蓖麻油基水性环氧固化剂的合成及性能

doi:10.3969/j.issn.0253-2417.2019.03.009

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (3): 65-71.doi: 10.3969/j.issn.0253-2417.2019.03.009

蓖麻油基水性环氧固化剂的合成及性能

杨小华^1,²,诸进华³,张燕^1,²,李守海^1,^2,³,李梅^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
3. 中国林科院林产化学工业研究所南京科技开发有限公司, 江苏南京 210042

收稿日期:2019-01-22 出版日期:2019-06-28 发布日期:2019-06-26
通讯作者: 李梅 E-mail:meiyu20032001@126.com
作者简介:杨小华(1981-),男,江苏南通人,工程师,硕士,主要从事生物质资源化学利用研究工作
基金资助:
江苏省自然科学基金面上项目(BK20171131)

Preparation and Properties of Waterborne Epoxy Curing Agents Based on Castor Oil

Xiaohua YANG^1,²,Jinhua ZHU³,Yan ZHANG^1,²,Shouhai LI^1,^2,³,Mei LI^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
3. Nanjing Science & Technology Development Co., Ltd., Institute of Chemical Industry of Forest Products, CAF, Nanjing 210042, China

Received:2019-01-22 Online:2019-06-28 Published:2019-06-26
Contact: Mei LI E-mail:meiyu20032001@126.com
Supported by:
江苏省自然科学基金面上项目(BK20171131)

摘要/Abstract

摘要：

以液化的二苯基甲烷二异氰酸酯（MDI）、蓖麻油酸（RA）为原料，先经MDI-RA加成后，再与乙二醇二缩水甘油醚经酯化反应得到蓖麻油基环氧活性中间体（RAE），RAE经二乙烯三胺（DETA）扩链得到RAE-DETA加成物，最后经缩水甘油封端制备得到蓖麻油基水性环氧固化剂（RAWCA）。当n（MDI）:n（RA）为1: 3和1: 4时分别制得RAWCA-1和RAWCA-2，利用红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）和凝胶色谱（GPC）表征了目标产物的结构，结果表明：制备的目标产物结构参数与设计的分子结构基本吻合，目标化合物的M_n和M_w分别为1 832和1 983。对RAWCA产物性能考察可知，目标产物均具有乳化液体环氧树脂E-51的功能，选择n（MDI）:n（RA）为1:3制备的RAWCA-1与E-51固化，漆膜的耐水性较佳，且漆膜柔韧性达1 mm、铅笔硬度达3H、抗冲击性达50 kg/cm，性能可与市售水性环氧固化剂产品相媲美。

关键词: 蓖麻油酸, 液化MDI, 水性环氧固化剂, 合成, 性能

Abstract:

The adducts MDI-RA were firstly synthesized from liquified diphenylmethane diisocyanate(MDI) and ricinoleic acid(RA). Then esterification reaction between ethylene diglycidyl ether and MDI-RA was carried out for the preparation of the castor oil based epoxy active intermediates(RAE). Finally, the chain reaction of RAE with diethylenetriamine(DETA) and glycidol was performed to obtained the waterborne epoxy curing agents based on castor oil. By this way, two kinds of target products(RAWCA-1 and RAWCA-2)were obtained from feeding ratio of the n(MDI):n(RA) of 1:3 and 1:4, respectively. The chemical structures of the intermediates and the target products were confirmed by Fourier transform infrared spectroscopy(FT-IR), proton nuclear magnetic resonance(¹H NMR) and gel permeation chromatography(GPC). The results showed that the structure parameters of target products were basically agreed with the designed molecular structure and the M_n and M_w of target products were 1 832 g/mol and 1 983 g/mol. The property study showed that the target products could emulsify liquid epoxy resin E-51. The properties of the two-component film obtained from the curing reaction of RAWCA-1 and liquid epoxy resin E-51 were as follows:flexibility 1 mm, pencil hardness 3H, impact resistance 50 kg/cm, good water resistance, which could meet a requirement with commercial waterborne epoxy curing agent products.

Key words: castor oil acid, liquified MDI, waterborne epoxy curing agent, synthesis, performance

中图分类号:

TQ35

杨小华,诸进华,张燕,李守海,李梅. 蓖麻油基水性环氧固化剂的合成及性能[J]. 林产化学与工业, 2019, 39(3): 65-71.

Xiaohua YANG,Jinhua ZHU,Yan ZHANG,Shouhai LI,Mei LI. Preparation and Properties of Waterborne Epoxy Curing Agents Based on Castor Oil[J]. Chemistry and Industry of Forest Products, 2019, 39(3): 65-71.

图/表 5

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表2

表3

参考文献 17

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g
样品 sample	RAE-DETA-1	RAE-DETA-2	RAWCA-1	RAWCA-2	E-51	混合型助剂 mixed additives
RAE-DETA-1/E-51	100	0	0	0	96.00	9.22
RAE-DETA-2/E-51	0	100	0	0	95.00	9.12
RAWCA-1/E-51	0	0	100	0	50.00	4.80
RAWCA-2/E-51	0	0	0	100	50.00	4.80

样品 sample	温度/时间 temp. /time	外观 appearance	柔韧性/mm flexibility	铅笔硬度 pencil hardness	抗冲击强度/(kg·cm^-1) impact strength	耐水性(24 h) water resistance
RAE-DETA-1/E-51	25 ℃/4 h+60 ℃/ 4 h+80 ℃/2 h	无色透明 colorless and transparent	1	H	≥50	不发白 non-whitish
	60 ℃/8 h	无色透明 colorless and transparent	1	3H	48	不发白 non-whitish
	100 ℃/6 h	黄色yellow	1	3H	48	不发白 non-whitish
RAWCA-1/E-51	25 ℃/4 h+60 ℃/ 4 h+80 ℃/2 h	无色透明 colorless and transparent	1	3H	≥50	不发白 non-whitish
	60 ℃/8 h	无色透明 colorless and transparent	3	3H	45	不发白 non-whitish
	100 ℃/6 h	黄色yellow	＞7	3H	45	不发白 non-whitish

样品sample¹⁾	外观 appearance	柔韧性/mm flexibility	铅笔硬度 pencil hardness	抗冲击强度/ (kg·cm^-1) impact strength	耐水性(24 h) water resistance	耐水性(48 h) water resistance
RAE-DETA-1/E-51	透明transparent	1	H	50	不发白non-whitish	不发白non-whitish
RAE-DETA-2/E-51	透明transparent	1	H	50	不发白non-whitish	白色斑点white spots
RAWCA-1/E-51	透明transparent	1	3H	50	不发白non-whitish	不发白non-whitish
RAWCA-2/E-51	透明transparent	1	2H	50	发白whitish	发白whitish
Anquamine721/E-51^[16]	透明transparent	1	3H	50	不起泡，不失光 no bubbling, no clouding	不起泡，不失光 no bubbling, no clouding
Anquamine721/AR555^[17]	—	2	2H	40	—	—

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蓖麻油基水性环氧固化剂的合成及性能

Preparation and Properties of Waterborne Epoxy Curing Agents Based on Castor Oil

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