环氧大豆油基水溶性醇酸树脂的合成、表征及酯化动力学研究

doi:10.3969/j.issn.1001-1803.2021.11.007

摘要/Abstract

摘要：

以环氧大豆油（ESO）、三羟甲基丙烷（TMP）、邻苯二甲酸酐（PA）和水性单体偏苯三酸酐（TMA）作为主要原料,采用醇解、酯化和中和等工艺路线合成水溶性醇酸树脂。以静态接触角为目标函数,通过正交试验设计优化水溶性醇酸树脂的较优合成条件,并对树脂的结构进行表征。结果表明：油度为40%,醇超量为1.2,TMA和PA的摩尔比为0.5∶1,最终酸值控制在60~80 mg KOH/g,水溶性醇酸树脂表现出优异的水溶性和稳定性。酯化动力学分析表明酯化反应符合二级反应动力学模型,由阿伦尼乌斯方程求得酯化反应活化能E_a为88.081 kJ/mol。

关键词: 环氧大豆油, 醇酸树脂, 酯化动力学, 水溶性

Abstract:

Epoxidized soybean oil （ESO）, trimethylolpropane （TMP）, phthalic anhydride （PA） and water-soluble monomer trimellitic anhydride （TMA） were used as the main raw materials to prepare water-soluble alkyd resin by alcoholysis, esterification and neutralization. With the static contact angle as the objective function, the synthesis conditions of water-soluble alkyd resin were optimized by the orthogonal experiment. The structure of the water-soluble alkyd resin was characterized. The results of Fourier transform infrared （FTIR） show that the water-soluble alkyd resin is successfully synthesized. The optimum conditions obtained by orthogonal test are as follows: the oil content is 40%; the alcohol excess is 1.2; the molar ratio of TMA to PA is 0.5∶1; the final acid value is controlled at 60-80 mg KOH/g. Through the transmittance testing and storage stability testing, the prepared water-soluble alkyd resin shows excellent water solubility and stability, indicating that epoxidized soybean oil can be used as the raw material for manufacture of waterborne alkyd coatings. The rotational rheological analysis shows that the water-soluble alkyd resin has good rheological properties and conforms to the pseudoplastic fluid. Esterification kinetics analysis shows that temperature has significant effect on the esterification reaction. With the increase of temperature, the reaction rate and conversion rate are significantly improved. The study on esterification kinetics finds that it conforms to the second-order reaction kinetics model, and the activation energy E_a of esterification reaction is 88.081 kJ/mol according to Arrhenius equation.

Key words: epoxidized soybean oil, alkyd resin, esterification kinetics, water solubility

中图分类号:

TQ658

马百峰,甄卫军,欧阳辰光,阿不拉江·玉素甫,欧全胜. 环氧大豆油基水溶性醇酸树脂的合成、表征及酯化动力学研究[J]. 日用化学工业, 2021, 51(11): 1080-1087.

Ma Baifeng,Zhen Weijun,Ouyang Chenguang,Abulajiang Yusupu,Ou Quansheng. Synthesis, characterization and esterification kinetics of epoxidized soybean oil based water soluble alkyd resin[J]. China Surfactant Detergent & Cosmetics, 2021, 51(11): 1080-1087.

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原料	w/%
ESO	42.79
TMP	23.24
PA	13.99
TMA	19.98
二甲苯	适量
三乙胺	适量
丙二醇甲醚	适量

因素标记	实验因素	水平
因素标记	实验因素	1	2	3
A	f	0.5:1	1:1	0.7:1
B	r	1.2	1.15	1.25
C	OL/%	50	40	45

水平	因素			接触角/（^o）
	A	B	C
	f	r	OL
1	1	1	1	53.9
2	1	2	2	64.0
3	1	3	3	57.2
4	2	1	2	49.0
5	2	2	3	65.9
6	2	3	1	65.5
7	3	1	3	57.0
8	3	2	1	59.8
9	3	3	2	58.7
K₁	58.37	53.3	59.73
K₂	60.13	63.23	57.23
K₃	58.5	60.47	60.03
R	1.77	9.93	2.8

温度/°C	反应级数	反应动力学拟合	反应速率常数k	线性相关系数R²
180	1	ln c_A=0.406-0.001 20x	0.001 20 min^-1	0.976
	2	1/c_A=0.629+0.001 09x	0.001 09 mol^-1·L·min^-1	0.993
	3	1/c_A²=0.304+0.002 17x	0.002 17 mol^-2·L²·min^-1	0.992
185	1	ln c_A=0.430-0.001 46x	0.001 46 min^-1	0.978
	2	1/c_A=0.608+0.001 40x	0.001 40 mol^-1·L·min^-1	0.985
	3	1/c_A²=0.269+0.002 76x	0.002 76 mol^-2·L²·min^-1	0.971
190	1	ln c_A=0.399-0.002 00x	0.002 00 min^-1	0.988
	2	1/c_A=0.618+0.002 05x	0.002 05 mol^-1·L·min^-1	0.992
	3	1/c_A²=0.248+0.004 30x	0.004 30 mol^-2·L²·min^-1	0.980
195	1	ln c_A=0.473-0.002 07x	0.002 07 min^-1	0.982
	2	1/c_A=0.539+0.002 21x	0.002 21 mol^-1·L·min^-1	0.984
	3	1/c_A²=0.058 8+0.004 90x	0.004 90 mol^-2·L²·min^-1	0.968
200	1	ln c_A=0.572-0.002 95x	0.002 95 min^-1	0.986
	2	1/c_A=0.470+0.002 98x	0.002 98 mol^-1·L·min^-1	0.987
	3	1/c_A²=-0.035 0+0.006 33x	0.006 33 mol^-2·L²·min^-1	0.959