丙氧基化双酚A缩水甘油醚的合成与固化性能

doi:10.16085/j.issn.1000-6613.2018-1852

摘要/Abstract

摘要：

以丙氧基化双酚A（D33）、环氧氯丙烷（ECH）和液碱为主要原料，采用两步法工艺合成了丙氧基化双酚A缩水甘油醚（DGEPBA）。考察了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响。结果表明：开环催化剂三氟化硼-乙醚（BF₃-Et₂O），质量分数0.1%，D33与ECH的质量比为1∶2.0，反应温度70℃，反应时间2.5h；闭环催化剂苄基三乙基氯化铵质量分数0.2%，D33与NaOH的质量比为1∶2.2，反应温度40℃，反应时间6h时，产物环氧值为0.291eq/100g，产率95.4%，黏度为1180mPa·s。通过FTIR和¹H NMR对产物结构进行表征，并将不同质量分数的DEEBAPO掺入到E-51环氧树脂中，与二乙烯三胺（DETA）进行固化，并对其固化物力学性能进行测试。因为DGEPBA的掺入，使得E-51固化物在抗拉伸、抗冲击方面均有明显提高。热失重（TGA）分析表明固化物热稳定性稍有提高，扫描电镜（SEM）显示断裂面为韧性断裂。

关键词: 丙氧基化双酚A, 环氧氯丙烷, 合成, 固化性能

Abstract:

Diglycidyl ether of propoxylated bisphenol A (DGEPBA) was synthesized by a two-step process using propoxylated bisphenol A (D33), epichlorohydrin (ECH) and liquid alkali as the main starting materials. The effects of the substrates ratio, catalyst loading, reaction temperature and reaction time were investigated for this reaction. The results showed that the 0.1% of BF₃-Et₂O, 1∶2.0 ratio of D33 to ECH, at 70℃ and reaction for 2.5h was the best condition for the ring-opening reaction. The optimized condition for the second step was the use of 0.2% triethylammonium chloride at 40℃ for 6h with the 1∶2.2 molar ratio of D33 to NaOH, which provided the desired product in 95.4% yield with 0.291eq/100g epoxy value and 1180mPa·s viscosity. The structure of the product was characterized by FTIR and ¹H NMR, and the different amounts of DEEBAPO were incorporated into E-51 epoxy resin and cured with diethylenetriamine (DETA). The properties of the cured product were tested, and the tensile strength and impact resistance of the E-51 cured product were significantly improved with the incorporation of DGEPBA. The thermogravimetric analysis (TGA) showed that the thermal stability of the cured product was slightly improved, and the scanning electron microscopy (SEM) indicated that the fracture surface was a ductile fracture.

Key words: propanolated bisphenol A, epichlorohydrin, synthesis, curing property

中图分类号:

TQ323.5

李书香, 汪宁, 李娅, 付博, 朱新宝. 丙氧基化双酚A缩水甘油醚的合成与固化性能[J]. 化工进展, 2019, 38(06): 2961-2967.

Shuxiang LI, Ning WANG, Ya LI, Bo FU, Xinbao ZHU. Synthesis and curing properties of propoxylated bisphenol A glycidyl ether[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2961-2967.

图/表 10

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试验号	A n(D33)∶n(ECH)	B 反应温度/℃	C 催化剂用量/%	D 时间/h	环氧值 /eq·(100)g^-1
1	1.8	50	0.1	2.5	0.281
2	1.8	60	0.2	3	0.269
3	1.8	70	0.3	4	0.261
4	2.0	50	0.2	4	0.270
5	2.0	60	0.3	2.5	0.259
6	2.0	70	0.1	3	0.284
7	2.2	50	0.3	3	0.258
8	2.2	60	0.1	4	0.277
9	2.2	70	0.2	2.5	0.275
k ₁	0.270	0.270	0.281	0.272	—
k ₂	0.271	0.268	0.271	0.270	—
k ₃	0.270	0.273	0.259	0.269	—
R	0.001	0.005	0.022	0.003	—

试验号	A n(D33)∶n(ECH)	B 反应温度/℃	C 催化剂用量/%	D 时间/h	环氧值 /eq·(100)g^-1
1	1.8	50	0.1	2.5	0.281
2	1.8	60	0.2	3	0.269
3	1.8	70	0.3	4	0.261
4	2.0	50	0.2	4	0.270
5	2.0	60	0.3	2.5	0.259
6	2.0	70	0.1	3	0.284
7	2.2	50	0.3	3	0.258
8	2.2	60	0.1	4	0.277
9	2.2	70	0.2	2.5	0.275
k ₁	0.270	0.270	0.281	0.272	—
k ₂	0.271	0.268	0.271	0.270	—
k ₃	0.270	0.273	0.259	0.269	—
R	0.001	0.005	0.022	0.003	—

E-51中DGEPBA质量分数/%	凝胶时间/min
0	115
5	97
10	120
15	130
纯DGEPBA样品	300

E-51中DGEPBA质量分数/%	凝胶时间/min
0	115
5	97
10	120
15	130
纯DGEPBA样品	300

E-51中样品DGEPBA掺入量/%	拉伸强度 /MPa	断裂伸长率 /%	弯曲强度 /MPa	冲击强度 /kJ·m^-2
0	69.7	4.7	23.3	8.3
5	85.2	6.8	26.0	9.4
10	82.6	5.6	21.8	13.8
15	76.6	4.7	21.8	25.8
纯DGEPBA样品	1.7	62.0	没断	没断