基于乙基纤维素-马来海松酸酯的酸酐类环氧固化剂的固化及性能研究

doi:10.3969/j.issn.0253-2417.2020.04.008

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (4): 57-62.doi: 10.3969/j.issn.0253-2417.2020.04.008

基于乙基纤维素-马来海松酸酯的酸酐类环氧固化剂的固化及性能研究

丘雨玲^1,²,郭晓亮^1,²,卢传巍^1,²,王春鹏^1,²,王基夫^1,^2,*(),储富祥^1,²

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2020-02-13 出版日期:2020-08-28 发布日期:2020-08-21
通讯作者: 王基夫 E-mail:wjf118@126.com
作者简介:丘雨玲(1993-),女,广西贵港人,硕士生,主要从事生物质材料功能化研究工作
基金资助:
国家自然科学基金资助项目(31971600)

Curing Kinetics and Properties of Anhydride Epoxy Curing Agent Based on Ethyl Cellulose-maleopimaric Acid Ester

Yuling QIU^1,²,Xiaoliang GUO^1,²,Chuanwei LU^1,²,Chunpeng WANG^1,²,Jifu WANG^1,^2,*(),Fuxiang CHU^1,²

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2020-02-13 Online:2020-08-28 Published:2020-08-21
Contact: Jifu WANG E-mail:wjf118@126.com

摘要/Abstract

摘要：

通过酯化反应将马来海松酸（MPA）接枝到乙基纤维素（EC）分子侧链，合成乙基纤维素马来海松酸酯（EC-g-MPA），并将EC-g-MPA作为高分子酸酐类环氧树脂固化剂，与环氧树脂（ER）进行固化反应制备了一系列的环氧树脂（EC-g-MPA/ER）聚合物。采用红外光谱对固化后的环氧树脂的化学结构进行了表征，非等温DSC对固化体系的固化动力学进行了研究，结果表明：固化后环氧树脂中归属于酸酐的红外特征吸收峰完全消失随着升温速率的增加固化速率逐渐增加，固化度逐渐降低。该固化体系的活化能（E_a）为73.94 kJ/mol，该固化体系的指前因子（A）为1.27×10⁶s^-1，反应级数（n）为0.9，表明该固化反应是一个复杂的过程。热力学性能研究表明：随着固化剂含量的增加，产物的玻璃化转变温度逐渐升高，且固化后的树脂具有优异的热稳定性。机械性能研究表明：随着固化剂EC-g-MPA含量的增加，固化产物的机械强度逐渐增加，可以通过调整固化剂含量制备具有不同机械性能的环氧聚合物。

关键词: 乙基纤维素, 松香, 酸酐固化剂, 环氧树脂, 固化动力学

Abstract:

The ethyl cellulose maleopimaric acid ester (EC-g-MPA) was synthesized by grafting maleopimaric acid (MPA) onto the cellulose backbone(EC). Then, a series of epoxy resin polymers(EC-g-MPA/ER) were prepared via curing reaction between EC-g-MPA, acting as acid anhydride epoxy resin curing agent, and epoxy resin(ER). FT-IR was carried out to confirm the chemical structure of the products. And non-isothermal DSC was carried out to investigate the curing kinetics of the curing system. The results showed that the FT-IR characteristic absorption peak attributed to anhydride disappeared completely after curing. The activation energy of the curing system was 73.94 kJ/mol, the pre-factor(A) of the curing system was 1.27×10⁶ s^-1, and the reaction order(n) was 0.9, indicating the curing reaction was a complex process. The thermodynamic performance study showed that the glass transition temperature of the product gradually increased with the increase of EC-g-MPA content, and the cured resin also showed excellent thermal stability. Mechanical properties study showed that the mechanical strength of the cured product increased with the increase of EC-g-MPA content, and the epoxy resins with different mechanical properties could be prepared by tuning the content of the curing agent.

Key words: ethyl cellulose, rosin, anhydride curing agent, epoxy resin, curing kinetics

中图分类号:

TQ326.4

丘雨玲,郭晓亮,卢传巍,王春鹏,王基夫,储富祥. 基于乙基纤维素-马来海松酸酯的酸酐类环氧固化剂的固化及性能研究[J]. 林产化学与工业, 2020, 40(4): 57-62.

Yuling QIU,Xiaoliang GUO,Chuanwei LU,Chunpeng WANG,Jifu WANG,Fuxiang CHU. Curing Kinetics and Properties of Anhydride Epoxy Curing Agent Based on Ethyl Cellulose-maleopimaric Acid Ester[J]. Chemistry and Industry of Forest Products, 2020, 40(4): 57-62.

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参考文献 16

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升温速率(β)/ (K·min^-1) heating rate	固化反应初始温度(T_i)/℃ initial temperature of curing reaction	峰顶温度 (T_p)/℃ peak temperature	固化反应终点温度(T_f)/℃ end point temperature of curing reaction	(1/T_p)× 10³/K^-1	-ln(β/T_p²)	ΔH/(J·g^-1)
5	116.01	139.05	160.35	2.426	10.43	-38.46
10	127.81	149.68	170.98	2.356	9.79	-33.18
15	140.00	158.67	180.79	2.316	9.43	-35.34
20	141.54	164.29	188.56	2.286	9.17	-49.40

样品 samples	拉伸强度/MPa tensile strength	断裂伸长率/% elongation at break
ER	1.29	89.01
EC-g-MPA(9%)/ER	3.49	80.07
EC-g-MPA(18%)/ER	10.33	103.51
EC-g-MPA(21%)/ER	16.06	98.69
EC-g-MPA(24%)/ER	19.97	86.21
EC-g-MPA(27%)/ER	22.56	87.26
EC-g-MPA(30%)/ER	25.46	71.28
EC-g-MPA(33%)/ER	27.60	64.09
EC-g-MPA(36%)/ER	30.20	38.95
EC-g-MPA(39%)/ER	35.62	21.56
EC-g-MPA(42%)/ER	39.96	9.60
EC-g-MPA(45%)/ER	42.33	8.05

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基于乙基纤维素-马来海松酸酯的酸酐类环氧固化剂的固化及性能研究

Curing Kinetics and Properties of Anhydride Epoxy Curing Agent Based on Ethyl Cellulose-maleopimaric Acid Ester

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