358化學試劑2012年4月化學試劑,2012,34(4),358~360單乙醇胺磷酸酯的合成尹振晏,李艷云·,梁祎(北京石油化工學院化學工程學院,北京102617)摘要:以乙醇胺、磷酸為原料,經(jīng)酯化反應合成了單乙醇胺磷酸酯。研究了影響反應的因素,優(yōu)化了反應條件。酯化反應的最優(yōu)條件為:n(乙醇胺):n(磷酸)=1.0:1.4,回流反應5h。經(jīng)減壓蒸餾除去溶劑癸烷得粗產(chǎn)品,收率達94.0%。再用90%乙醇純化得目標產(chǎn)品?；厥章?5.0%。對目標產(chǎn)品進行熔點測定、元素分析和紅外光譜表征,可確認該產(chǎn)品為標題化合物。該產(chǎn)品長期依賴進口,該方法已擴大試驗,有待實現(xiàn)工業(yè)化。關鍵詞:單乙醇胺磷酸酯;乙醇胺;磷酸;酯化;合成中圖分類號:TQ423文獻標識碼:A文章編號:0258-3283(2012)04035803單乙醇胺磷酸酯是一種新型的家畜飼料添加學純,北京化工廠)劑,屬磷酸酯類。國外很早有過研究12,但未見1.2反應過程工業(yè)化報道;目前國內(nèi)研究較少,至今未見任何報在裝有電動攪拌器、溫度計、分水器接冷凝管道。單乙醇胺磷酸酯也是一種重要的陰離子表面的500mL三口瓶中加人150mL癸烷溶劑及活性劑,可廣泛應用于化纖、紡織、皮革、塑料、造80.7g(0.7ml)85%的磷酸,在10℃以下滴加紙、化妝品等工業(yè)領域3。它具有優(yōu)良的抗靜電30.5g(0.5mol)乙醇胺,不斷攪拌,滴完后加熱性與乳化分散性,并有潤滑洗凈、耐酸堿等特性,回流反應5h,分出反應生成的水,最后經(jīng)減壓蒸在化妝品領域越來越受到重視。據(jù)文獻[69]報出溶劑,冷卻,加入50mL乙醇,攪拌,再移至錐形道,合成其他乙醇胺磷酸酯的工藝路線較多,利用瓶中,冷卻結(jié)晶,抽濾,得663g粗品,收率不同的合成條件和磷酸酯化試劑得到的產(chǎn)物性能%4.0%;再經(jīng)90%乙醇重結(jié)晶,收率95.0%。差別很大。本文采用磷酸為磷酸酯化試劑合成磷p234~237℃(文獻值:234~238℃)。元酸酯,與經(jīng)典的三氯氧磷、五氧化二磷為磷酸酯化素分析,實測值(計算值),%:C17.43(17.40);H5.56(5.58);N8.98(9.01)試劑相比,原料穩(wěn)定性高,毒性低,工藝簡單、溶劑循環(huán)利用、無污染,具有廣泛的應用前景。其合成2結(jié)果與討論路線如下所示。2.1正交方案及結(jié)果H, N-CH2-CH2 -OH+H,PO-+從對反應的分析以及實驗的初步摸索,考察原料物質(zhì)的量比、反應時間溶劑用量等因素對反H2N一CH2-CH10P0+H2O應的影響,選用三因子三水平正交實驗。三因子三水平正交實驗方案如表1所示。衰1正交實驗方案1實驗部分Tab1 Program of orthogonal experiment1.1主要儀器與試劑FIR750傅里葉變換紅外分光光度計(美國n(乙醇胺)n(磷酸)1.0:1.21.0:141.0:1.6Nicole公司); Flash EA1112元素分析儀(美國熱B反應時間/h電公司);XTA顯微熔點測定儀(北京電光科學c溶劑用量/mL50200250儀器廠);SXHW調(diào)溫型電熱套(河北省黃驊市新興電器廠);SH2D循環(huán)水式真空泵(鞏義市英峪予華儀器廠)。收稿日期:201107408作者蒿介:尹振中國煤化工陣則教乙醇胺(化學純,成都化學試劑廠);85%磷授,主要從事生物CNMHG酸(化學純,上海試劑一廠);無水乙醇、癸烷(化通訊作者:李艷云,E-mne bipt. edu. caa第34卷第4尹振晏等:單乙醇肢磷酸酯的合成359正交實驗結(jié)果見表22.5重結(jié)晶溶劑的選擇豪2正交實驗結(jié)果該產(chǎn)品易溶于水,但結(jié)晶困難,而在大多數(shù)有Tab. 2 The result of orthogonal experiment機溶劑中溶解度又很小,所以給產(chǎn)品的純化造成實驗號收率/%定的困難,經(jīng)多次試驗最后確定:90%乙醇為最74.5好,實驗結(jié)果如表3所示。表3不同試劑中重結(jié)晶的結(jié)果在68.8Tab. 3 The recrystallized result of different reagents46.1重結(jié)晶試劑無水乙醇90%乙醇水異丙醇222392.295.0231產(chǎn)品回收率/%85.550.3加熱易溶,不溶,不溶,產(chǎn)品性狀54.6仍不溶易結(jié)晶結(jié)晶困難發(fā)粘發(fā)粘注:取10.0g產(chǎn)品溶于10mL溶劑中進行重結(jié)晶實驗進行結(jié)60.3比對217.80175.20227.0069.28由表3結(jié)果可見,選擇90%乙醇作為重結(jié)晶試劑效果最好。182.30214.20215.60y總=623.575.66774.4660.3003產(chǎn)品IR表征結(jié)果將純化所得產(chǎn)品進行紅外光譜分析,譜圖見0.0331圖1所示,各官能團特征吸收峰分析如下。因為對于產(chǎn)物來說收率越高越好,因此從計算出的M得出A2、B2、C1最好。由公式算出的本實驗中各S的值可以看出:S2>S>S1(故表明各因子A、C、B對結(jié)果的影響依次減小);磷酸酯化反應的最優(yōu)工藝條件為:A2B2C1,即原料物質(zhì)的量比為:n(乙醇胺):n(磷酸)=1.0:14,反應2000時間5h,150mL癸烷溶劑。圖1產(chǎn)品的IR譜圖2.2原料物質(zhì)的量比對酯化反應的影響Fig 1 IR Spectrum of product反應為酯化反應,一般需采用酸催化,所以磷在2906.2cm1附近為飽和烴的C一H彎曲酸既是催化劑又是酯化試劑,在反應過程中其用振動吸收;269412642.0cm附近為CH2量應適當增加試驗結(jié)果表明:原料物質(zhì)的量比為CH2的對稱伸縮振動吸收;1452.1cm處為Cn(乙醇胺):n(磷酸)=1:1.4為最佳磷酸過H變形振動吸收;1162.9cm附近存在P-0的少反應不充分,過多則難以去除,也增加成本。振動吸收峰;10857和1031.7cm附近為P2.3加料溫度的影響0—C的伸縮振動吸收;7656cm處有較穩(wěn)定的磷酸酯化反應對溫度的要求很高,而且該反弱吸收峰,說明分子中含有多個CH2基團。應放熱顯著,所以在滴加乙醇胺的過程中需保持由此證實了產(chǎn)品為預期結(jié)構(gòu)的磷酸酯產(chǎn)物。較低溫度,以促進酯化反應順利進行,經(jīng)實驗發(fā)現(xiàn)應采取冰鹽浴,控制在10℃以下滴加,而且緩慢4結(jié)論滴加效果較好。以乙醇胺磷酸為原料,經(jīng)酯化反應合成了單2.4反應時間的影響乙醇胺磷酸酯。研究了影響反應的因素,優(yōu)化了該磷酸酯化反應是在常壓下進行的,反應速反應條件酯化反應的最優(yōu)條件為:n(乙醇胺)度較慢,而對于大多數(shù)酯化反應來說,增加反應時n(磷酸)=1.0:1.4,回流反應5h。經(jīng)減壓蒸餾間可使反應物的轉(zhuǎn)化率提高反應時間太短反應除去溶劑得粗盧中國煤化工0%的乙不完全,轉(zhuǎn)化率低,但時間過長必然增加成本。經(jīng)醇純化得目標CNMH試驗確定反應最佳時間5h為宜。對目標產(chǎn)品進點測足、兀系分忻和紅外360化學試劑2012年4月光譜表征,可確認該產(chǎn)品為標題化合物。該工藝[9]何幼鶯椰油酸單乙醇酞胺磷酸醋的合成與性質(zhì)研究已進行了工業(yè)化實驗,可基本實現(xiàn)工業(yè)化。[門]武漢生物工程學院學報,20073(2):8284[10 ]Kendall Company, Baston, Mass. Method of making 2參考文獻:aminoethyl phosphate: US, 3 644 603[P].1972-02-22[1JEMILIANO V, FERRARI G Improvents in or relating to[11]閻長泰有機分析基礎[M].北京:高等教育出版社1999:31he preparation of 2-amino-ethyl-monophosphste GB, 886504[P].196201-10[2]CIBA LIMITED. Complete specification. process for the Synthesis of monoethanolamine phosphate YIN Zhen-yananufacture of phosphoric acid esters and piperauI Yan-yun, LIANG Yi( College of Chemical Engineeringne anmorpholine derivatives: GB, 861 463[P].1961-02-22Beijing Institute of Petro-Chemical Technology, Beijing[3]王志峰.飼料磷酸鹽的市場與生產(chǎn)現(xiàn)狀[J].四川化工102617, China), Huaxue Shij,2012,34(4),358-360與腐蝕控制,1999,2(2):4447Abstract: Monoethanolamine phosphate was synthesized by[4]姜萍.飼用磷酸鈣現(xiàn)狀與前景[].魯藥與飼料添加ethanolamine and phosphoric acid as raw materials throughesterification. Factors influencing the reactions were invest-劑,1999,4(1):1920[5]貢長生磷酸醋類表面活性劑的合成和應用[冂]現(xiàn)代tal conditionsnized. The opti-mum conditions of the esterification are described as follows化工,1996,(9):21-25.[6]張涑戎,劉翠華,張艦新型磷酸酯兩性表面活性劑的(ethanolamine): n( phosphoric acid ) 1.0: 1. 4, refluxed合成及性能研究[J].北京輕工業(yè)學院學報,2000,18for 5 h, 150 mL decane solvent. The product was obtained(1):2226with a yield of 94. 0%. After the product was recrystallized[7]陳遠霞周海陳文納,等油酸二乙醇酰胺磷酸酯的wih90% alcohol, the yield was95.0%. Then the product合成及其防銹潤滑性能研究[J].化工技術與開發(fā)was determined by the analysis of elements, IR and meltingnt. The method has been magnified and industrialized2008,37(3):10-13[8]周富榮鄧芳月桂釀二乙醇酸胺磷酸醋鹽的合成及 ey words: monoethanolamine phosphate; ethanolamine性質(zhì)[JJ表面活性劑工業(yè),2000,(4):2729phosphoric acid; esterification; synthesis(上接第318頁)paration of two novel ditopic ligands derived from Schiff[7]FUSON R C, MCKEEVER C H Chloromethylation of aro. base GAO Wei,WANG Qiang(Engineering Research Centermatic compounds[ J]. Org. React., 1942, 1: 63-90for Clean Production of Textile Dyeing and Printing, Ministry[8]劉海彬,王梅新型多溴代水楊醛及其Schi堿配體的of Education, School of Chemistry and Chemical Engineering合成與表征[].化學試劑,2010,32(2):102-104Wuhan Textile University, Wuhan 430020, China ), Huaxue[9]JIN Chun, FAN Wei-bi, JIA Yin- juan, et al. EncapsulaShji,2012,34(4),315-318;360Abstract: 5-Methyl-3-methylene piperidin salicylaldehyde,5-tion of transition metal tetrahydro schiff base complexesbromo-3-methylene piperidine salicylaldehyde and 5-bromo-3in zeolite Y and their catalytic properties for the oxidationmethylene morpholine salicylaldehyde were synthesizedof cycloalkanes[ J].J. Mol. Catal. A: Chem., 2006, 249Salen-type Schiff base containing a secondary amine backbone(1/2):23-30was prepared from condensation of salicylaldehyde and dieth10 ]DEKKERS J, GOODWIN H A. Tridentates and quadri- ylenetriamine and the reduced product with NaBH, was alsedentate Schiff bases from primary diamines[ J].Aust. J.reported. The stability and hydrolysis of the metal salt com-Chem.,1966,19(12):2241-2250plex with Schiff base were demonstrated. The compounds werecharacterized by NMR, IR and MsSynthesis of several salicylaldehyde derivatives and pre- Key words: salicylaldehyde derivatives; Salen; ditopic ligand(上接第348頁)limit of detection was 0. 2 mg/L and the limit of quantificationmobile phase was methanol. 1 mol/L phosphate buffer( pHwas 1.2 mg/L. The method was simple, rapid, accurate and3)(60: 40): UV-210 nm detector the flow rate was 1.0 reproducible and good for the determination of trially isocyamL'min. The linear range was from 1.0 to 200. 0 mg/L as therelated coefficient was 0.999 9Key words: high中國煤化工;may99.33%.The relative standard derivation was 1.81% the isocyanurate; determiHCNMHG