Green synthesis of gemini surfactant decyne diol

doi:10.16085/j.issn.1000-6613.2023-0424

Abstract

Abstract:

Gemini surfactant decyne diol (S104), namely 2,4,7,9-tetramethyl-5-decyne-4,7-diol, is a widely used alkyne diol surfactant. S104 is synthesized by ethynylation of methyl isobutyl ketone with acetylene in the presence of alkali catalyst. Currently, there are two types of synthesis processes: solid KOH catalytic ethynylation and liquid ammonia-KOH catalytic ethynylation, but both have serious environmental problems and other shortcomings. In this paper, the synthesis of S104 from acetylene and methyl isobutyl ketone by solid potassium isobutoxide catalyst suspended in solvent xylene was studied. The effects of various process conditions on the conversion of methyl isobutyl ketone and the yield of S104 were investigated by using single factor experiments. Based on this, a response surface experiment was applied for optimization. Under optimized reaction conditions (reaction temperature 35℃, reaction time 9h, molar ratio of potassium isobutoxide to methyl isobutyl ketone 1.5∶1, mass ratio of solvent xylene to methyl isobutyl ketone 4.5∶1), the yield of S104 was 86.52% ± 2.02%. The KOH solution obtained by hydrolysis after the reaction was returned to the potassium isobutoxide preparation step for recycling, and no significant changes in the conversion of methyl isobutyl ketone and the yield of S104 were observed. The process was carried out under atmospheric pressure and the waste alkali liquor was recycled, avoiding wastewater discharge. It was safe, environmentally friendly, and had high green value.

Key words: synthesis, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, acetylene, catalysis, optimization

摘要：

双子表面活性剂癸炔二醇（S104），即2,4,7,9-四甲基-5-癸炔-4,7－二醇，是一种用途广泛的炔二醇类表面活性剂。S104由甲基异丁基酮和乙炔在碱催化下进行炔化反应合成，目前的合成工艺有两种：固体KOH催化炔化法和液氨-KOH催化炔化法，但都存在严重的环保问题等缺点。为此本研究以悬浮于溶剂二甲苯中的固体异丁醇钾为催化剂催化乙炔和甲基异丁基酮的反应合成S104。采用单因素实验探究了各工艺条件对甲基异丁基酮转化率和S104收率的影响，并以此基础进行了响应面实验优化。在优选反应条件（反应温度35℃，反应时间9h，异丁醇钾与甲基异丁基酮摩尔比1.5∶1，溶剂二甲苯与甲基异丁基酮的质量比4.5∶1）下，S104的收率为86.52%±2.02%。将反应结束后水解得到的氢氧化钾溶液返回到异丁醇钾制备阶段循环使用，甲基异丁基酮转化率和S104收率无明显变化。该工艺在常压下进行，废碱液循环使用，避免了废水排放，安全环保，具有较高的绿色价值。

关键词: 合成, 2,4,7,9-四甲基-5-癸炔-4,7-二醇, 乙炔, 催化, 优化

CLC Number:

TQ214

WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.

王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.

Figures/Tables 20

References 30

1	GALGOCI E C, CHAN S Y, KHALIL Y. Innovative, gemini-type molecular defoamer technology for improved coating aesthetics[J]. JCT Research, 2006, 3(1): 77-85.
2	LEE F J. Acetylenic glycol-based surfactants for use in fountain solutions[J]. American Ink Maker, 1998,76(9): 30-36.
3	ZHANG P, KING D M, KARWACKI E J. Evaluating the impact of an acetylenic diol-type surfactant on DUV lithography performance[J]. Micro, 2002,20(6): 51-55.
4	JIAO Qingbin, ZHU Chunlin, TAN Xin, et al. The effect of ultrasonic vibration and surfactant additive on fabrication of 53.5gr/mm silicon echelle grating with low surface roughness in alkaline KOH solution[J]. Ultrasonics Sonochemistry, 2018, 40: 937-943.
5	TEDESCHI R J. Acetylene-based chemicals from coal and other natural resources[M]. New York: M. Dekker, 1982.
6	KELLAND M A, DIRDAL E G. Powerful synergy of acetylenic diol surfactants with kinetic hydrate inhibitor polymers—Choosing the correct synergist aqueous solubility[J]. Energy & Fuels, 2021, 35(19): 15721-15727.
7	CHRISTINE Louis. New additives for waterbased coatings: A new class of defoamers is born! [J]. Pitture e Vernici, European Coatings, 2003,79(20): 7-19.
8	DOUGLAS Bohn. The global waterborne coatings market keeps growing[J]. European Coatings Journal, 2021, 10: 16-17.
9	TROFIMOV B A, SCHMIDT E Y E. Reactions of acetylenes in superbasic media. recent advances[J]. Russian Chemical Reviews, 2014, 83(7): 600-619.
10	TROFIMOV B A, NOSYREVA V V, MAL'KINA A G. The role of potassium cation in the favorskii ethynylation of acetone: Effect of dibenzo-18-crown-6[J]. Russian Journal of Organic Chemistry, 2005, 41(9): 1254-1259.
11	DANILKINA N, VASIL'EVA A A, BALOVA I. A.E.Favorskii’s scientific legacy in modern organic chemistry: Prototropic acetylene-allene isomerization and the acetylene zipper reaction[J]. Russian Chemical Reviews, 2020, 89: 125-171.
12	TEDESCHI R J, WILSON M F, SCANLON J, et al. The reaction of alkali metal hydroxides with tertiary acetylenic carbinols and glycols[J]. The Journal of Organic Chemistry, 1963, 28(9): 2480-2483.
13	TEDESCHI R J. The mechanism of base-catalyzed ethynylation in donor solvents[J]. The Journal of Organic Chemistry, 1965, 30(9): 3045-3049.
14	周飞, 陶川东, 李杰灵, 等. 游离碱对合成2,5-二甲基己炔二醇的影响[J]. 华东科技: 综合, 2018, 1(12): 399-401.
	ZHOU Fei, TAO Chuandong, LI Jieling, et al. Effect of free base on the synthesis of 2,5 -dimethylhexynediol[J]. East China Technology: Comprehensive, 2018, 1(12): 399-401.
15	方善伦, 王丽蓉, 张征林. 叔炔醇的合成及用途[J]. 天然气化工(Cl化学与化工), 2003, 28(6): 43-47.
	FANG Shanlun, WANG Lirong, ZHANG Zhenglin. Synthesis and application of tertiary alkynols[J]. Natural Gas Chemical Industry (C1 Chemistry and Technology), 2003, 28(6): 43-47.
16	SHACHAT N, BAGNELL J J. Catalytic ethynylation of Ketones[J]. The Journal of Organic Chemistry, 1962, 27(5): 1498-1504.
17	GERHARD Thelen. Process for the manufacture of alkynediols by reaction of ketones with acetylene: US4960959[P]. 1990-10-02.
18	齐建国, 周全凯, 金凤龙. 一种合成癸炔二醇的工艺: CN102964216A[P]. 2013-03-13.
	QI Jianguo, ZHOU Quankai, JIN Fenglong. Decyne glycol synthesizing technology: CN102964216A[P]. 2013-03-13.
19	王立峰, 杨智, 孙健. 一种炔二醇系列产品的清洁生产工艺: CN103304376A[P]. 2013-09-18.
	WANG Lifeng, YANG Zhi, SUN Jian. Clean production process of alkyne diol serial products: CN103304376A[P]. 2013-09-18.
20	程霜莉, 张一甫, 黄波. 一种炔二醇系列产品的生产方法: CN103242140A[P]. 2013-08-14.
	CHENG Shuangli, ZHANG Yifu, HUANG Bo. Production method of acetylenic diol series products: CN103242140A[P]. 2013-08-14.
21	钟传蓉, 卢艾. 炔醇的应用与生产[J]. 油田化学, 2000, 17(3): 285-288.
	ZHONG Chuanrong, LU Ai. The uses and production of alkynols: A review[J]. Oilfield Chemistry, 2000, 17(3): 285-288.
22	LI Sifang. Manufacture of fine chemicals from acetylene[M]. Berlin: De Gruyter, 2021.
23	芦艾, 饶增科. 醇钾催化合成甲基戊炔醇[J]. 化学工程师, 1998, 12(5): 5-7.
	LU Ai, RAO Zengke. Synthesis of methyl pentynol with potassium alcoholate used as catalyst[J]. Chemical Engineer, 1998, 12(5): 5-7.
24	KINDLER Alois, BRUNNER Melanie, TRAGUT Christian, et al. Method for producing alkyne diols: US6297407[P]. 2001-10-02.
25	刘星玉. 2,5-二甲基己炔二醇的反应工程开发[J]. 天然气化工(C1化学与化工), 1996, 21(6): 36-40.
	LIU Xingyu. Reaction engineering development of 2,5 dimethyl hexynediol[J]. Natural Gas Chemical Industry(C1 Chemistry and Technology), 1996, 21(6): 36-40.
26	BADISCHE Anilin, SODA Fabric, AKTIENGESELL Schaft. Production of tertiary acetylenic glycols by reaction of acetylene with ketones: GB1329815A[P]. 1973-09-12.
27	BADISCHE Anilin, SODA Fabric, AKTIENGESELL Schaft. Production of acetylene glycols: GB1354011A[P]. 1974-5-22.
28	刘栋昌, 李世模. 酮的乙炔化反应的化学平衡[J]. 成都科技大学学报, 1993, 25(6): 31-39.
	LIU Dongchang, LI Shimo. Chemical equilibrium of the ethynation of ketones[J]. Journal of Chengdu University of Science and Technology, 1993, 25(6): 31-39.
29	方聪, 刘怡雪, 黎四芳. 爱德万甜中间体3-羟基-4-甲氧基肉桂醛的合成[J]. 化工进展, 2022, 41(11): 6053-6060.
	FANG Cong, LIU Yixue, LI Sifang. Synthesis of 3-hydroxy-4-methoxycinnamaldehyde, an intermediate of advantame[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6053-6060.
30	HORT E V, TAYLOR P. Kirk-Othmer encyclopedia of chemical technology, Vol. 1[M]. 5th ed. New Jersey: John Wiley and Sons, 2003.

实验因素	水平
实验因素	-1	0	1
反应温度（A）/℃	25	35	45
反应时间（B）/h	6	9	12
异丁醇钾与甲基异丁基酮摩尔比（C）	1∶1	1.5∶1	2∶1
溶剂用量（D）	3∶1	4.5∶1	6∶1

实验因素	水平
实验因素	-1	0	1
反应温度（A）/℃	25	35	45
反应时间（B）/h	6	9	12
异丁醇钾与甲基异丁基酮摩尔比（C）	1∶1	1.5∶1	2∶1
溶剂用量（D）	3∶1	4.5∶1	6∶1

方差来源	平方和	自由度	均方	F	P	显著性
回归方程	1936.259	14	138.3042	51.60691	< 0.0001	+ +
反应温度A	273.512	1	273.512	102.0584	< 0.0001	+ +
反应时间B	142.761	1	142.761	53.26993	< 0.0001	+ +
异丁醇钾与甲基异丁基酮摩尔比C	903.9352	1	903.9352	337.2949	< 0.0001	+ +
溶剂用量D	8.619075	1	8.619075	3.216127	0.0945
AB	0.81	1	0.81	0.302244	0.5911
AC	17.1396	1	17.1396	6.395481	0.0241	+
AD	2.5×10^-5	1	2.5×10^-5	9.33×10^-6	0.9976
BC	8.4681	1	8.4681	3.159792	0.0972
BD	3.591025	1	3.591025	1.339957	0.2664
CD	0.893025	1	0.893025	0.333224	0.5729
A²	378.1677	1	378.1677	141.1097	< 0.0001	+ +
B²	64.48482	1	64.48482	24.0619	0.0002	+ +
C²	298.6574	1	298.6574	111.4412	< 0.0001	+ +
D²	25.18619	1	25.18619	9.397988	0.0084	+ +
残差	37.51937	14	2.679955
失拟项	31.64865	10	3.164865	2.156373	0.2388
纯误差	5.87072	4	1.46768
总和	1973.778	28

方差来源	平方和	自由度	均方	F	P	显著性
回归方程	1936.259	14	138.3042	51.60691	< 0.0001	+ +
反应温度A	273.512	1	273.512	102.0584	< 0.0001	+ +
反应时间B	142.761	1	142.761	53.26993	< 0.0001	+ +
异丁醇钾与甲基异丁基酮摩尔比C	903.9352	1	903.9352	337.2949	< 0.0001	+ +
溶剂用量D	8.619075	1	8.619075	3.216127	0.0945
AB	0.81	1	0.81	0.302244	0.5911
AC	17.1396	1	17.1396	6.395481	0.0241	+
AD	2.5×10^-5	1	2.5×10^-5	9.33×10^-6	0.9976
BC	8.4681	1	8.4681	3.159792	0.0972
BD	3.591025	1	3.591025	1.339957	0.2664
CD	0.893025	1	0.893025	0.333224	0.5729
A²	378.1677	1	378.1677	141.1097	< 0.0001	+ +
B²	64.48482	1	64.48482	24.0619	0.0002	+ +
C²	298.6574	1	298.6574	111.4412	< 0.0001	+ +
D²	25.18619	1	25.18619	9.397988	0.0084	+ +
残差	37.51937	14	2.679955
失拟项	31.64865	10	3.164865	2.156373	0.2388
纯误差	5.87072	4	1.46768
总和	1973.778	28

循环次数	甲基异丁基酮转化率/%	S104收率/%
新配氢氧化钾溶液	92.46	85.91
1	89.14	83.19
2	90.29	83.77
3	93.82	87.16
4	93.11	86.87
5	91.22	84.52