摘要
本论文以N-甲基二乙醇胺与溴代十二烷为原料,分别采用了微波和无溶剂合成的方法,合成了新型的表面活性剂十二烷基甲基二羟乙基溴化铵(DBMAC)。经IR和1H NMR分析鉴定了产物的结构。
通过响应面分析法(RSM)建立了反应转化率与各因素之间的数学关系模型,对微波合成十二烷基甲基二羟乙基溴化铵的工艺进行了优化;确定了最佳反应条件为:溶剂体积为6.90mL,微波功率为636W,反应时间为23min,转化率为92.18%。该法与传统方法相比,合成时间仅为传统方法的5.48%。
无溶剂合成十二烷基甲基二羟乙基溴化铵的最佳反应条件为:温度90℃,反应时间为150min,反应物的摩尔比为1:1,转速为200 r·min-1,转化率为90.2%。将产品进行放大研究,提出了影响放大合成过程和产率的温度梯度及浓度梯度、反应周期等因素的解决方案。
对产物的表面性能和应用性能进行测试研究,得到其表面张力为24.2N·m-1,临界胶束浓度为1.67×10-4mol·L-1,克拉夫点小于0℃,熔点为111.2-111.9℃;其增溶性能、再润湿力很好,有一定的乳化性能、发泡力和柔软性能,以及其对织物白度的影响较小。
同时对表面活性剂十二烷基甲基二羟乙基溴化铵的合成,分别在微波作用以及传统加热两种方式下,通过在不同的沸腾温度下反应,获得微波合成反应的动力学参数,分析微波作用。结果表明,微波的作用没有改变反应级数,两种情况下都是一级反应。微波作用下的活化能为Ea=41.44kJ /mol;而传统加热的活化能为Ea =61.21 kJ /mol。本实验研究提出以单位时间单位容积内,微波作用下反应物的变化量减去相同温度条件下传统加热时的变化量,作为微波对反应速率的贡献量△(-rA )的概念。实验结果表明,在同一温度条件下,反应时间越短,即反应物浓度越高,微波对反应速率的贡献量△(-rA)就越大;在其它条件相同时,反应温度越低,微波对反应速率的贡献量△(-rA)就越大。
A new type cationic surfucant– dodecyl methyl dihydroxyethyl ammonium bro- ide(DBMAC)was syhthesized from N-Methyldiethanolamine and bromododecane in this study. The structure of the product was characterized with IR and 1 H NMR.
Through RSM, the mathematical relational model between conversion rate and factors was established, and the microwave synthesis technique of dodecyl methyl dihydroxyethyl ammonium Bromide was optimized. The results showed that the most suitable condition for the reaction were as follow as: solvent volume was 6.9 mL,the microwave irradiation power was 636 W,the radiation time was 23min,and the yield reached up to 92.18%.Compared with traditional method,the time of synthesis was only 5.48%.
The most suitable condition for the synthesis of dihydroxyethylbenzylmethyl ammonium Bromide was optimized. The results showed as follow as: the temperature was 90℃,the radiation time was 150min,the mole ratio was 1:1, the rotate speed was 200 r·min-1,and the yield reached up to 90.2%. According to the best reaction conditions amplification experiment was made.The amplify of synihesis course was studied,The solvents of influence of temperature grads and concentration grads,and reaction periods etc.
Through determination and study on the surface properties and application performance of DBMAC, the CMC was 1.67×10-4mol·L-1, surface tension was 24.2N·m-1, Krafft Point was below 0℃and melting point of the product was 111.2~111.9℃. At the same time, it showed good solubilization and deuto-wetting property of the surfactant. Its emulsification property, foaming power and softening property were also quite well; besides the effect on fabric whiteness was lower.
The reaction were studied under microwave irradiation and conventional heating on the different boiling temperature point of the solvents. The kinetic parameters were obtained and analysis the effect of microwave.Results show that,the effect of microwave did not alter order of reaction. The activation energy is 41.44kJ /mol under microwave irradiation.while the actactivation energy is 61.21kJ /mol under normal heating. The new concep t of microwave devotion△(-rA) for chemical reaction was proposed in this paper. It is the increment of the reaction rate of microwave reaction and traditional reaction. The experimental result indicated that in the same temperature, the lower reactant concentration, the higher of the microwave devotionΔ(-rA). And the lower of temperature, the higher of the microwave devotionΔ( - rA ).
引文
[1] Dogmak G, Eine neue klasse von disinfection smitteln [J].Dtsch Med Wochenschr.1935, 61:829-831.
[2]郭祥峰,贾丽华.阳离子表面活性剂及应用[M].北京:化学工业出版社,2002:89-134.
[3]包永照.季铵盐的研究进展[J].精细化工.2002,19(8):14-16.
[4]张颖,毛培坤.阳离子表面活性剂在现代工业生产中的应用新进展[J].表面活性剂工业.2000,4:38-41.
[5] Olin J F.3-(Alkylmercapto)-2-hydroxypropyl quaternary ammonium halides[P].U. S:2 548679, Apr 10 ,1951.
[6]陈功,黄鹏程,马云容,等.一种双子表面活性剂的合成[J].精细化工.2001,18(8):440-442.
[7]马家骧,腾凤云.含羟基季铵盐杀生剂的合成[J].南京化工学院学报.1994,16(12): 115- 118.
[8]刘波,司波.氯化十二烷基二甲基羟乙基铵的合成及性能[J].辽宁化工.2006,35(1): 13- 14.
[9]贾丽华,郭祥峰,季富华.二羟基丙基二甲基十二烷基氯化铵的合成及性能[J].精细石油化工.1996,9(5):10-12.
[10]冯薇,傅德才.多功能季铵盐型阳离子表面活性剂的合成及应用[J].印染助剂.1995,12(1):12-15.
[11]赵剑曦.新一代表面活性剂:Geminis[J].化学进展.1999,11(4):348-357.
[12]杨栋梁.织物的柔软整理(二)[J].印染助剂.1999 ,16(2):35-36.
[13]周绍箕.阳离子型柔软剂的合成、性能及应用[J].印染助剂.2002,19(3):1-5.
[14]钟宛芸.织物柔软剂的应用概况[J].精细化工.2002,19(增刊):116-117,121.
[15]邹文苑.织物柔软剂的发展趋势[J].日用化学品科学.1999 ,(5):11-16.
[16]黄茂福.纺织助剂的基本特性,检测与应用(二) :柔软剂[J ] .染整科技.1996 , (4):46-55.
[17]王宇明,任秀艳,李晓岭.阳离子表面活性剂用于消除涤纶纤维静电[J].吉林工学院学报.2002,3(2):45-46.
[18]张亨.抗静电研究进展[J].精细石油化工进展.2000,1(9):39-43.
[19]刘磊力,王正祥,张广友.阳离子表面活性剂发展概况[J].精细化工.1997,11(2):144-148.
[20]孙记夫,李秋小,李运玲.双癸基甲基羟乙基氯化铵的合成与杀菌性能[J].精细化工. 2008,25(6):565-569.
[21]常青春.季铵盐型阳离子表面活性剂的发展及应用[J].佳木斯大学学报.2003,21 (4):503-506.
[22]Omo A M A ,Abdel Khalek. Cationic surfactants flotation collectors[J]. Tenside.1997,34 (3):78.
[23]王则臻,宋召霞,孙亚文.降解壳聚糖季铵盐的制备及其在亚麻染色中的应用[J].应用科技.2009,17(22) :16-18.
[24]黄卡玛,杨晓庆.微波加快化学反应中非热效应研究的新进展[J].自然科学展.2006,(3):273-279.
[25]孙晓娟,苏跃增,金凤明.微波化学非热效应初探[J].江苏石油化工学院报.2000,3(12): 42-44.
[26]R N Gedye.Microwave assisted syntheses in household microwave ovens [J]. Tetrahedron Letters.1986,27(3):279-283.
[27]许家喜.微波与有机化学反应的选择性[J].化学进展.2007,19(5):700-712.
[28]雷向欣,李俊,沈瀛坪.微波对乙酸甲酯水解的作用及反应动力学研究[J].化学反应工程与工艺.2002,18(3):97-102.
[29]杨晓庆.微波与反应系统的相互作用特殊效果研究[D].四川大学,2006.
[30]王娟娟,汪明芳,张关永.S-苯基-L-半胱氨酸合成的反应动力学及反应机理的研究[J].化学世界.2007,(5):257-261.
[31]Bose AK.Highly accelerated reaetions in a mierowave oven [J]. Synthesis of Heteroeyele, 1991,30(2):742-749.
[32]M. Antonia Herrero,Jennifer M. Kremsner,C. Oliver Kappe. Nonthermal Microwave Effects Revisited: On the Importance of Internal Temperature Monitoring and Agitation in Microwave Chemistry[J]. J. Org. Chem.,2008,73 (1):36-47.
[33]金钦汉.微波化学[M].北京:科学出版社,1999.
[34]张志斌,周兰香.不同频率微波辐照合成二苯硫脲[J].扬州大学学报(自然科学版),2000, 3 (4):14-16.
[35]S Horikoshi,T Hamamura ,M Kajitani et al.Green Chemistry with a Novel 5.8-GHz Microwave Apparatus. Prompt One-Pot Solvent-Free Synthesis of a Major Ionic Liquid: The 1-Butyl-3-methylimidazolium Tetrafluoroborate System[J]. Org. Process Res. Dev.2008,12 (6) :1089～1093.
[36]黄卡玛,杨晓庆.微波加快化学反应中非热效应研究的新进展[J].自然科学进展.2006, 3(16):273-278.
[37]王禹,孙海涛,王宝辉等.微波的热效应与非热效应[J].辽宁化工,2006,35(3):167-169.
[38]S Kalhori,B Minaev,S Stone-Elander et al. Quantum Chemical Model of an SN2 Reaction in a Microwave Field[J]. J . Phys. Chem. A.2002,106 (37) :8516-8524.
[39]许家喜.微波与有机化学反应的选择性[J].化学进展.2007,19 (5):700-712.
[40]Haswell S J,Howarth N.Perturbation of a solid phase separation process by a non-thernal microwave effect[J].Analytica Chimica Acta.1999,387:113-120.
[41]Barnhardt E K.Advancing rnicrowave energy to new heights with simultancous cooling.European Science Foundation Exploratory Workshop [J]. Scientific Reporton Microwave Chemistry and Specific Microwave Effects,Austria,2005:19.
[42]H Shimizu,Y Yoshimura,H Hinou et al. Microwave Promoted organic reaction[J]. Tetrahedron,2008 ,64 :10091-10096.
[43]J G P Binner,N A Hassine,T E Cross. The possible role of the pre-exponential factor in explaining the increased reaction rates observed during the microwave synthesis of titanium carbide[J]. J . Mater. Sci.1995,30 :5389-5393.
[44]G Sivalingam,N Agarwal,G Madras. .Photocatalytic degradation of various dyes by Combustion synthesized nano anatase TiO2.[J]. J . Appl . Polym. Sci.2004,91:1450-1456.
[45]S Chatti,M Bortolussi,A Loupy. Synhtesis of diethers derives from diahnydrohextiols by Phase transfer catalysis under mierowave[J]. Tetrhaedron Letter.2000,41(18):3367- 3370.
[46]Tanaka K,Toda F. Solvent - free Organic Synthsis[J ].Chen Rev.2000 ,100(3):1025-1074.
[47]李晓陆,王永梅,孟继本.固态有机合成新进展[J ].有机化学.1998 ,18 (1):20-28
[48]藏洪俊,李正名,王宝雷.固态有机合成反应进展[J ].有机化学.2003,23 (10):1058-1063.
[49]王兰明.固态有机合成反应[J ] .化学通报.1992 , (6) :14-18.
[50] (日)田中孝一.无溶剂有机合成[M].刘群. 1-1.化学工业出版社,2005:1-484.
[51]Rasmussen M O,Axelsson O ,Tanner D A. Practical Procedure for the Solid - phade Synthesis of Racemic 2 ,2- Dihydroxy-1 ,1′-binaphthyl[J ].Synth Commun,1997, (23) :4027-4030
[52]Ghiaci M, Imanzadeh G H. A Facile Beckmann Rearrangement of Oximes with AlCl3 in the Solid State[J ].Syngy Commun,1998,28 (12) :2275-2280.
[53]李汝雄,王建基.无溶剂有机合成[J ].化学通报.2003 ,66 (3) :W020.
[54]F Toda , KMori. Enantioselective reduction of ketones in optically active host compounds with a borane - ethylenediamine complex in the solid state[J ] . Chem. Commun.1989, (17):1245 - 1246.
[55]F Toda, K Tanaka. Design of a new chiral host compound trans-4 ,5-bis(hydroxydiphenyl methyl)-2 ,2-dimethyl-1. 3-dixacyclopentane. An effective optical resolution of bicyclic enones through host-guese complex formation[J ] .Tetrahed. Lett.1988 , 29(5):551 - 554.
[56]金津.微波作用下染料等有机化合物的固态合成研究[D].天津:南开大学,1999.
[57]Bram G,Loupy A ,Majdoub M. Microwave Irrdiation Plus Solid -lipuid Phase Transfer Catalysis without Solvent :Further Improvement in Anionic Activation[J ]. Syngy Commun ,1990 ,20 (1) :125-129.
[58]尹显洪.微波干介质反应[J ].化学通报.2003 , (6) :393-403.
[59]李慧章,李同双,于涛等.微波辐射下苯偶姻的干法氧化反应[J ]..有机化学.1998,18 (2) :180-182.
[60]Kidwei M,Misra P ,Bhushan K R. Microwave Assisted Synthesis of Novel Organomercurials in Dry Media[J ]. Polyhedron ,1999 ,18 (20) :2641-2643
[61]朱新海,陈功,许遵乐等.甲酸催化的室温无溶剂条件下利用Paal-Knorr合成吡咯衍生物的方法[J].有机化学.2008,28(1):115-119.
[62]赵辉,于海丰,林春.无气味的4,4-二乙硫/苄硫基-3-烯-2-丁酮作乙/苄硫醇代替试剂的无溶剂缩硫醛/酮化反应[J].北华大学学报(自然科学版).2008,9(3):210-212.
[63]Lang J . P. , Xin X. Q. Solid state synthesis of Mo (w) - S cluster compounds at low heating temperatures [J ]. J . Solid State Chem.1994,108 (1):118-127.
[64]Xin X. Q. , Zheng L. M. Solid state reactions of coordination compounds at low heating temperatures[J ] . J . Solid State Chem.1993,106 (2):451-460.
[65]王夔.化学进展与化学教育的前景[J ] .大学化学.1995 ,10 (6) :5.
[66]李晓陆,王永梅,杜大明,等.含氮杂环化合物固相化学反应研究——Ⅱ.吲哚与羰基化合物的固相化学反应[J ] .中国科学,B辑.1997 ,27 (3) :202 - 207.
[67]李晓陆,杜大明,王永梅,等.含氮杂环化合物固相化学反应研究——Ⅰ. 3-甲基-1-苯基-5-吡唑啉酮与羰基化合物的固相反应[J ] .中国科学,B辑.1997 ,27 (2) :104-111.
[68]丁奎岭,王洋,吴养洁,等.固态“绝对”不对称合成[J ] .有机化学.1996 ,16 (1) :1-10.
[69]Meng J . B. , Wang W. G. , Xiong G. X. et al. Solid-state photochemistry of indoles with naphthalene and phenanthrene [J ]. J .Photochem. Photobiol. A: Chem. 1993,57(4):597- 602.
[70]崔易.胭脂虫天然红色素反应纯化工艺研究[D].西北大学,2007:19.
[71]孙曼灵,郑高锋.胺类环氧固化剂胺值测定方法的探讨[J].热固性脂.2006,21(2):31-32.
[72]谢瑜,张昌辉,徐旋.三烷基季铵盐阳离子表面活性剂的合成研究[J].2007,10(16):10-13.
[73]Wang Fenghe,Wang Jing,Lei Wu.et al. Study of Steam Stripping Process during Synthesis of 3 - Chloro-2-Hydroxypropyl Trimethyl Ammonium Chloride [J].Advances in Fine Fetrochemicals.2002(9):29-31.
[74]张智宏,沈钟,邵长生.新型季铵盐型表面活性剂应用研究[J].日用学工业,1999,(3):1-3.
[75]查敏,丁运.Gemini型表面活性剂的研究与应用进展[J].日用化学品科学.2008,31(3):14 -16.
[76]张建华,杨瑜蓉,张水凤.吸收光谱线型分析用于十六烷基溴化铵临界胶束浓度的测量[J].应用化学,2007,24(3):306-309.
[77]毛培坤.表面活性剂产品工业分析[M].化学工业出版社2003:508.
[78]郑宝江.驱油用阴离子Gemini表面活性剂的制备及性能表征[D].天津:天津大学,2005.
[79]金瑞娣,张跃华. Gemini型磺基琥珀酸酯钠表面活性剂的结构与性能的关系[J].化学研究与应用.2008,2(20):158-161.
[80]王友国,王佩维,姚晨之等.不同酯化度的酯基季铵盐的制备和性能研究[J].日用化学工业.2005,35(3):145.
[81]张昌辉,谢瑜,曹娟.一种季铵盐阳离子表面活性剂的合成与性质[J].日用化学工业,2007,37(6):364-416.
[82]冯玉军,孙玉海,陈志等.双子表面活性剂的应用[J].精细与专用化学品.2006,(14):12 -21.
[83]张昌辉,谢瑜,徐旋.表面活性剂在纺织工业中的应用及发展[J].日用化学工业.2008,31 (1):19-23.
[84]刘彩娟.表面活性剂的应用与发展[J].河北化工.2007,30(4):20-21.
[85]袁先友.微波促进杂多酸催化精细有机化学品合成的应用研究[D].湘潭大学,2005, (25):1049-1052.
[86]Emil C Buruiana,Tinca Buruiana. Synthesis and characterization of novel polyurethane cationomers with dipeptide sequences and alkylammonium groups[J].Journal of Biomaterials Science (Polymer Edition),2004,15(6):781–795.