, which were 288%, 392% and 57.7% higher than those of pure PUS, respectively. Additionally, the sponges modified with spherical CaCO3 and nano-sized CaCO3 showed a significant improvement in the adsorption capacity for carbon tetrachloride. Particularly, the etched nano-sized CaCO3 modified hydrophobic PUS displayed superior oil adsorption performance. The maximum absorption capacity reached 60.5 g/g, which markedly outperformed samples with other morphological modification, revealing its outstanding adsorption capacity toward heavy‑oil. Moreover, after five consecutive adsorption‑squeezing cycles for EPUS/RCC, the adsorption capacities for the three types of oils exhibited negligible decline. The adsorption recovery rate remained stable at nearly 100% upon repeated cycles, which verified the superior cyclic stability and recyclability of EPUS/RCC. In oil‑water separation tests, PUS/RCC hydrophobic sponge achieves separation efficiencies of 96.9% for oil and 98.6% for water, confirming its prominent oil‑water separation capability.  
    关键词：different morphologies;calcium carbonate;polyurethane sponge;hydrophobic and oleophilic;porous skeleton   
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    更新时间：2026-08-06

    QI Gaoyun, LUO Zhonglin, WANG Biaobing

    DOI：10.3969/j.issn.1001-3539.2026.07.003
    摘要：Poly (lactic acid)(PLA), as a biodegradable polymer, is limited in high-end applications due to its inherent flammability, poor char-forming ability, and severe melt-dripping during combustion. By using diethylenetriamine penta (methylene phosphonic acid)(DTPMPA) and the natural amino acid arginine (Arg) as raw materials, a bio-based flame retardant, D5Arg, was synthesized in aqueous solution. PLA/D5Arg composites were prepared via melt blending, and the combustion behaviors, flame retardancy and flame mechanism of PLA/D5Arg composites were investigated. The successful synthesis of D5Arg was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Flame retardant tests show that with 4.8 wt% D5Arg, the prepared PLA/D5Arg-5 composite achieves a limiting oxygen index of 25.7% and a V-0 rating in vertical burning test, effectively inhibiting melt-drip ignition. Thermogravimetric analysis reveals that D5Arg reduces the thermal decomposition rate of PLA composites, and the char residue at 800 ℃ increases from 0.09% of neat PLA to 1.12% of composite, an increase of 11.4-fold. Cone calorimeter test results indicate that, compared with neat PLA, PLA/D5Arg-5 reduces total heat release by about 9.54% , total smoke production by about 26.9% and average effective combustion heat by about 16.1%, demonstrating good smoke suppression and flame retardant effects. Thermogravimetric-infrared analysis shows that D5Arg decomposes to produce phosphorus-containing volatiles, NH3 and CO2 when heated, quenching active free radicals and diluting combustible gases and heat in the gas phase. Morphological and X-ray photoelectron spectroscopy analysis of the residual char confirm that D5Arg catalyzes the formation of a dense surface char layer rich in phosphorus and nitrogen during PLA combustion, effectively acting as a barrier to heat and oxygen transfer, thereby exerting the flame retardant effect of condensed phase. The tensile strength of PLA composites decreases after adding flame retardants, while the impact strength slightly increases. This study provides a simple and efficient preparation strategy for the development of high-performance, environmentally friendly flame-retardant PLA materials.  
    关键词：poly(lactic acid);diethylenetriamine penta(methylene phosphonic acid);arginine;bio-based flame retardant;flame retardancy   
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    更新时间：2026-08-06

    HUANG Yeting, WANG Dong, SONG Ru, YU Min, HAN Xiaoyu

    DOI：10.3969/j.issn.1001-3539.2026.07.004
    摘要：Aiming at limited functionality of single photochromic materials and the irreversible degradation of donor-acceptor Stenhouse adducts (DASAs) under UV irradiation, by combining the positive photochromism of spiropyran (SP) and negative photochromism of DASAs, a novel photoresponsive SP-DASAs covalent compound SD was designed and synthesized through an alkyl chain covalent coupling strategy. Structure and light response properties of SD were characterized by nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and UV-visible absorption spectroscopy. Its solvatochromic effect, dark stability and photochromic behavior were systematically investigated. The interaction mechanism between SP and DASAs units was preliminarily explored via control and physical mixing experiments, and the potential applications of covalent coupling compound SD in the field of polymers were further studied.The results indicate that SD presents prominent solvatochromic behavior and superior dark-state stability in low-polarity solvents. 365 nm UV light selectively triggers the ring-opening of SP units, relieving the oxidative degradation to some extent and improving the UV structural stability of DASAs. Based on these photoresponsive features, SD can be compounded with polyurethane to fabricate light-controllable writing films and dynamic QR code anti-counterfeiting materials, achieving reversible pattern display driven by UV and information encryption. This covalent coupling strategy improves stability of DASAs, offering a new idea for molecular design, performance regulation and smart polymer applications of high-stability photochromic systems.  
    关键词：spiropyran;donor-acceptor Stenhouse adducts;photochromism;smart materials;photoresponsive behavior   
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    MIAO Tongtao, WANG Ziyao, YU Chengchen, SUN Guohua, LIANG Shuang, YU Xinran

    DOI：10.3969/j.issn.1001-3539.2026.07.005
    摘要：A polyurethane urea (PUU) system containing dynamic disulfide bonds and hydrogen bonding synergistic effects was constructed to solve the problem of structural control difficulties in achieving synergistic performance of high strength, high ductility and efficient self-healing of PUU elastomers (PUUE). Polycaprolactone (PCL) and bis (2-hydroxyethyl) disulfide (HEDS) were used as soft segments and were reacted with isophorone diisocyanate, followed by chain extension with phthalic acid hydrazide, to obtain self-healing polyurethane urea elastomers (SPUUE) materials with different compositions. Structural characterization was carried out using spectroscopic and diffraction techniques. The results confirmed the complete consumption of isocyanate groups. Disulfide bonds were successfully introduced. A distinct crystalline structure was observed at specific compositions, indicating a well-defined and tunable network. SPUUE materials exhibit good thermal stability below 270 ℃ .The thermal decomposition temperatures decrease with increasing disulfide content, while the glass transition temperature increases. The sample with a molar quantitye ratio of PCL to HEDS of 8:2 exhibits the optimal comprehensive mechanical properties. Its tensile strength reaches 48.4 MPa, and its elongation at break reaches 923%. The tear energy is 160.77 kJ/m². The cyclic tensile results show that energy dissipation increases significantly when the strain exceeds 400%, indicating excellent energy dissipation capability. Self-repair experiments have shown that the repair efficiency increases with increasing temperature.After healing at 90 ℃ for 3 h, SPUUE1 sample achieves a tensile strength recovery of 98.4% and an elongation recovery of 99.9%. The recycling results show that the material retains 89.6% of its original strength after the first cycle and 70.1% of that after five cycles. These results demonstrate that regulating the soft segment composition and introducing dynamic disulfide bonds enables a balanced combination of mechanical performance, self-healing capability and recycling stability in PUUE materials.  
    关键词：polyurethane urea;self-healing;recyclable;disulfide bond;hydrogen bonding   
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    MIAO Wei, WANG Jinrui, WANG Shaoshuai, LI Jinling, CHENG Wenxi, SONG Weiqiang, WANG Tao, WANG Chenyu

    DOI：10.3969/j.issn.1001-3539.2026.07.006
    摘要：Polylactic acid (PLA) is a fully biodegradable green packaging material with promising prospects in the field of fresh food packaging. Nevertheless, neat PLA suffers from drawbacks including poor mechanical properties and absence of antibacterial activity, which greatly hinder its industrial popularization. To optimize the overall performance of PLA, adopting maleic anhydride-butyl acrylate copolymer (PBM) as a compatibilizer, a series of PLA/ZnO/PBM nanocomposite films with PBM contents ranging from 0.5 wt% to 2 wt% were fabricated via melt blending followed by hot-pressing, and pure PLA and PLA/ZnO films were used as controls. Multiple characterization techniques were utilized to systematically investigate the effects of PBM loading on the microstructure and performances of composite films, and broccoli preservation tests were carried out to evaluate their practical application performance. Proton nuclear magnetic resonance results verified that the synthesized product was PBM. Differential scanning calorimetry and thermogravimetric analysis measurements revealed that PBM effectively increased the crystallinity and thermal stability of composites. Mechanical tests demonstrated that PBM simultaneously boosted tensile strength and toughness of films. The maximum tensile strength of 74.06 MPa was achieved at 1 wt% PBM, 1.25 times that of PLA/ZnO film, proving that PBM significantly improved the dispersion of nano-ZnO and interfacial compatibility within PLA matrix. Antibacterial tests indicated that nano-ZnO endowed the film with basic antibacterial capacity, which was further enhanced by incorporating PBM. At PBM of 1.5 wt%, the antibacterial rates against Staphylococcus aureus and Escherichia coli reached 92.27% and 93.55%, respectively. Broccoli storage experiments confirmed that the composite film obviously reduced weight loss and decay rate of fruits and vegetables during storage, retarded yellowing and senescence, and extended the shelf life of broccoli to 6 days. This study successfully remedies the performance deficiencies of neat PLA, providing reliable experimental references for the development and application of high-performance biodegradable food packaging materials.  
    关键词：polylactic acid;nano-zinc oxide;maleic anhydride -butyl acrylate copolymer;compatibilization;antibacterial activity   
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    KONG Yiru, LIANG Bing, LONG Jiapeng

    DOI：10.3969/j.issn.1001-3539.2026.07.007
    摘要：Using dichloromethane as the solvent, benzenphosphonyl dichloride and ethylenediamine (EDA) were added to synthesize the flame-retardant curing agent (PN-EDA) containing phosphorus and nitrogen elements. Flame-retardant epoxy resin(EP) composites were then prepared by curing epoxy resin EP with PN-EDA. The structure of PN-EDA was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance hydrogen spectrum (1H NMR), etc. The flame retardancy of the composites was evaluated via limiting oxygen index (LOI), vertical burning, etc. The morphology of the residual char after combustion was observed by scanning electron microscopy. The mechanical properties of EP composites were tested with a tensile testing machine and an impact tester. The results show that LOI of PN-EDA/EP composites gradually increases with the rising addition of PN-EDA. When phosphorus content is 0.64%, LOI of the composite reach 28.4%, which is significantly higher than 20.1% of EP without PN-ED, achieving a V-0 rating of vertical burning with no dripping observed. Cone calorimeter tests reveal that compared with EP without PN-EDA, the peak heat release rate of PN-EDA/EP decreases from 620 kW/m2 to 286 kW/m2, a reduction of 53.9%. The total heat release drops from 121 MJ/m2 to 52 MJ/m2, a decrease of 57.0%, and the fire performance index increases from 0.176 s·m2/kW to 0.255 s·m2/kW, indicating that PN-EDA remarkably suppresses heat release during combustion. In terms of mechanical properties, the tensile strength and flexural strength of EP composites show an upward trend with increasing PN-EDA content, while the impact strength decrease slightly. At a phosphorus content of 0.64%, the tensile strength of EP composites reaches 70.64 MPa, the flexural modulus is 5 408.59 MPa and the impact strength is 8.50 kJ/m2. The composites exhibites favorable overall mechanical properties, making them suitable for applications requiring high strength and high rigidity.  
    关键词：Epoxy resin;synthesis;composite;flame retardant property;mechanical property   
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