烷基苯型双子表面活性剂的合成
摘要
双子表面活性剂(Gemini surfactants)是具有两个亲水基团和两个亲油基团的一类特殊结构的表面活性剂。本论文主要对烷基苯型双子表面活性剂的合成进行了研究,主要有以下几个方面的工作。
一、以十二烷基苯,1,2-二氯乙烷为反应物,在催化剂无水三氯化铝作用下反应合成双烷基二苯乙烷,考察了反应物摩尔比,催化剂的加入量,反应温度,反应时间,溶剂类型对反应的影响。通过研究发现:十二烷基苯在三氯化铝的作用下会发生歧化和重排反应,在现有的实验条件下以十二烷基苯与1,2-二氯乙烷在三氯化铝的催化下反应不能生成二(十二烷基苯基)乙烷。
二、以1,2-二苯乙烷,1-卤代烷为反应物,在催化剂无水三氯化铝作用下反应合成烷基二苯乙烷,考察了不同的反应物摩尔比(1,2-二苯乙烷:1-卤代烷)对目标产物生成的影响。当1,2-二苯乙烷:1-卤代烷(摩尔比)为1:4时,主要产物为多烷基二苯乙烷;当1,2-二苯乙烷:1-卤代烷(摩尔比)是从2:1到4:1的范围,主要产物为单烷基二苯乙烷。
三、以1,2-二苯乙烷,十二酰氯为反应物,环己烷做溶剂,在催化剂无水三氯化铝作用下反应合成双十二酰基二苯乙烷,1,2-二苯乙烷:十二酰氯(摩尔比)为1:2.5时,能较好的得到目标产物4,4-二(十二酰基)二苯乙烷。4,4-二(十二酰基)二苯乙烷进行羰基还原反应,得到4,4-二(十二烷基)二苯乙烷,接着在20~25℃,四氯化碳做溶剂条件下和65%发烟硫酸发生磺化反应,得到双烷基苯型磺酸盐。
四、以苯甲醛,氢氧化钾,三氯甲烷和二苯甲烷为反应物合成出1,4-二苄基苯。以苯和对二氯苄为反应物,在无水三氯化铁催化下,合成出1,4-二苄基苯。并对苯,1,2-二苯乙烷,二苯甲烷,1,4-二苄基苯的荧光光谱进行对比。
Gemini surfactant which has two hydrophilic groups and two hydrophobic groups is a new kind of surfactant with special molecular structure versus the traditional surfactant (only one hydrophilic group and hydrophobic-based).The synthesis of alkylbenzene sulfonates -Gemini surfactant conducted a study on the following work.
1. The dialkyl diphenylethane has planed to be prepared with dodecylbenzene and 1,2-dichloroethane over anhydrous aluminum chloride catalyst. The effect of molar ratio of reactants, catalyst dosage, reaction temperature, reaction time and solvent type on the reaction were also discussed. It was indicated that the dodecylbenzene disproportionation and rearrangement reactions under the aluminum chloride can be taken placed, and then the didodecylbenzeneethane cannot be synthesised under the above reactive conditions.
2. It has been designed to synthesize the alkyl-diphenylethane with reactants of 1,2-diphenylethane and 1-haloalkane over anhydrous aluminum chloride catalyst. Having been carried out the effect of different reactants molar ratio (1,2-diphenylethane : 1-haloalkane) on target product, it was found that the multialkyl diphenylethane was obtained when 1,2-diphenylethane :1-haloalkane is 1:4 (mole ratio), and the monoalkyl diphenylethane was obtained while the mole ratio of 1,2-diphenylethane and 1-haloalkane was from 2:1 to 4:1.
3. The dilauroyl diphenylethane has been successfully synthesized with the reactants mole ratio of 2.5 times of lauroyl chloride to 1,2-diphenylethane under the reaction conditions of cyclohexane solvent and anhydrous aluminum chloride catalyst.The 4,4ˊ-bis (dodecyl) diphenylethane was obtained by carbonyl reduction reaction of 4,4ˊ- bis(dodecanoyl) diphenylethane . The double-alkylbenzene sulfonate was prepared with the sulfonated reaction and neutralization agent. The sulfonation conditions were as follows: carbon tetrachloride as solvent, temperature 20~25℃and 65% oleum as sulfonating agent.
4. The 1,4-dibenzylbenzene has been successfully synthesized with the reactants of benzaldehyde, potassium hydroxide, chloroform and diphenylmethane under concentrated sulfuric acid catalyst. The 1,4-dibenzylbenzene has been also synthesized by the reactants of dichloro-p-xylene and benzene over anhydrous ferric chloride catalyst. The fluorescence spectras of benzene, 1,2-diphenylethane,diphenylmethane and 1,4-dibenzylbenzene were analysised respectively.
一、以十二烷基苯,1,2-二氯乙烷为反应物,在催化剂无水三氯化铝作用下反应合成双烷基二苯乙烷,考察了反应物摩尔比,催化剂的加入量,反应温度,反应时间,溶剂类型对反应的影响。通过研究发现:十二烷基苯在三氯化铝的作用下会发生歧化和重排反应,在现有的实验条件下以十二烷基苯与1,2-二氯乙烷在三氯化铝的催化下反应不能生成二(十二烷基苯基)乙烷。
二、以1,2-二苯乙烷,1-卤代烷为反应物,在催化剂无水三氯化铝作用下反应合成烷基二苯乙烷,考察了不同的反应物摩尔比(1,2-二苯乙烷:1-卤代烷)对目标产物生成的影响。当1,2-二苯乙烷:1-卤代烷(摩尔比)为1:4时,主要产物为多烷基二苯乙烷;当1,2-二苯乙烷:1-卤代烷(摩尔比)是从2:1到4:1的范围,主要产物为单烷基二苯乙烷。
三、以1,2-二苯乙烷,十二酰氯为反应物,环己烷做溶剂,在催化剂无水三氯化铝作用下反应合成双十二酰基二苯乙烷,1,2-二苯乙烷:十二酰氯(摩尔比)为1:2.5时,能较好的得到目标产物4,4-二(十二酰基)二苯乙烷。4,4-二(十二酰基)二苯乙烷进行羰基还原反应,得到4,4-二(十二烷基)二苯乙烷,接着在20~25℃,四氯化碳做溶剂条件下和65%发烟硫酸发生磺化反应,得到双烷基苯型磺酸盐。
四、以苯甲醛,氢氧化钾,三氯甲烷和二苯甲烷为反应物合成出1,4-二苄基苯。以苯和对二氯苄为反应物,在无水三氯化铁催化下,合成出1,4-二苄基苯。并对苯,1,2-二苯乙烷,二苯甲烷,1,4-二苄基苯的荧光光谱进行对比。
Gemini surfactant which has two hydrophilic groups and two hydrophobic groups is a new kind of surfactant with special molecular structure versus the traditional surfactant (only one hydrophilic group and hydrophobic-based).The synthesis of alkylbenzene sulfonates -Gemini surfactant conducted a study on the following work.
1. The dialkyl diphenylethane has planed to be prepared with dodecylbenzene and 1,2-dichloroethane over anhydrous aluminum chloride catalyst. The effect of molar ratio of reactants, catalyst dosage, reaction temperature, reaction time and solvent type on the reaction were also discussed. It was indicated that the dodecylbenzene disproportionation and rearrangement reactions under the aluminum chloride can be taken placed, and then the didodecylbenzeneethane cannot be synthesised under the above reactive conditions.
2. It has been designed to synthesize the alkyl-diphenylethane with reactants of 1,2-diphenylethane and 1-haloalkane over anhydrous aluminum chloride catalyst. Having been carried out the effect of different reactants molar ratio (1,2-diphenylethane : 1-haloalkane) on target product, it was found that the multialkyl diphenylethane was obtained when 1,2-diphenylethane :1-haloalkane is 1:4 (mole ratio), and the monoalkyl diphenylethane was obtained while the mole ratio of 1,2-diphenylethane and 1-haloalkane was from 2:1 to 4:1.
3. The dilauroyl diphenylethane has been successfully synthesized with the reactants mole ratio of 2.5 times of lauroyl chloride to 1,2-diphenylethane under the reaction conditions of cyclohexane solvent and anhydrous aluminum chloride catalyst.The 4,4ˊ-bis (dodecyl) diphenylethane was obtained by carbonyl reduction reaction of 4,4ˊ- bis(dodecanoyl) diphenylethane . The double-alkylbenzene sulfonate was prepared with the sulfonated reaction and neutralization agent. The sulfonation conditions were as follows: carbon tetrachloride as solvent, temperature 20~25℃and 65% oleum as sulfonating agent.
4. The 1,4-dibenzylbenzene has been successfully synthesized with the reactants of benzaldehyde, potassium hydroxide, chloroform and diphenylmethane under concentrated sulfuric acid catalyst. The 1,4-dibenzylbenzene has been also synthesized by the reactants of dichloro-p-xylene and benzene over anhydrous ferric chloride catalyst. The fluorescence spectras of benzene, 1,2-diphenylethane,diphenylmethane and 1,4-dibenzylbenzene were analysised respectively.
引文
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[2] 杨新富.羧酸盐Gemini表面活性剂性质以及与相反电荷普通表面活性剂的相互作用——相行为、表面活性剂、胶团化及流变特性, 福州大学硕士学位论文,2004.
[3] 朱友益.韩冬.沈平平.表面活性剂结构与性能的关系[M]. 石油工业出版社. 2003.
[4] R.Zana, C.Holmberg(Ed.),Novel Surfacanfs:Prearation,Applications and Biodegradability, M.Dekker Inc,New York, 1998, 241 Chapter 8.
[5] R.Zana,H.Levy;D.Papoutsi;G.Beinert;Micellization of two triquatermary ammonium surfactants in aqueous solution. Langmuir 1995,11:3694～3698.
[6] F. M. Menger, C. A. Littau, Gemini-surfactants:synthesis and properties. J. Am. Chem. Soc. 1991, 113:1451～1452.
[7] T.Yoshimura, A.Ohno, K.Esumi.Mixed micellar properties of cationic Trimeric-type quaternary ammonium salts anf anionic sodium n-octyl sulfate surfactants J.Colloid Interface Sci., 2004,272:191～ 196.
[9] R.Zana,Y.Talmon. Dependence of aggregate morphology on structure of dimeric surfactants. Nature, 1993,362:228～230.
[10] M.J.Rosen, Geminis: a new generation of surfactant. Chemtech, 1993,30～33.
[11] Menger F.M.Littau C.A.,Gemini surfactants:A New Class of Self-assembling Molecules, J Am Chem Soc, 1993, 115:10083一10090.
[12] Devinsky F. L., Novel Gemini Micelles from Dimeric Surfactants with Oxyethylene Spacer Chain: Small Angle Neutron Scattering and Fluorescence Studies, J Phys Chem B, 1998, 102(32): 6152一6160 .
[13] Bhattacharya S., Vesicle Formation from Dimeric Surfactants through Ion-pairing:Adjustment of Polar Headgroup Separation Leads to Control over VesicularThermotropic Properties, J Chem Soc, Chem Commun, 1995, 651一655。
[14] Kern H., Lequeux F., Zana R. et al., Dynamical Properties of Salt-Free Viscoelastic Micellar Solutions [J], Langmuir, 1994, 10: 1714一1723.
[15] Menger F. M., Littau C. A., Gemini Surfactants: Sythesis and Properties, J Am Chem Soc,1991, 113:1451一1452。
[16] Zana R., Benrraou M., Rueff R., Alkanediyl-α,ω-bis(dimethylalkylammonium bromide)surfactants 1、Effect of the Spacer Chain Lenghth on the Critical Micelle Concentration and Micelle Ionization Degree, Langmuir, 1991, 7:1072~1075.
[17] 唐世华,李锰,Gemini(孪联)表面活性剂的界面性质与应用,日用化学工业,2001, 31 (6): 26一29
[18] Zana R., Dimeric and Oligomeric Sufactants.Behavior at Interface and in Aqueous Solution:A Review,Advances in Colloid and Interface Science, 2002,97: 205-253.
[19] Zana R., Levy H., Kwetkat K., Mixed Micellization of Dimeric (Gemini)Surfactants and ConventionalSurfactants, 1.Mixtures of an Anionic Dimeric Surfactant and of the Surfactants C12E5 and C12E8, J Colloid Interf Sci, 1998, 197:370~376.
[20] 郑利强,游毅,双子表面活性剂溶液的表面活性的研究,化学学报,2001,59(5):637一642.
[21] Knaebel A., Lamellar Structure in Aqueous Solutions of A Dimeric Surfactant, Langmuir, 2000, 16: 24892494
[22] 刘世伟,新一代表面活性剂双子表面活性剂,新产品世界,1993 (7):57～59
[23] 赵国玺,表面活性剂科学的一些进展,物理化学学报,1997, 13(8):760～768
[24] Zana R., Dimeric (Gemini) Surfactants: Effect of the Spacer Group on the Association Behavior in Aqueous Solution, J Colloid Interf Sci, 2002, 248(2):203220
[26] 付冀峰,杨建新,徐宝财. 二聚表面活性剂的制备、性质与应用[J] . 精细化工,2001,18(1):14~17
[27] Menger F M,Littau C A。Gemini surfactants : a new class of self-assembling molecules [J].J Am Chem Soc,1993,115:10083;Gemini surfactants:synthesis and properties [J].
[28] Bhattacharya S,De S. Vesicle formation from dimeric surfactants through ion-pairing. Adjustment of polar headgroup separation leads to control over vesicular thermotropic properties[J]. J Chem Soc ,Chem Commun,1995,651.
[29] Renouf P,Mioskowski C,Lebeau L. Dimeric surfactants: first synthesis of an asymmetrical Gemini compound [J].Tetrahedron Letters, 1998,39:1357.
[30] Pinazzo A,Diz M,Solans C,et al.Synthesis and properties of cationic surfactants containing a disulfide bond[J]. J Am Oil Chem Soc,1993,70:37.
[31] Zhu Y P,Masuyama A,Kobata Y,et al. Double-chain surfactants with two caroxylate groups and their relation to similar double-chain compounds[J]. J Colloid Interface Sci,1993,158:40.
[32] 李刚.新型高效双子表面活性剂的合成及表面性质研究.郑州大学硕士学位论文,2005.
[33] Voort P V D, Mathieu M, Mees F,Vansant E F.J.Phys.Chem.B,1998,102:448847-448851.
[34] Rosen M,Li F.J.Colliod and Interface Science,2001,234(2):418-424.
[35] Fredric M M, Jason S K Angew. Chem Int,Ed.2000,39:1906-1920.
[36] Patrick Camilleri ,Gemini Surfactants: New Synthetic Vectors for Gene Transfection[J].Angewandte Chemie, 2003, 42(2): 1448-1457.
[37] Chen K D. Journal of Chromatography A, 1998, 822:281-290.
[38] 黄涛,张治民,有机化学实验(第二版)[M].高等教育出版社,1998。
[39] 周科衍,高占先. 有机化学实验(第三版)[M].高等教育出版社,2000.
[40] 梁晓天,核磁共振[M]. 科学出版社,1976。
[41] 张华等,现代有机波谱分析[M]. 化学工业出版社,2005.
[42] 吴谋成,仪器分析[M]. 科学出版社,2003.
[43] 张志德,陈玉琴,耿玉敏. 1,2-二苯乙烷的合成研究[J].精细石油化工,1998,(4):15～17
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