原儿茶酸环氧树脂的制备与应用性能测试

曹兆林; 姚玉成; 谈继淮; 程振朔; 程存照; 朱新宝

doi:10.13801/j.cnki.fhclxb.20211018.006

原儿茶酸环氧树脂的制备与应用性能测试

doi: 10.13801/j.cnki.fhclxb.20211018.006

1.
南京林业大学　化学工程学院，南京 210037
2.
安徽省环氧树脂及助剂工程技术研究中心，黄山 245900
3.
黄山科宏生物香料股份有限公司，黄山 245200

基金项目: 江苏省重点研发计划项目(BE2019111)；国家重点研发计划项目(2018YFD0600402)

详细信息

通讯作者:
朱新宝，硕士，教授，博士生导师，研究方向为精细有机合成　E-mail: zhuxinbao@njfu.com.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-07-06
- 修回日期: 2021-09-30
- 录用日期: 2021-10-10
- 网络出版日期: 2021-10-19
- 刊出日期: 2022-07-30

Preparation and application of epoxy resin derived from protocatechuic acid

1.
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
2.
Anhui Engineering Research Center of Epoxy Resin and Additives, Huangshan 245900, China
3.
Huangshan Kehong Bio-Flavors Co., Ltd., Huangshan 245200

摘要

摘要: 环氧树脂质脆需要增韧才能满足应用要求，以天然原儿茶酸(Protocatechuic acid，PA)和环氧氯丙烷为原料，通过两步法反应合成原儿茶酸环氧树脂(PA-EP)，并将其作为特种环氧树脂用于双酚A环氧树脂(E-51)的改性研究。采用傅里叶红外光谱仪(FTIR)、核磁共振(¹HNMR)、电位滴定仪和黏度仪对产物进行结构表征和性能测试。FTIR和¹HNMR分析表明成功合成目标产物，环氧值为0.73 eq/100 g，25℃下黏度为43.2 Pa·s。力学性能分析表明，当PA-EP与E-51质量比为10%时，PA-EP/E-51固化物的力学性能最佳，拉伸强度、弯曲强度和冲击强度比纯E-51分别提升了37.4%、17.2%和82.9%。冲击断面的扫描电子显微镜(SEM)结果表明，10%PA-EP/E-51固化物呈现良好的韧性断裂特征。动态机械分析(DMA)和热重分析(TG)结果表明，随着PA-EP含量的增加，固化物的玻璃化转变温度(T_g)由纯E-51的116.0℃提高到12.5%PA-EP/E-51的137.3℃，失重10%的温度和最大分解速率的温度都略微下降，但800℃残渣量由纯E-51的5.9%提高到12.5% PA-EP/E-51的9.8%。
- 原儿茶酸 /
- 环氧树脂 /
- 力学性能 /
- 热性能 /
- 原位增韧
Abstract: The brittleness of epoxy resin needs toughening to meet the application requirements. Protocatechuic acid epoxy resin (PA-EP) was synthesized from protocatechuic acid (PA) and epichlorohydrin via two-step reaction, and used as special epoxy resin for the modification of bisphenol A epoxy resin. The structure and properties of the PA-EP were characterized by fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance spectroscopy (¹HNMR), potentiometric titration and viscosity tester. FTIR, ¹HNMR and viscosity analyses indicate that the target product are synthesized with epoxy value of 0.73 eq/100 g and viscosity of 43.2 Pa·s at 25℃. The mechanical properties of PA-EP/E-51 thermosets are better than others when the mass ratio of PA-EP to E-51 is 10%. The tensile strength, flexural strength and impact strength are increased by 37.4%, 17.2% and 82.9%, respectively. The scanning electron microscope (SEM) images of impact section show that PA-EP/E-51 thermosets exhibit ductile fracture characteristics. Dynamic mechanical analysis (DMA) and thermogravimetry (TG) results indicate that the glass transition temperature (T_g) increases from 116.0℃ (neat E-51) to 137.3℃ with 12.5% of PA-EP/E-51. The weight loss 10% and the maximum decomposition rate temperature are decreased slightly while the residue content of 800℃ increases from 5.9% (neat E-51) to 9.8% (12.5% PA-EP/E-51).
- protocatechuic acid /
- epoxy resin /
- mechanical properties /
- thermal properties /
- in situ toughening

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图 1 原儿茶酸环氧树脂(PA-EP)的反应方程

Figure 1. Chemical equation of protocatechuic acid-epoxy resin (PA-EP)

TEBAC—Benzyltriethylammonium chloride

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图 2 PA-EP合成及PA-EP/E-51固化物制备

Figure 2. Schematic synthetic route of PA-EP and typical preparation process of PA-EP/E-51 thermosets

PA—Protocatechuic acid; EP—Epoxy resin; DETA—Diethylenetriamine; E-51—Diglycidyl ether of bisphenol A

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图 3 PA和PA-EP的FTIR图谱

Figure 3. FTIR spectras of PA and PA-EP

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图 4 不同PA-EP质量比的PA-EP/E-51固化物的FTIR图谱

Figure 4. FTIR spectras of PA-EP/E-51 cured products with different PA-EP mass ratios

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图 5 PA和PA-EP的¹HNMR图谱

Figure 5. ¹HNMR spectras of PA and PA-EP

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图 6 不同PA-EP质量比的PA-EP/E-51固化物的损耗角正切tanδ曲线

Figure 6. Loss tangent tanδ curves of PA-EP/E-51 cured products with different PA-EP mass ratios

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图 7 PA-EP/E-51固化物的拉伸强度(a)、弯曲强度(b)和冲击强度(c)

Figure 7. Tensile strength (a) , flexural strength (b) and impact strength (c) of PA-EP/E-51 cured products

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图 8 纯E-51 (a)和10%PA-EP/E-51 (b)冲击断面SEM图像

Figure 8. SEM images of impact section of pure E-51 (a) and 10%PA-EP/E-51 (b)

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图 9 PA-EP/E-51固化物的TG (a)和DTG (b)曲线

Figure 9. TG (a) and DTG (b) curves of PA-EP/E-51 cured products

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表 1 PA-EP/E-51固化物的玻璃化转变温度T_g

Table 1. Glass transition temperature T_g of PA-EP/E-51 cured products

Sample	T_g/℃
E-51	116.0
2.5%PA-EP/E-51	121.4
5%PA-EP/E-51	129.9
7.5%PA-EP/E-51	130.0
10%PA-EP/E-51	130.5
12.5%PA-EP/E-51	137.3

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表 2 不同PA-EP质量比的PA-EP/E-51固化物热失重数据

Table 2. Thermogravimetric date of PA-EP/E-51 cured products with different PA-EP mass ratios

Sample	T_10%/℃	T_max/℃	Residual mass/%
E-51	349.5	370.1	5.9
2.5%PA-EP/E-51	345.9	368.0	6.3
5%PA-EP/E-51	344.8	367.5	7.6
7.5%PA-EP/E-51	343.3	369.4	8.4
10%PA-EP/E-51	341.9	367.1	9.1
12.5%PA-EP/E-51	337.1	364.2	9.8
Notes：T_10%—Temperature at which the weight loss rate of the cured substance is 10%; T_max—Temperature at the maximum decomposition rate.

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