微乳化条件下ECH和TMAC的合成反应及反应动力学研究
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摘要
微乳体系作为一种高度分散的热力学稳定体系，其分散相胶束为纳米级，这一特殊的微环境能对化学反应产生一定的影响，例如能提高分析化学中被检测离子的灵敏度；在无机材料合成方面可用于制备高纯超细颗粒及纳米材料；在生物化学中能形成对蛋白质的保护作用及改变酶的催化效率；在有机液液两相反应中能对反应起强化作用等。
本文应用微乳化方法进行ECH和TMAC的液液两相合成反应，探究该反应中进行微乳化的可行性方案，并配制微乳化体系。液液两相合成反应由于反应物间的相接触程度不佳，制约了反应的进行。微乳体系中油水两相间具有很大的相界面积，能改善两相间的接触，强化反应过程。分别在微乳化条件下和非微乳化条件下进行该合成反应，通过液相色谱分析和气相色谱分析联用的方法分别测定两种条件下不同反应时间的各物质的量，并将所得结果进行比较，实验结果证明微乳体系中的反应速率远高于非微乳体系，其原因在于微乳体系中极大的油水相界面积，而这一区域正好是反应物离子相互接触进行反应的场所，而且表面活性剂的静电效应也对反应速度的增加起了至关重要的作用。本文根据不同温度条件下各物质的量随时间的变化关系，还建立了微乳化条件下ECH和TMAC液液两相合成反应的动力学方程，通过实验数据拟合各动力学方程参数，得
到微乳化条件下的反应动力学方程理论化模型。
Microemulsion is a high-dispersed and stabilized thermodynamic system, where the micells produced by dispersed phase are in nanometer size. Such especial micro-environment can affect chemical reaction, such as enhancing sensitivity of detected ions in analytical chemistry, producing high-pure particulates and nano materials in the synthesis of inorganic materials, protecting protein and altering the catalytic efficiency of enzyme, intensifying some reactions in liquid- liquid phase .
The liquid-liquid bi-phase synthesis reaction of ECH and TMAC was processed in microemulsion，include seeking feasible projects and putting up the microemulsion. In model reaction, because of poor contact of two liquid reactants, synthesis reactions are restricted in liquid- liquid biphase. Microemulsion has large interface area between oil and water phases, which could improve the interface contact and strengthen the reaction. We process liquid-liquid diphase synthesis reaction in microemulsion and in non-microemulsion respectively, measuring and comparing every matter’s molar quantity in different reaction time by combined analysis of LC and GC. The results proved that reaction rates in microemulsion are much higher than ones in non-microemulsion, the rational reason is the large interface area
between oil and water in microemulsion, where the ions of reactants contact and react. In addition, surfactant’s electrostatic effect plays an important role in enhancing the reaction rates. According to the change between every matter’s molar quantity with time in different temperatures, we set up two kinetic equations of liquid-liquid biphase synthesis reaction of ECH and TMAC in microemulsion. Finally kinetic parameters are obtained and the theoretic model is established.
本文应用微乳化方法进行ECH和TMAC的液液两相合成反应，探究该反应中进行微乳化的可行性方案，并配制微乳化体系。液液两相合成反应由于反应物间的相接触程度不佳，制约了反应的进行。微乳体系中油水两相间具有很大的相界面积，能改善两相间的接触，强化反应过程。分别在微乳化条件下和非微乳化条件下进行该合成反应，通过液相色谱分析和气相色谱分析联用的方法分别测定两种条件下不同反应时间的各物质的量，并将所得结果进行比较，实验结果证明微乳体系中的反应速率远高于非微乳体系，其原因在于微乳体系中极大的油水相界面积，而这一区域正好是反应物离子相互接触进行反应的场所，而且表面活性剂的静电效应也对反应速度的增加起了至关重要的作用。本文根据不同温度条件下各物质的量随时间的变化关系，还建立了微乳化条件下ECH和TMAC液液两相合成反应的动力学方程，通过实验数据拟合各动力学方程参数，得
到微乳化条件下的反应动力学方程理论化模型。
Microemulsion is a high-dispersed and stabilized thermodynamic system, where the micells produced by dispersed phase are in nanometer size. Such especial micro-environment can affect chemical reaction, such as enhancing sensitivity of detected ions in analytical chemistry, producing high-pure particulates and nano materials in the synthesis of inorganic materials, protecting protein and altering the catalytic efficiency of enzyme, intensifying some reactions in liquid- liquid phase .
The liquid-liquid bi-phase synthesis reaction of ECH and TMAC was processed in microemulsion，include seeking feasible projects and putting up the microemulsion. In model reaction, because of poor contact of two liquid reactants, synthesis reactions are restricted in liquid- liquid biphase. Microemulsion has large interface area between oil and water phases, which could improve the interface contact and strengthen the reaction. We process liquid-liquid diphase synthesis reaction in microemulsion and in non-microemulsion respectively, measuring and comparing every matter’s molar quantity in different reaction time by combined analysis of LC and GC. The results proved that reaction rates in microemulsion are much higher than ones in non-microemulsion, the rational reason is the large interface area
between oil and water in microemulsion, where the ions of reactants contact and react. In addition, surfactant’s electrostatic effect plays an important role in enhancing the reaction rates. According to the change between every matter’s molar quantity with time in different temperatures, we set up two kinetic equations of liquid-liquid biphase synthesis reaction of ECH and TMAC in microemulsion. Finally kinetic parameters are obtained and the theoretic model is established.
引文
[1] L. M. Prince，Microemulsions Theory and Practice，New York：Academic Press，1977，178~182
[2] K. Shinoda，S. Friberg，Adv Colloid Interface Sci.，1975，4：281~285
[3] M. L. Robbins，Micellization, Solubilization and Microemulsion, New York：Plenum Press，1977，713~715
[4] D. J. Michell，B. W. Ninham，J. Chem. Soc. Faraday Trans，1981，77：601~606
[5] P. A. Winsor，Trans. Faraday Soc，1984，44：376~380
[6] B. Lindman，Microemulsion，New York：Plenum Press ，1982：115～158
[7] R. N. Hwan，J. Colloid Interface Sci.，1979，68：221~225
[8] F. Currie，K. Holmberg，G. Westman，Regioselective nitration of phenols and anisols in microemulsion，Colloid. Surf. A，2001，182：321~327
[9] A. S. Chhatre，R. A. Joshi，B. D. Kulkarni，Microemulsions as media for organic synthesis: selective nitration of Phenol to ortho-nitrophenol using dilute nitric acid，J. Colloid Interf. Sci，1993，158：183~187
[10] F. Currie，K. Holmberg，G. Westman，Bromination in microemulsion，Colloids and Surfaces A：Physicochem. Eng. Aspects，2003，215：51~54
[11] S. Gutfelt，J. Kizling，K. Holmberg，Microemulsions as reaction medium for surfactant systhesis，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1997，128：265~271
[12] R. A. Thompson，S. Allenmark，Factor influencing the micellar catalyzed hydrolysis of long-chain alkyl betainates，J. Colloid Interface Sci，1992，148：241~246
[13] Seong-Geun Oh，Jerzy Kizling，Krister Holmberg，Microemulsions as reaction media for the synthesis of sodium decyl sulfonate 1：Role of microemulsion compositon，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1995，97：169~179
[14] K. Anderson，J. Kizling，K. Holmberg，et al，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1998，144：259~266
[15] Seong-Geun Oh，Jerzy Kizling, Krister Holmberg，Microemulsions as reaction media for synthesis of sodium decyl sulfonate 2.Role of ionic surfactants，Colloids and Surfaces A： Physicochemical and Engineering Aspects，1995，104：217~222
[16] Maria Hager， Krister Holmberg，A substitution reaction in an oil-in-water microemulsion catalyzed by a phase transfer catalyst，Tetrahedron Letters，2000，41：1245~1248
[17] R. Schomacker，K. Stickdorn，W. Knoche，Chemical reactions in microemulsions:
kinetics of the alkylation of 2-alkylindan-1,3-diones in microemulsions and polar organic solvents，J. Chem. Soc. Faraday Trans，1991，87：847~851
[18] 曾宪诚，李启麟，秦自明，王茜，邹萍，李干佐，皇起中，阳、阴、非离子表面活性剂胶束对酯碱性水解的影响，高等学校化学学报，1995，16(6)：937~942
[19] 钱俊红，张晓红，郭荣，CTAB/n－C5H11OH/H2O体系对青霉素G钾盐水解的抑制作用，物理化学学报，2000，16(1)：80~86
[20] 李启麟 邹萍，阴离子和非离子表面活性剂胶束对酯碱性水解反应的影响，四川大学学报（自然科学版），1997，34(1)：71~76
[21] 钱俊红，沈明，郭荣，O/W微乳液对蔗糖水解反应的抑制作用，扬州大学学报.自然科学版，1999，2(3)：13~16
[22] 赵振国，焦天恕，2，4—二硝基氯苯碱性水解胶束催化的活化能，高等学校化学学报，1999，20(2)：281~285
[23] 柴金岭，郝京诚，尚树川，黄汝琪，2，4－二硝基苯氯在微乳液中的水解动力学，应用化学，1999, 16(5):29~32
[24] 柴金岭、肖利华、微乳液中2，4－二硝基氯苯水解反应的研究，环境化学，1999，18(4)：349~353
[25] 何玉萼，张菊仙，胶束催化2，4－二硝基氯苯碱水解反应动力学研究，化学研究与应用，2000，12(2)：234~236
[26] F. M. Menger，A. R. Elrington，Organic reactivity in microemulsion systems，J. Am. Chem. Soc，1991，113：9621~9624
[27] J. H. Ramsder，R. S. Drago，R. Riley，A kinetic study of oxidation by sodium hypochlorite using phase-transfer catalysis，J. Am. Chem. Soc，1989，111：3958~3961
[28] P. Lopez，A. Rodriguez，C. Gomez-Herrera，et al，Oxidation of Fe（CN）64- by S2082- in AOT-oil-water microemulsions，J. Chem. Soc. Faraday Trans，1992，88：2701~2704
[29] M. L. Moya，C. Izquierdo，J. Casado，Microemulsions as a medium in chemical kinetics：The persulfate-iodide reaction，J. Phys. Chem，1991，95：6001~6004
[30] 于澍，李云平，李溪滨，胶束催化氧化合成对硝基苯甲酸，石油化工，2000，29(9)：658~660
[31] Maria Hager，Krister Holmberg，Antonio M. d’A，et al，Oxidation of azo dyes in oil-in-water microemulsions catalyzed by metalloporphyrins in presence of lipophilic acids，Colloids and Surfaces A：Physicochemical and Engineering Aspects，2001，183~185：247~257
[32] L. Tinucci，F. Platone，Eniricherche，EP：0380154，1990-8-1
[33] F. V. Vyve，A. Renken，Hydroformylation in reverse micellar systems，Catal. Today，1999，48：237~243
[34] M. Haumann，H. Koch，P. Hugo，et al，Appl. Catal. A: Gen.，2002，225：239~249
[35] Marco Haumann，Hulya Yildiz，Herbert Koch，et al，Hydroformylation of
7-tetradecene using Rh-TPPTS in a microemulsion，Applied Catalysis A: General，2002，236：173~178
[36] Hydroformylation of Hexene in Microemulsion，Journal of Colloid and Interface Science，2001，244：426~426
[37] Besson, B，Kolck, P，Thorez, A[P]，EP：0179004，1986-4-23
[38] Varre, C，Desbois M，Nouvel.J，Fr：2561650，1985-9-27
[39] Fell, B，Schobben.C，Papadogianakis.G，Hydroformylated homologous ω-alkene carboxylic acid esters with water-soluble rhodiumcarbonyl/triphenylphine-m-trisulfonic acid sodium salt-catalyst，J. Mol. Cata，1995, 101：179~186
[40] T. Bartik，B. Bartik and B. E. Hanson，Aqueous phase rhodium hydroformylation of Octene-1 with trisulfonated tris(ω-phenyl) alkylphosphines and trisulfonated triphenyl phosphine：Reaction selectivity as an indication of rhodium-phosphine complex chemistry，J. Mol. Catal，1994，88：43~56
[41] 花文廷编著，杂环化学[M]，北京：北京大学出版社，1990：39~44
[42] Eugene F. Paschall，Orland Park. Starch ethers containing nitrogen and process for making the same[P]，US：2876217，1959-3-3
[43] Arthur M. Goldstein， Plainview, Erwin M. Heckman，Long Beach et al，Process for making starch ethers[P]，US：3649616，1972-3-14
[44] 松富徹，武田静雄，文野森幸成等，3-氯-2-羟丙基三甲基氯化铵水溶液的制造法[P]，JP：145054，1992-5-19
[45] 杨锦宗，张永华，菅秀君等，3-氯-2-羟丙基三甲基氯化铵的合成方法[P]，CN：1187484A，1998-7-15.
[46] 曾宪诚，李启麟，王茜，泰自明，邹萍，胶束催化进展，化学研究与应用，1996，8（1）：7~12
[47] 刘付方，孙洁，孙惠莲，气相色谱法分析3－氯－2－羟丙基氯化铵中的微量有机杂质，色谱，2002，20(4)：362~363
[48] 赵国玺，朱步瑶，表面活性剂作用原理，北京：中国轻工业出版社，2003，27~51
[49] Joseph L. Deavenport，Bladimir I. Lopez，Process for preparation of halohydroxyproxyl-trialkylammonium halides[P]， US:5463127，1995-10-31
[50] 刘程，表面活性剂应用手册，北京：化学工业出版社，1992，9~10
[2] K. Shinoda，S. Friberg，Adv Colloid Interface Sci.，1975，4：281~285
[3] M. L. Robbins，Micellization, Solubilization and Microemulsion, New York：Plenum Press，1977，713~715
[4] D. J. Michell，B. W. Ninham，J. Chem. Soc. Faraday Trans，1981，77：601~606
[5] P. A. Winsor，Trans. Faraday Soc，1984，44：376~380
[6] B. Lindman，Microemulsion，New York：Plenum Press ，1982：115～158
[7] R. N. Hwan，J. Colloid Interface Sci.，1979，68：221~225
[8] F. Currie，K. Holmberg，G. Westman，Regioselective nitration of phenols and anisols in microemulsion，Colloid. Surf. A，2001，182：321~327
[9] A. S. Chhatre，R. A. Joshi，B. D. Kulkarni，Microemulsions as media for organic synthesis: selective nitration of Phenol to ortho-nitrophenol using dilute nitric acid，J. Colloid Interf. Sci，1993，158：183~187
[10] F. Currie，K. Holmberg，G. Westman，Bromination in microemulsion，Colloids and Surfaces A：Physicochem. Eng. Aspects，2003，215：51~54
[11] S. Gutfelt，J. Kizling，K. Holmberg，Microemulsions as reaction medium for surfactant systhesis，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1997，128：265~271
[12] R. A. Thompson，S. Allenmark，Factor influencing the micellar catalyzed hydrolysis of long-chain alkyl betainates，J. Colloid Interface Sci，1992，148：241~246
[13] Seong-Geun Oh，Jerzy Kizling，Krister Holmberg，Microemulsions as reaction media for the synthesis of sodium decyl sulfonate 1：Role of microemulsion compositon，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1995，97：169~179
[14] K. Anderson，J. Kizling，K. Holmberg，et al，Colloids and Surfaces A：Physicochemical and Engineering Aspects，1998，144：259~266
[15] Seong-Geun Oh，Jerzy Kizling, Krister Holmberg，Microemulsions as reaction media for synthesis of sodium decyl sulfonate 2.Role of ionic surfactants，Colloids and Surfaces A： Physicochemical and Engineering Aspects，1995，104：217~222
[16] Maria Hager， Krister Holmberg，A substitution reaction in an oil-in-water microemulsion catalyzed by a phase transfer catalyst，Tetrahedron Letters，2000，41：1245~1248
[17] R. Schomacker，K. Stickdorn，W. Knoche，Chemical reactions in microemulsions:
kinetics of the alkylation of 2-alkylindan-1,3-diones in microemulsions and polar organic solvents，J. Chem. Soc. Faraday Trans，1991，87：847~851
[18] 曾宪诚，李启麟，秦自明，王茜，邹萍，李干佐，皇起中，阳、阴、非离子表面活性剂胶束对酯碱性水解的影响，高等学校化学学报，1995，16(6)：937~942
[19] 钱俊红，张晓红，郭荣，CTAB/n－C5H11OH/H2O体系对青霉素G钾盐水解的抑制作用，物理化学学报，2000，16(1)：80~86
[20] 李启麟 邹萍，阴离子和非离子表面活性剂胶束对酯碱性水解反应的影响，四川大学学报（自然科学版），1997，34(1)：71~76
[21] 钱俊红，沈明，郭荣，O/W微乳液对蔗糖水解反应的抑制作用，扬州大学学报.自然科学版，1999，2(3)：13~16
[22] 赵振国，焦天恕，2，4—二硝基氯苯碱性水解胶束催化的活化能，高等学校化学学报，1999，20(2)：281~285
[23] 柴金岭，郝京诚，尚树川，黄汝琪，2，4－二硝基苯氯在微乳液中的水解动力学，应用化学，1999, 16(5):29~32
[24] 柴金岭、肖利华、微乳液中2，4－二硝基氯苯水解反应的研究，环境化学，1999，18(4)：349~353
[25] 何玉萼，张菊仙，胶束催化2，4－二硝基氯苯碱水解反应动力学研究，化学研究与应用，2000，12(2)：234~236
[26] F. M. Menger，A. R. Elrington，Organic reactivity in microemulsion systems，J. Am. Chem. Soc，1991，113：9621~9624
[27] J. H. Ramsder，R. S. Drago，R. Riley，A kinetic study of oxidation by sodium hypochlorite using phase-transfer catalysis，J. Am. Chem. Soc，1989，111：3958~3961
[28] P. Lopez，A. Rodriguez，C. Gomez-Herrera，et al，Oxidation of Fe（CN）64- by S2082- in AOT-oil-water microemulsions，J. Chem. Soc. Faraday Trans，1992，88：2701~2704
[29] M. L. Moya，C. Izquierdo，J. Casado，Microemulsions as a medium in chemical kinetics：The persulfate-iodide reaction，J. Phys. Chem，1991，95：6001~6004
[30] 于澍，李云平，李溪滨，胶束催化氧化合成对硝基苯甲酸，石油化工，2000，29(9)：658~660
[31] Maria Hager，Krister Holmberg，Antonio M. d’A，et al，Oxidation of azo dyes in oil-in-water microemulsions catalyzed by metalloporphyrins in presence of lipophilic acids，Colloids and Surfaces A：Physicochemical and Engineering Aspects，2001，183~185：247~257
[32] L. Tinucci，F. Platone，Eniricherche，EP：0380154，1990-8-1
[33] F. V. Vyve，A. Renken，Hydroformylation in reverse micellar systems，Catal. Today，1999，48：237~243
[34] M. Haumann，H. Koch，P. Hugo，et al，Appl. Catal. A: Gen.，2002，225：239~249
[35] Marco Haumann，Hulya Yildiz，Herbert Koch，et al，Hydroformylation of
7-tetradecene using Rh-TPPTS in a microemulsion，Applied Catalysis A: General，2002，236：173~178
[36] Hydroformylation of Hexene in Microemulsion，Journal of Colloid and Interface Science，2001，244：426~426
[37] Besson, B，Kolck, P，Thorez, A[P]，EP：0179004，1986-4-23
[38] Varre, C，Desbois M，Nouvel.J，Fr：2561650，1985-9-27
[39] Fell, B，Schobben.C，Papadogianakis.G，Hydroformylated homologous ω-alkene carboxylic acid esters with water-soluble rhodiumcarbonyl/triphenylphine-m-trisulfonic acid sodium salt-catalyst，J. Mol. Cata，1995, 101：179~186
[40] T. Bartik，B. Bartik and B. E. Hanson，Aqueous phase rhodium hydroformylation of Octene-1 with trisulfonated tris(ω-phenyl) alkylphosphines and trisulfonated triphenyl phosphine：Reaction selectivity as an indication of rhodium-phosphine complex chemistry，J. Mol. Catal，1994，88：43~56
[41] 花文廷编著，杂环化学[M]，北京：北京大学出版社，1990：39~44
[42] Eugene F. Paschall，Orland Park. Starch ethers containing nitrogen and process for making the same[P]，US：2876217，1959-3-3
[43] Arthur M. Goldstein， Plainview, Erwin M. Heckman，Long Beach et al，Process for making starch ethers[P]，US：3649616，1972-3-14
[44] 松富徹，武田静雄，文野森幸成等，3-氯-2-羟丙基三甲基氯化铵水溶液的制造法[P]，JP：145054，1992-5-19
[45] 杨锦宗，张永华，菅秀君等，3-氯-2-羟丙基三甲基氯化铵的合成方法[P]，CN：1187484A，1998-7-15.
[46] 曾宪诚，李启麟，王茜，泰自明，邹萍，胶束催化进展，化学研究与应用，1996，8（1）：7~12
[47] 刘付方，孙洁，孙惠莲，气相色谱法分析3－氯－2－羟丙基氯化铵中的微量有机杂质，色谱，2002，20(4)：362~363
[48] 赵国玺，朱步瑶，表面活性剂作用原理，北京：中国轻工业出版社，2003，27~51
[49] Joseph L. Deavenport，Bladimir I. Lopez，Process for preparation of halohydroxyproxyl-trialkylammonium halides[P]， US:5463127，1995-10-31
[50] 刘程，表面活性剂应用手册，北京：化学工业出版社，1992，9~10