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反应性丙烯酸酯三嵌段共聚物与纳米SiO2协同增韧环氧树脂

向艳丽 葛攀峰 任强 汪称意 李坚

向艳丽, 葛攀峰, 任强, 等. 反应性丙烯酸酯三嵌段共聚物与纳米SiO2协同增韧环氧树脂[J]. 复合材料学报, 2024, 41(4): 1830-1839. doi: 10.13801/j.cnki.fhclxb.20230818.001
引用本文: 向艳丽, 葛攀峰, 任强, 等. 反应性丙烯酸酯三嵌段共聚物与纳米SiO2协同增韧环氧树脂[J]. 复合材料学报, 2024, 41(4): 1830-1839. doi: 10.13801/j.cnki.fhclxb.20230818.001
XIANG Yanli, GE Panfeng, REN Qiang, et al. Synergistically toughening epoxy resins with reactive acrylate-based block copolymers and nano-SiO2[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1830-1839. doi: 10.13801/j.cnki.fhclxb.20230818.001
Citation: XIANG Yanli, GE Panfeng, REN Qiang, et al. Synergistically toughening epoxy resins with reactive acrylate-based block copolymers and nano-SiO2[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1830-1839. doi: 10.13801/j.cnki.fhclxb.20230818.001

反应性丙烯酸酯三嵌段共聚物与纳米SiO2协同增韧环氧树脂

doi: 10.13801/j.cnki.fhclxb.20230818.001
基金项目: 国家自然科学基金(51873025);江苏高校品牌专业建设工程资助项目;江苏高校优势学科建设工程资助项目
详细信息
    通讯作者:

    任强,博士,教授,硕士生导师,研究方向为聚合物基纳米复合材料,涂料、聚合物合成及改性 E-mail: renqiang@cczu.edu

  • 中图分类号: TB332

Synergistically toughening epoxy resins with reactive acrylate-based block copolymers and nano-SiO2

Funds: National Natural Science Foundation of China (51873025); Top-notch Academic Programs Project of Jiangsu Higher Education Institutions; Priority Academic Program Development of Jiangsu Higher Education Institutions
  • 摘要: 利用引发剂可连续再生催化剂原子转移自由基聚合(ICAR-ATRP)合成了两种反应性丙烯酸酯三嵌段共聚物:聚(甲基丙烯酸甲酯-co-甲基丙烯酸缩水甘油酯)-b-聚丙烯酸丁酯-b-聚(甲基丙烯酸甲酯-co-甲基丙烯酸缩水甘油酯) (PMGBMG)和聚甲基丙烯酸甲酯-b-聚(丙烯酸丁酯-co-甲基丙烯酸缩水甘油酯)-b-聚甲基丙烯酸甲酯(PMBGM)。并将硅烷偶联剂KH-550改性的纳米SiO2接枝于嵌段共聚物,用于对环氧树脂E-51进行增韧。研究结果表明:仅加入5%PMGBMG-SiO2,相对纯E-51体系其断裂韧性参数临界应力强度因子(KIC)提高了145%,拉伸强度和模量分别提高了8%和31%,明显优于不接枝的嵌段共聚物和PMBGM-SiO2,实现了韧性和刚性的同时提高,并且材料的耐热性保持较好。

     

  • 图  1  嵌段前后的聚合物GPC曲线

    Figure  1.  GPC curves of polymer before and after block

    PMGBMG—P(MMA-co-GMA)-b-PBA-b-P(MMA-co-GMA); PBG—Poly(BA-co-GMA); PMBGM—PMMA-b-P(BA-co-GMA)-PMMA; MMA—Methyl methacrylate; BA—Butyl acrylate; GMA—Glycidyl methacrylate

    图  2  嵌段共聚物的1H NMR图谱

    Figure  2.  1H NMR spectra of block copolymer

    图  3  KH-550、纳米SiO2和KH550-SiO2的红外图谱

    Figure  3.  IR spectra of KH-550, nano-SiO2 and KH550-SiO2

    图  4  改性的纳米SiO2接枝嵌段共聚物前后的红外光谱

    Figure  4.  IR spectra of block copolymers before and after grafting with modified nano-SiO2

    图  5  不同SiO2添加量环氧树脂体系临界应力强度因子KIC及拉伸性能

    Figure  5.  Critical stress intensity factor KIC and tensile properties of epoxy resin system with different amounts of SiO2

    图  6  5wt%添加量的嵌段共聚物增韧E-51体系的断面形貌:((a), (b)) E-51;((c), (d)) 5%PMBM-40/E-51;((e), (f)) 5%PMBGM/E-51;((g), (h)) 5%PMGBMG/E-51

    Figure  6.  Section morphologies of 5wt% addition block copolymers toughened E-51 system: ((a), (b)) E-51; ((c), (d)) 5%PMBM-40/E-51; ((e), (f)) 5%PMBGM/E-51; ((g), (h)) 5%PMGBMG/E-51

    图  7  5%PMGBMG-SiO2/E-51混合体系断面形貌((a), (b))及EDS测试硅元素分布图(c)

    Figure  7.  Cross section morphologies of 5%PMGBMG-SiO2/E-51 thermosets ((a), (b)) and silicon distribution map from EDS (c)

    图  8  环氧树脂及增韧环氧体系DMA曲线

    Figure  8.  DMA curves of epoxy and toughening epoxy thermosets

    tanδ—Loss factor

    表  1  嵌段共聚物的分子量及其分布

    Table  1.   Molecular weight and distribution of block copolymer

    Sample Mn(GPC) PDI ωMMA/wt%
    PMBM-40 12 K-41 K-12 K 1.51 37.3
    PMBGM 14 K-37 K-14 K 1.31 43.1
    PMGBMG 15 K-40 K-15 K 1.28 42.9
    Notes: PMBM-40—PMMA-b-PBA-b-PMMA; Mn(GPC)—41 K in a-12 K-41 K-12 K corresponds to the relative molecular weight of the middle soft segment of the triblock copolymer, and 12 K corresponds to the relative molecular weight of the hard segment at both ends, the same below; PDI—Polydisperse index; ωMMA—Mass fraction of MMA relative to the total molecular chain, which is obtained by nuclear magnetic resonance hydrogen spectroscopy.
    下载: 导出CSV

    表  2  嵌段共聚物-SiO2增韧环氧树脂的拉伸性能和断裂韧性

    Table  2.   Tensile properties and fracture toughness of block copolymer-SiO2 toughened epoxy resin

    Sample Tensile strength/MPa Elastic modulus/GPa KIC/
    (MPa·m1/2)
    E-51 77±5 2.42±0.14 1.56±0.14
    5%PMBM-40/
    E-51
    76±4.5 2.31±0.12 3.14±0.21
    5%PMBGM/
    E-51
    56±6 2.08±0.16 1.96±0.13
    5%PMBGM-SiO2/E-51 65±4 2.60±0.11 2.11±0.12
    5%PMGBMG/
    E-51
    75±5 2.37±0.15 3.09±0.14
    5%PMGBMG-SiO2/E-51 83±4 3.17±0.12 3.82±0.10
    下载: 导出CSV
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  • 收稿日期:  2023-06-12
  • 修回日期:  2023-07-24
  • 录用日期:  2023-08-03
  • 网络出版日期:  2023-08-18
  • 刊出日期:  2024-04-15

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