反应性丙烯酸酯三嵌段共聚物与纳米SiO<sub>2</sub>协同增韧环氧树脂

向艳丽; 葛攀峰; 任强; 汪称意; 李坚

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

常州大学　材料科学与工程学院，常州 213164

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
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出版历程
- 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: 2024-04-01

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

School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China

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

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(K_IC)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。
- ICAR-ATRP /
- 嵌段共聚物 /
- 纳米SiO₂ /
- 协同增韧 /
- 环氧树脂 /
- 力学性能
Abstract: Two reactive acrylate triblock copolymers including poly(methyl methacrylate-co-glycidyl methacrylate)-b-poly(butyl acrylate)-b-poly(methyl methacrylate-co-glycidyl methacrylate) (PMGBMG) and poly(methyl methacrylate)-b-poly(butyl acrylate-co-glycidyl methacrylate)-b-poly(methyl methacrylate) (PMBGM) were synthesized via initiator for continuous activator regeneration atom transfer radical polymerization (ICAR-ATRP). Nano-SiO₂ modified by 3-ainopropyltriethoxysilane (KH-550) was grafted on block copolymer to prepare PMGBMG-SiO₂ and PMBGM-SiO₂ as tougheners for epoxy resin. Results show that addition of 5%PMGBMG-SiO₂ in E-51 epoxy resin can increase the critical stress intensity factor (K_IC) by 145% compared with pure epoxy matrix. Meanwhile, the tensile strength and modulus are increased by 8% and 31% respectively, which are superior to the resins modified by pure copolymer and PMBGM-SiO₂. The toughness and rigidity are improved simultaneously, while heat resistance is also well maintained.
- ICAR-ATRP /
- block copolymer /
- nano-SiO₂ /
- synergistic toughening /
- epoxy resin /
- mechanical properties

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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

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图 2 嵌段共聚物的¹H NMR图谱

Figure 2. ¹H NMR spectra of block copolymer

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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

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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

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图 5 不同SiO₂添加量环氧树脂体系临界应力强度因子K_IC及拉伸性能

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

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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

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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)

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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

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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	M_n_(GPC)	PDI	ω_MMA/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; M_n_(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; ω_MMA—Mass fraction of MMA relative to the total molecular chain, which is obtained by nuclear magnetic resonance hydrogen spectroscopy.

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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	K_IC/ (MPa·m^1/2)
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

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