橡胶籽油基类环氧丙烯酸酯树脂的合成及其性能研究

doi:10.3969/j.issn.0253-2417.2020.04.013

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (4): 93-99.doi: 10.3969/j.issn.0253-2417.2020.04.013

橡胶籽油基类环氧丙烯酸酯树脂的合成及其性能研究

陆剑彧^1,²,吴琼^1,³,汤继俊¹,任晓丽²,周永红²,刘承果^2,*()

1. 江苏科技大学材料科学与工程学院, 江苏镇江 212003
2. 中国林业科学研究院林产化学工业研究所, 江苏南京 210042
3. 南京林业大学材料科学与工程学院, 江苏南京 210037

收稿日期:2020-01-14 出版日期:2020-08-28 发布日期:2020-08-21
通讯作者: 刘承果 E-mail:liuchengguo@icifp.cn
作者简介:陆剑彧(1996-),男,江苏南通人,硕士生,主要从事高分子材料的研究
基金资助:
中国林业科学研究院基本科研业务费专项资金资助项目(CAFYBB2017QB006)

Synthesis and Property of Rubber Seed Oil-based Epoxy Acrylate Resin

Jianyu LU^1,²,Qiong WU^1,³,Jijun TANG¹,Xiaoli REN²,Yonghong ZHOU²,Chengguo LIU^2,*()

1. College of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
2. Institute of Chemical Industry of Forest Products, CAF, Nanjing 210042, China
3. School of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

Received:2020-01-14 Online:2020-08-28 Published:2020-08-21
Contact: Chengguo LIU E-mail:liuchengguo@icifp.cn

摘要/Abstract

摘要：

利用环氧化橡胶籽油（ERSO）与甲基丙烯酸羟乙酯化马来酸半酯（HEMAMA）发生开环反应，制备了新型的橡胶籽油基类环氧丙烯酸酯（HMMERSO）预聚体，采用FT-IR和¹H NMR确认其化学结构，研究了HMMERSO与不同稀释剂混合所得光固化材料的最终性能。研究结果显示：所得HMMERSO中每一个甘油三酯分子具有4.85个C=C官能团，含生物基71.2%。HMMERSO材料展示了优良的性能，纯HMMERSO材料在常温下储能模量能达752.8 MPa，玻璃化转变温度（T_g）为67.4℃，拉伸强度和模量分别为9.84和365.5 MPa，其值分别是纯环氧大豆油丙烯酸酯（AESO）材料值的7.7倍、4倍、5.1倍和9.7倍。用30%甲基丙烯酸羟乙酯稀释剂改性后材料的性能更佳，其拉伸强度达到26.1 MPa，T_g达到90.9℃。

关键词: 橡胶籽油, 环氧丙烯酸酯, 光固化涂料

Abstract:

Epoxidized rubber seed oil (ERSO) and hydroxyethyl methacrylate maleate (HEMAMA) precursors underwent epoxide-opening reaction to prepare a new rubber seed oil-based epoxy acrylate (HMMERSO). Polymer and its chemical structure were confirmed by FT-IR and ¹H NMR. The final properties of the photocurable materials obtained by mixing HMMERSO with different diluents were also studied. The obtained HMMERSO had 4.85 C=C functional groups in per triglyceride molecule, and the bio-based content was 71.2%. The HMMERSO material was found to exhibit excellent performance. The storage modulus of HMMERSO material at normal temperature could reach 752.8 MPa, the glass transition temperature (T_g) was 67.4 ℃ and the tensile strength and modulus were 9.84 and 365.5 MPa, which were 7.7, 4, 5.1 and 9.7 times of the values of the epoxidized soybean oil acrylate(AESO) material, respectively. The performance of the material modified with 30% hydroxyethyl methacrylate diluent was better, and its tensile strength reached 26.1 MPa and T_g reached 90.9 ℃.

Key words: rubber seed oil, epoxy acrylate, photocurable coating

中图分类号:

TQ35

陆剑彧,吴琼,汤继俊,任晓丽,周永红,刘承果. 橡胶籽油基类环氧丙烯酸酯树脂的合成及其性能研究[J]. 林产化学与工业, 2020, 40(4): 93-99.

Jianyu LU,Qiong WU,Jijun TANG,Xiaoli REN,Yonghong ZHOU,Chengguo LIU. Synthesis and Property of Rubber Seed Oil-based Epoxy Acrylate Resin[J]. Chemistry and Industry of Forest Products, 2020, 40(4): 93-99.

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样品 samples	25℃储存模量 (E′₂₅)/MPa 25℃ storage modulus	玻璃化转变温度(T_g)/℃ transition temp.	交联密度(ν_e)/ (mol·m^-3) crosslinking density	5%热失重温度(T₅)/℃ 5% weight loss temp.	最大热降解温度(T_p)/℃ maximum thermal degradation temp.	成炭率 (w_char)/% char yield
HMMERSO	752.8	67.4	4.63×10³	279.9	421.4	3.3
AESO	96.9	16.9	3.63×10³	332.8	398.7	2.1
HMMERSO/HEA30	624.5	47.2	2.47×10³	285.9	423.9	5.5
HMMERSO/HEMA30	1287.0	90.9	2.24×10³	273.4	425.5	3.1
HMMERSO/TEGDA30	1005.0	77.1	7.91×10³	301.3	430.3	3.0
HMMERSO/TMPTA30	1445.0	69.3	41.30×10³	312.9	458.7	3.9

样品 samples	拉伸强度/MPa tensile strength	拉伸模量/MPa tensile modulus	断裂伸长率/% elongation at break	漆膜附着力 film adhesion	铅笔硬度 pencil hardness	漆膜柔韧性/mm flexibility of paint film
HMMERSO	9.84±0.88	365.5±23.4	5.2±0.2	2	2B	2
AESO	1.93±0.12	37.7±1.8	5.9±0.2	3	4B	2
HMMERSO/HEA30	12.1±0.77	355.5±40.9	11.7±2.3	2	3H	2
HMMERSO/HEMA30	26.1±0.2	391.9±15.1	7.8±0.7	2	2H	2
HMMERSO/TEGDA30	13.3±1.1	622.9±24.4	3.8±0.3	2	H	3
HMMERSO/TMPTA30	8.09±0.7	1009.4±36.0	2.3±0.7	2	2B	2

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橡胶籽油基类环氧丙烯酸酯树脂的合成及其性能研究

Synthesis and Property of Rubber Seed Oil-based Epoxy Acrylate Resin

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