单乙醇胺磷酸酯的合成

358化学试剂2012年4月化学试剂,2012,34(4),358~360单乙醇胺磷酸酯的合成尹振晏,李艳云,梁祎(北京石油化工学院化学工程学院,北京102617摘要:以乙醇胺、磷酸为原料,经酯化反应合成了单乙醇胺磷酸酯。研究了影响反应的因素,化了反应条件。酯化反应的最优条件为:n(乙醇胺):n(磷酸)=1.0:1.4,回流反应5h。经减压蒸馏除去溶剂烷得粗产品,收率达94.0%。再用90%乙醇纯化得目标产品。回收率95.0%。对目标产品进行熔点测定、元素分析和红外光谱表征,可确认该产品为标题化合物。该产品长期依赖进口,该方法已扩大试验,有待实现工业化。关键词:单乙醇胺磷酸酯;乙醇胺;磷酸;酯化;合成中图分类号:TQ423文献标识码:A文章编号0258-3283(2012)04-0358-03单乙醇胺磷酸酯是一种新型的家畜饲料添加学纯,北京化工厂)。剂,属磷酸酯类。国外很早有过研究,但未见1.2反应过程工业化报道;目前国内研究较少,至今未见任何报在装有电动搅拌器、温度计、分水器接冷凝管道。单乙醇胺磷酸酯也是一种重要的阴离子表面的500mL三口瓶中加入150mL癸烷溶剂及活性剂,可广泛应用于化纤、纺织、皮革、塑料造80.7g(0.7mol)85%的磷酸,在10℃以下滴加纸、化妆品等工业领域。它具有优良的抗静电30.5g(0.5mol)乙醇胺,不断搅拌,滴完后加热性与乳化分散性,并有润滑、洗净、耐酸碱等特性,回流反应5h,分出反应生成的水,最后经减压蒸在化妆品领域越来越受到重视。据文献[69报出溶剂,冷却,加入50mL乙醇,搅拌,再移至锥形道,合成其他乙醇胺磷酸酯的工艺路线较多,利用瓶中,冷却结晶,抽滤,得66.3g粗品,收率不同的合成条件和磷酸酯化试剂得到的产物性能94.0%;再经90%乙醇重结晶,收率95.0%差别很大。本文采用磷酸为磷酸酯化试剂合成磷m.p.234237℃(文献值:234~238℃)。元酸酯,与经典的三氯氧磷、五氧化二磷为磷酸酯化素分析,实测值(计算值),%C17.43(17.40);h5.56(5.58);n8.98(9.01)试剂相比原料稳定性高,毒性低工艺简单溶剂循环利用、无污染,具有广泛的应用前景。其合成2结果与讨论路线如下所示。2.1正交方案及结果从对反应的分析以及实验的初步摸索,考察0ch2-ch2O--p--+H2原料物质的量比反应时间溶剂用量等因素对反应的影响,选用三因子三水平正交实验。三因子 OH三水平正交实验方案如表1所示。表1正交实验方案FR-750傅里叶变换红外分光光度计(美国因子1实验部分 ab. Program of orthogonal experiment1.1主要仪器与试剂,3An(乙醇胺):n(磷酸)1.0:1.21.0:1.41.0:1.6 Nicolet公司); Flash EA1112元素分析仪(美国热B反应时间/4.05.06.0电公司);XTA显微熔点测定仪(北京电光科学C溶剂用量/mL150200250仪器厂);SXHW调温型电热套(河北省黄骅市新兴电器厂);SH2-D循环水式真空泵(巩义市英峪予华仪器)。收日:2010708作者介:尹振晏(1963-),男,河北石家庄人本科,则教乙醇胺(化学纯,成都化学试剂厂);85%磷授主要从事生物质及精细化工等方面的研究。酸(化学纯,上海试剂一厂);无水乙醇、癸烷(化通讯作者:李艳 E-mail liyanyun biptduc第34卷第4期尹振晏等:单乙醇胺磷酸酯的合成359正交实验结果见表2。2.5重结晶溶剂的选择表2正交实验结果该产品易溶于水,但结晶困难,而在大多数有 Tab.2 The result of orthogonal experiment机溶剂中溶解度又很小,所以给产品的纯化造成实验号A收率/%一定的困难,经多次试验最后确定:90%乙醇为最B1274.5好,实验结果如表3所示。2C123274.5表3不同试剂中重结晶的结果368.8 Tab.3 The recrystallized result of different reagents312312346.1重结晶试剂无水乙醇90%乙醇水丙酮异丙醇22233323131292.2产品回收率/%85.595.050.380.184.2685.1产品性状加热溶,易溶,不溶,不溶,754.6仍不溶易结晶结晶困难发粘发粘867.410制进行重是验进行结注:取10.0g产品溶于10mL溶剂中进行重结晶实验进行结960.3果比对。M217.80175.20227.00y平均=69.28180.90由表3结果可见,选择90%乙醇作为重结晶M2223.40234.10M,182.30214.20215.60y总值=623.5试剂效果最好。m72.60058.40075.667m274.46778.03360.3003产品IR表征结果m,60.76771.40071.867将纯化所得产品进行红外光谱分析,谱图见.038s0.03310.05980.0384图1所示,各官能团特征吸收峰分析如下。因为对于产物来说收率越高越好,因此从计算出的M得出A2、B2、C1最好。由公式算出的本实验中各S的值可以看出:S2>S3>S1(故表明各因子A、C、B对结果的影响依次减小);磷酸酯25化反应的最优工艺条件为:A2B2C1,即原料物质的量比为:n(乙醇胺):n(磷酸)=1.0:1.4,反应4000300020001000 vlem"时间5h,150mL癸烷溶剂。图1产品的1R谱图2.2原料物质的量比对酯化反应的影响 Fig.1 IR Spectrum of product反应为酯化反应,一般需采用酸催化,所以磷在2906.2cm-1附近为饱和烃的C—H弯曲酸既是催化剂又是酯化试剂,在反应过程中其用振动吸收;2694.1、2642.0cm附近为CH2一量应适当增加,试验结果表明:原料物质的量比为CH2的对称伸缩振动吸收;1452.1cm处为Cn(乙醇胺):n(磷酸)=1.0:1.4为最佳,磷酸过H变形振动吸收;1162.9cm附近存在P一0的少反应不充分,过多则难以去除,也增加成本。振动吸收峰;1085.7和1031.7cm附近为P一2.3加料温度的影响0—C的伸缩振动吸收;765.6cm处有较稳定的磷酸酯化反应对温度的要求很高,而且该反弱吸收峰说明分子中含有多个CH2基团。应放热显著,所以在滴加乙醇胺的过程中需保持由此证实了产品为预期结构的磷酸酯产物。较低温度,以促进酯化反应顺利进行,经实验发现应采取冰盐浴,控制在10℃以下滴加,而且缓慢4结论滴加效果较好。以乙醇胺、磷酸为原料,经酯化反应合成了单2.4反应时间的影响乙醇胺磷酸酯。研究了影响反应的因素,优化了该磷酸酯化反应是在常压下进行的,反应速反应条件,酯化反应的最优条件为:n(乙醇胺):度较慢,而对于大多数酯化反应来说,增加反应时n(磷酸)=1.0:1.4,回流反应5h。经减压蒸馏间可使反应物的转化率提高,反应时间太短反应除去溶剂得粗产品,收率达94.0%用90%的乙不完全,转化率低,但时间过长必然增加成本。经醇纯化得目标产品,收率95.0%试验确定反应最佳时间5h为宜。对目标产品进行熔点测定、元素分析和红外360化学试剂2012年4月光谱表征,可确认该产品为标题化合物。该工艺[9何幼鹭椰油酸单乙醇酞胺磷酸醋的合成与性质研究已进行了工业化实验,可基本实现工业化。[J]武汉生物工程学院学报,2007,3(2):82-84 [10] Kendall Company, Baston, Mass. Method of making 2-参考文献: aminoethyl phosphate: US, 644 603[ P]. 1972-02-22.]EMILIANO V, FERRARI G. Improvents in or relating to[11]阎长泰有机分析基础[M].北京:高等教育出版社, the preparation of 2-amino-ethyl-monophosphste:GB,8861999:31.504[p].1962-01-10 [2] CIBA LIMITED. Complete specification. process for the Synthesis of monoethanolamine phosphate YIN Zhen-yan, ineering manufacture of phosphoric acid esters and piperazine and U Yan-yun'", LIANG College of Chemical Enginering, morpholine derivatives: GB, 861 463[ P]. 1961-02-22. Beijing Institute of Petro-Chemical Technology, Beijing3]王志峰饲料磷酸盐的市场与生产现状[]四川化工102617, China), Huaxue Shiji,2012,34(4),358-360 Abstract: Monoethanolamine phosphate was synthesized by与腐蚀控制,1999,2(2):4447 anolamine a4]姜萍饲用磷酸钙现状与前景[]兽药与饲料添加 etha ine and phosphoric acid as raw materials through剂,1999,4(1):19-20. esterification. Factors influencing the reactions were invesit5]贡长生磷酸醋类表面活性剂的合成和应用[]现at. The experimental conditions were optimized. The opti化工,1996,(9):21-25 mum conditions of the esterification are described as follows n(ethanolamine): n phosphoric acid 1.0: 1.4, refluxed6]张速戎,刘翠华,张舰新型磷酸酯两性表面活性剂的合成及性能研究[J].北京轻工业学院学报,2000,18 for h, 150 mL decane solvent. The product was obtained(1):22-26. with a yield of 94. 0%. After the product was recrystallized with 90% alcohol, the yield was 95.0%. Then the product【7]陈远霞,周海,陈文纳,等油酸二乙醇酰胺磷酸酯的 was determined by the analysis of elements IR and melting合成及其防锈润滑性能研究[】化工技术与开, od has been magified and industri ndustrialize008,37(3):10-13.8]周富荣,邓芳月桂酸二乙醇酸胺磷酸醋盐的合成及 Key words: monoethanolamine phosphate ethanolamine性质[].表面活性剂工业,2000,(4):27-29 phosphoric acid; esterification :synthesis(上接第318页) paration of two novel ditopie ligands derived from Schifr [7] FUSON C, MCKEEVER H. Chloromethylation of aro- base GAO Wei, WANG Qiang'(Engineering Research Center matic compounds J]. Org. React., 1942,1: 63-90.8]刘海彬,王梅新型多溴代水杨醛及其Schif碱配体的8,.cbadeumdho《CkmindChemieIEngncmgchooihmisryandhecalnneng合成与表征[].化学试剂,2010,32(2):102-104 Wuhan Textile University, Wuhan 430020, China), Huaxue []JIN Chun, FAN Wei-bi, JIA Yin-juan, et al. Encapsula- Shiji,2012,34(4),315-318;360 Abstract: 5-Methyl-3-methyle piperidin salicylaldehyde,5. tion of transition metal tetrahydro-Schiff base complexes in zeolite Y and their catalytic properties for the oxidation bromo-3-methylene piperidine salicylaldehyde and 5-bromo-3. methylene morpholine salicylaldehyde were synthesized. ary amine backbone was prepared from condensation of salicylaldehyde and dieth- [10] DEKKERS J, GOODWIN H A. Tridentates and quadri ylenetriamine and the reduced ct with NaBH, was also Mlate Schiff bases from primary diamines]. Ast.. reported. The stability and hy denta lysis of the metal salt com-m.,19662-250 plex with Schiff base d. The compounds were characterized by NMR, IR and MS. Syothesis of several salicylaldehyde derivatives and pre- Key words: salicylaldehyde derivatives; Salen; ditopic ligand(上接第348页) limit of detection was 0. 2 mg/ and the limit of quantificationd mobile phase was methanol-0. I mol/L phosphate buffer (pH was 1. 2 mg/L. The method was simple, rapid, accurate a 3)(60: 40): Uv-210 nm detector the flow rate was 1.0 reproducible and good for the determination of trially isocyam/min. The linear range was from1.0to200.0mg/ as the nurate9 related coefficient was 0. 999 9 and the re ecovery as Key words: high performance liquid chromatography; trially 99.33%. The relative standard derivation was 1. 81%,the isocy ocyanurate;determination