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聚环氧棕榈油/聚乳酸共混物的动态硫化制备与性能

吴宇超 李超 陈婷婷 刘文地 邱仁辉 邱建辉

吴宇超, 李超, 陈婷婷, 等. 聚环氧棕榈油/聚乳酸共混物的动态硫化制备与性能[J]. 复合材料学报, 2022, 39(6): 2668-2678. doi: 10.13801/j.cnki.fhclxb.20210916.003
引用本文: 吴宇超, 李超, 陈婷婷, 等. 聚环氧棕榈油/聚乳酸共混物的动态硫化制备与性能[J]. 复合材料学报, 2022, 39(6): 2668-2678. doi: 10.13801/j.cnki.fhclxb.20210916.003
WU Yuchao, LI Chao, CHEN Tingting, et al. Preparation and properties of poly(epoxidized palm oil)/poly(lactic acid)blends via dynamic vulcanization[J]. Acta Materiae Compositae Sinica, 2022, 39(6): 2668-2678. doi: 10.13801/j.cnki.fhclxb.20210916.003
Citation: WU Yuchao, LI Chao, CHEN Tingting, et al. Preparation and properties of poly(epoxidized palm oil)/poly(lactic acid)blends via dynamic vulcanization[J]. Acta Materiae Compositae Sinica, 2022, 39(6): 2668-2678. doi: 10.13801/j.cnki.fhclxb.20210916.003

聚环氧棕榈油/聚乳酸共混物的动态硫化制备与性能

doi: 10.13801/j.cnki.fhclxb.20210916.003
基金项目: 国家自然科学基金(32071699;31800486)
详细信息
    通讯作者:

    刘文地,博士,教授,硕士生导师,研究方向为生物质复合材料 E-mail:wendi.liu@fafu.edu.cn

    邱仁辉,博士,教授,博士生导师,研究方向为生物质复合材料 E-mail:renhuiqiu@fafu.edu.cn

  • 中图分类号: TB332

Preparation and properties of poly(epoxidized palm oil)/poly(lactic acid)blends via dynamic vulcanization

  • 摘要: 聚乳酸(PLA)具有优异的力学性能,无毒性、可再生、可生物降解,且生物相容性好,是目前应用最广泛的生物基塑料之一。然而,PLA价格高、脆性大、韧性差等缺点严重限制了其在更多领域的应用。为克服这些缺点,采用双螺杆挤出和注塑成型技术制备生物基的聚环氧棕榈油(PEPO)/聚乳酸(PLA)共混物以增强PLA的韧性,表征了共混物的结晶行为、流变性能、力学性能、热稳定性和微观形貌,以揭示PEPO与PLA的动态硫化机制及PEPO橡胶相对PLA的增韧机制。结果表明:环氧棕榈油(EPO)与PLA熔融共混过程中,EPO在阳离子引发剂的作用下发生自聚,进而在PLA基体中形成颗粒状PEPO橡胶相;两相结构的形成使共混物受力时发生塑性形变,导致PLA的韧性显著提升;当PEPO的用量为20wt%时,共混物的断裂伸长率和拉伸韧性分别从纯PLA的10%和4.7 MJ/m3提高至100%和30.4 MJ/m3,但其拉伸强度、拉伸模量、储存模量和玻璃化转变温度均呈现下降趋势。

     

  • 图  3  (a) 过氧酸法合成EPO路线;(b) BF3NH2Et引发EPO的阳离子聚合

    Figure  3.  (a) Synthesis of EPO by peroxylation; (b) Proposed cationic polymerization of EPO initiated by BF3NH2Et

    图  1  棕榈油(PO)和环氧棕榈油(EPO)的ATR-FTIR图谱

    Figure  1.  ATR-FTIR spectra of palm oil (PO) and epoxidized palm oil (EPO)

    图  2  EPO的1H NMR (a) 和13C NMR (b) 图谱

    Figure  2.  1H NMR (a) and 13C NMR (b) spectra of EPO

    图  4  EPO阳离子聚合过程的DSC曲线 (a)、聚环氧棕榈油(PEPO)/聚乳酸(PLA)中PLA的GPC曲线 (b)

    Figure  4.  DSC curve of cationic polymerization of EPO (a) and GPC profiles ofpoly(lactic acid) (PLA) dissolved from poly(epoxidized palm oil) (PEPO)/PLA blends (b)

    图  5  PEPO/PLA共混物的DSC曲线

    Figure  5.  DSC curves of PEPO/PLA blends

    Tg—Glass transition temperature; Tcc—Cold crystallization temperature; Tm—Melting temperature

    图  6  190°C时PEPO/PLA共混物的复数黏度 (a)、相角δ (b)、弹性模量和损耗模量 (c) 随频率的函数关系

    Figure  6.  Complex viscosity (a), phase angle δ (b), elasticity modulus and loss modulus (c) vs. frequency of PEPO/PLA blends at 190 °C

    图  7  PEPO/PLA共混物的DMA曲线:(a) 储能模量;(b) 阻尼参数

    Figure  7.  DMA curves of PEPO/PLA blends: (a) Storage modulus; (b) Damping parameter

    图  8  PEPO/PLA共混物拉伸应力-应变 (a)、弯曲强度和模量 (b)、拉伸强度和断裂伸长率 (c)、拉伸模量和拉伸韧性 (d)

    Figure  8.  Tensile stress-strain (a), flexural strength and modulus (b), tensile strength and fracture elongation (c) and tensile modulus and toughness of PEPO/PLA blends (d)

    图  9  PLA (a)、5wt%PEPO/PLA (b)、10wt%PEPO/PLA (c)、15wt%PEPO/PLA (d)、20wt%PEPO/PLA (e)和高倍数(×20000)20wt%PEPO/PLA低温断面 (f) 的SEM图像

    Figure  9.  SEM images of cryo-fractured surfaces of PLA (a), 5wt%PEPO/PLA (b), 10wt%PEPO/PLA (c), 15wt%PEPO/PLA (d), 20wt%PEPO/PLA (e), and 20wt%PEPO/PLA with higher magnification (×20000) (f)

    图  10  PLA (a)、5wt%PEPO/PLA (b)、10wt%PEPO/PLA (c)、15wt%PEPO/PLA (d)、20wt%PEPO/PLA (e)和高倍数(×20000)20wt%PEPO/PLA拉伸断面 (f) 的SEM图像

    Figure  10.  SEM images of tensile-fractured surfaces of PLA (a), 5wt%PEPO/PLA (b), 10wt%PEPO/PLA (c), 15wt%PEPO/PLA (d), 20wt%PEPO/PLA (e), and 20wt%PEPO/PLA with higher magnification (×20000) (f)

    表  1  PEPO/PLA共混物的DSC分析结果

    Table  1.   DSC results of PEPO/PLA blends

    SampleTg/°CTcc/°CTm/°CΔHcc/(J·g−1)ΔHm/(J·g−1)Xc/%
    Pure PLA66.9103.3172.428.931.83.1
    5wt%PEPO/PLA66.899.8171.525.235.711.8
    10wt%PEPO/PLA66.399.1172.124.836.714.1
    15wt%PEPO/PLA66.297.0173.420.334.718.2
    20wt%PEPO/PLA65.996.4172.37.636.138.1
    Notes: ΔHcc—Cold crystallization enthalpy; ΔHm—Melting of the blend; Xc—Crystallinity.
    下载: 导出CSV

    表  2  PEPO/PLA共混物的DMA测试结果

    Table  2.   DMA results of PEPO/PLA blends

    SamplesE′ at 25°C/GPaTg/°C
    Pure PLA2.7868.2
    5wt%PEPO/PLA2.3367.4
    10wt%PEPO/PLA2.2166.7
    15wt%PEPO/PLA2.0666.2
    20wt%PEPO/PLA1.6565.8
    Note: E′—Storage modulus.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-05-24
  • 修回日期:  2021-08-11
  • 录用日期:  2021-08-29
  • 网络出版日期:  2021-09-16
  • 刊出日期:  2022-06-01

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