Microwave synthesis and properties of dioctadecyl tetrahydroxyethyl dibromopropane diammonium

doi:10.11949/j.issn.0438-1157.20181393

Abstract

Abstract:

A gemini surfactant called dioctadecyl tetrahydroxyethyl dibromopropane diammonium (DTDD) was synthesized via quaternization reaction under the condition of microwave and high pressure using octadecyl diethanolamine and 1,3-dibromopropane as the main raw materials. The target compound was characterized by IR and¹H NMR, and its purity was determined by HPLC-ELSD. By analysing the single-factor and orthogonal array design experiments, the optimal synthesis conditions for the synthesis of DTDD by microwave method were determined as follows: microwave power was set to 900W, reaction time was 8h and reaction temperature was 140°C, reaching a yeild of 92%. Compared with the traditional heating method, the reaction rate using microwave synthesis was greatly increased. The critical micelle concentration (CMC), surface tension, Kraft point, and foam properties of the product and the traditional surfactant octadecylmethyldihydroxyethyl ammonium bromide (OMDAB) were determined. The performance test results showed that compared with OMDAB, the target product had good surface properties with the critical micelle concentration of 0.087 g/L and the corresponding surface tension γ_(CMC) of 31.09 mN/m.

Key words: polyhydroxyl, surfactants, high-pressure, microwave, interface, synthesis

摘要：

以十八烷基二乙醇胺、1,3-二溴丙烷为主要原料，在微波高压条件下进行季铵化反应合成了一种双子表面活性剂双十八烷基四羟乙基二溴丙二铵（DTDD），通过红外光谱（IR）和核磁共振（¹H NMR）对DTDD进行了表征，并用液相色谱-质谱联用（LC-MS）测定了其纯度。通过单因素、正交实验得到了微波法合成目标产物的最佳合成条件为：设置微波功率为900 W，反应时间8 h，反应温度为140℃，产品收率达92%以上。与传统加热法对比, 使用微波合成法反应速率大大提高。性能测试结果表明：对比单链季铵盐（OMDAB），目标产物DTDD具有良好的表面性能，其临界胶束浓度为0.087 g/L，相应的表面张力γ_(CMC)为31.09 mN/m。

关键词: 多羟基, 表面活性剂, 高压, 微波, 界面, 合成

CLC Number:

TQ 423.99

Siyu PENG, Cheng ZHENG, Taoyan MAO, Yuan WEI, Huafeng SONG. Microwave synthesis and properties of dioctadecyl tetrahydroxyethyl dibromopropane diammonium[J]. CIESC Journal, 2019, 70(S1): 202-210.

彭思玉, 郑成, 毛桃嫣, 魏渊, 宋华峰. 双十八烷基四羟乙基二溴丙二铵的微波合成及其性能研究[J]. 化工学报, 2019, 70(S1): 202-210.

Figures/Tables 17

Fig.1 Synthetic route of DTDD (a) and structural formula of OMDAB (b)

Table 1 Effect of different solvents on product yield

溶剂	收率/%
乙醇	53.14
正丙醇	56.26
异丙醇	48.93
甲醇	59.15
正丁醇	64.54

Fig.2 Effect of molar ratio of reactants on product yield

Fig.3 Effect of reaction temperature on product yield

Fig.4 Effect of microwave radiation power on product yield

Fig.5 Effect of reaction time on product yield

Table 2 Factors and levels of orthogonal experiments

水平	A(功率)/W	B(反应时间)/ h	C(温度)/℃
1	700	6	130
2	800	7	140
3	900	8	150

Table 3 Program and result of orthogonal experiments

实验号	A	B		C	收率/ %
1	700	6		130	90.11
2	700	7		140	91.83
3	700	8		150	90.72
4	800	6		140	92.03
5	800	7		150	90.74
6	800	8		130	92.04
7	900	6		150	92.27
8	900	7		130	92.00
9	900	8		140	92.22
K₁	272.66	274.41		274.15
K₂	274.81	274.57		276.08
K₃	276.49	274.98		273.73
k₁	90.89	91.47		91.38
k₂	91.6	91.52		92.03
k₃	92.16	91.66		91.24
极差R	3.83	0.57		2.35
因素：主→次			A→C→B
最优方案			A₃B₃C₂ 900 W, 8 h, 140℃
重复实验			平均收率: 92.38%

Table 4 Comparison of various techniques

合成方法	反应时间/h	收率/%
微波反应法	4	64.54
传统加热法	8	36.51

Fig.6 IR spectrum of DTDD and octadecyl diethanolamine

Fig.7 1H NMR spectrum of DTDD

Fig.8 Thermogravimetric analysis of DTDD

Fig.9 HPLC chromatogram of DTDD

Fig.10 γ-lgC curve of DTDD and OMDAB

Fig.11 Relation between benzene content and absorbance in sample solution

Table 5 Emulsification time of various surfactant solutions for various lubricating oil phases

样品	乳化时间
样品	煤油	苯	松节油
DTDD	7 min 47 s	32 min10 s	1 h 20 min
OMDAB	7 min10 s	19 min 6 s	1 h 2 min

Table 6 Foam performance test results for different surfactants

样品	泡沫高度/cm		泡沫稳定性/%
样品	0min	5min	泡沫稳定性/%
DTDD	15.9	15.1	95.0
OMDAB	10.1	9.0	89.1

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