表面活性剂的合成

Chapter7表面活性剂的合成7.1阴离子表面活性剂的合成一．阴离子表面活性剂的分类1.羧酸盐型（-COOH）代表：C17H35COONa硬脂酸钠R-CON-CH2COONaCH3N-甲基酰胺羧酸盐R-CO-NCONnRRCOONa雷米邦2.磺酸盐型（－SO3Na）代表：SO3NaR————烷基苯磺酸盐SO3NaR－烷基磺酸盐CH-CH2SO3NaR－CHa－烯基磺酸钠C17H33CONCH2CH2SO3NaCH3N－甲基油酰胺牛磺酸钠NaO3S-CH-COORCH-COOR琥珀酸磺酸盐3.硫酸酯盐型（－OSO3Na）代表：OSO3NaR－脂肪醇硫酸钠CH2CH2OnR－O脂肪醇聚氧乙烯醚硫酸钠4.磷酸酯盐型（－OPO3Na）ROPNaOONaO单酯ROPROONaO双酯二、磺酸基的引入方法1.烷基苯磺酸盐H2SO4SO3HNaOHSO3HR－+浓R－R－2.烷基磺酸盐⑴磺氯化工艺（氯磺化工艺）SO2Cl2RSO2ClRH+++HClhvRSO2ClRSO3Na+2NaOH+NaCl+H2O该反应属自由基反应，机理如下：Cl2SO2RSO2RSO2Cl2RSO2Clhv2Cl.Cl.+RHR.R.+..++Cl.（主）（次）⑵磺氧化工艺（氧磺化工艺）SO2O2RSO3HRH++30℃反应机理为：SO2SO2SO2SO2SO2RSO2RSO2Cl2RSO2OORSO2OORSO2OORSO2OOSO2RSO3HH2SO4RSO2ClRSO3NaRHR.+H.（基态）hvhv*（激发态）RH+*R.+H.+R.+..+.烷基过氧磺酰自由基.+RHH+R.烷基过氧磺酸H++++2NaOH+NaCl+H2OH2O3.α－烯基磺酸盐（AOS）CH2CHCH2SO3CHCH2SO3NaCH2CH2SO3NaOHR－+NaOHRCH或R－CHCH2SO3HHCH2SO2HCH2CHCHSO3HHCHCHCH2SO3H－CHδ+δ-+SOOOδ+δ-亲电加成－CH－CH－CH－+-31周环－－CH－CHO1,2－磺内酯消除1－烯基磺酸消除3－烯基磺酸4.琥珀酸酯磺酸盐琥珀酸即丁二酸琥珀酸酯双酯磺酸盐单酯磺酸盐NaO3S-CH-C-ONaCH-C-OROONaO3S-CH-C-ORCH-C-OROO'引入磺酸基的方法：通过亚硫酸钠与马来酸（顺丁烯二酸）酯的加成反应。CH-C-ONaCH-C-ORNaHSO3NaO3S-CH-C-ONaCH-C-OROO(R')+OO(R')a.渗透剂AerosolOT（快速渗透剂OT）CH3(CH2)3CHCH2OHC2H5H2SO4-H2OCH2CH(CH)3CH3CH2CH(CH)3CH3C2H5C2H5CH－COCH－COO+2CH－COCH－COOONaHSO3CH2CH(CH)3CH3CH2CH(CH)3CH3C2H5C2H5NaO3SCH－COCH－COOOb.脂肪醇聚氧乙烯醚琥珀酸单酯磺酸钠，如AESM或AESS，有良好的乳化、分散、润湿和增溶效果。月桂醇聚氧乙烯醚琥珀酸单酯磺酸钠C12H25O(CH2CH2O)3HC12H25O(CH2CH2O)3OCCHNa2SO3C12H25O(CH2CH2O)3OCCHSO3Na+CH－CCH－COOOCatCHCOOHCHCOONa25.高级脂肪酰胺磺酸盐(CH2)2SO3NaR'CONRR'=H或烷基a.羟基磺酸盐的合成(CH2)2SO3NaNaHSO3H-C-HHOCH2SO3NaNaHSO3CH2-CH2HOCH2CH2SO3NaNaHSO3CH2-CH-CH2ClClCH2CHCH2SO3NaOHR'CONRR'=H或烷基+O+O+Ob.氨基烷基磺酸盐的合成由羟基磺酸盐在高温高压下与有机胺反应制得RNH2HOCH2SO3NaRNHCH2SO3NaRNH2HOCH2CH2SO3NaRNHCH2CH2SO3Na++++H2OH2O另外，ClCH2CH2ClNa2SO3ClCH2CH2SO3NaRNH2RNHCH2CH2SO3Na+-HClc.最终产物——表面活性剂的合成RNHCH2SO3NaR'CONCH2SO3NaRNHCH2CH2SO3NaR'CONCH2CH2SO3NaRNHCH2CHCH2SO3NaR'CONCH2CHCH2SO3NaR'COCl+RR'COCl+RR'COCl+ROHOH实例：a.净洗剂209Igepon（依加邦）C17H33CONCH2CH2SO3NaCH3NaHSO3CH2-CH2HOCH2CH2SO3Na+O①T:70－80℃P:26.7KPa保温110×1.5hCH3NH2HOCH2CH2SO3NaCH3NHCH2CH2SO3Na+②C17H33COOHPCl3C17H33COCl3+3③C17H33COClCH3NHCH2CH2SO3NaC17H33CONCH2CH2SO3NaCH3+④N－油酸基－N－甲基牛磺酸钠b.净洗剂LSC17H33CONHSO3NaOMeC17H33COOHPCl3H3PO3C17H33COClH2NOMeSO3H2NSO3HOMeC17H33COClH2NSO3HOMeC17H33CONHSO3NaOMe+3++三、硫酸酯盐类表面活性剂①SO3作硫酸化试剂R-OHSO3R-OSO3HROSO3Na+NaOH如AESRO(C2H4O)HSO3OSO3HC2H4OnOSO3NaC2H4On+RONaOHRO②浓H2SO4硫酸化C12H25OHH2SO4C12H25OSO3H++H2O③氯磺酸硫酸化RCH2OHClSO3HR-CH2OSO3HR-CH2OSO3Na+NaOH④氨基磺酸化硫酸化试剂CH2CH2OnH2NSO3HCH2CH2OnSO3NH2CH2CH2OnSO3NaROH+RONaOHRO四、磷酸酯表面活性剂的合成1.醇与五氧化二磷ROHP2O5ROHP2O5(RO)2PO(OH)P2O5(OH)2ROHP2O5(RO)2PO(OH)ROPO(OH)2+ROPOHOOPOHORONaOH2OPONaONaORNaOHROPOROONa+42+2ROH++2ROPO+3+H2OH2O醇与P2O5的配比（2－4）：1（物质量之比）单烷基磷酸酯70％－45％双烷基磷酸酯30％－35％2.醇与焦亚磷酸反应ROHH4P2O7(RO)PO(OH)2H3PO4++3.PCl3与过量的脂肪醇反应PCl3(RO)2P-HCl2(RO)2-P-ClOH2(RO)2-P-OH3ROH+O+RCl+2HCl通入O+HClO4.用三氯氧化磷与醇反应ROHPOCl3ROPOCl2ROPOCl2(OH)2ROHPOCl3(RO)2POCl(RO)2PO(OH)ROHPOCl3(RO)3POCl(RO)2PO(OH)++HCl+2ROPO+HCl单酯2++HCl22+HCl双酯++HCl33三酯H2OH2OH2O五、羧酸盐型阴离子表面活性剂取代羧酸盐酸的盐饱和或不饱和高级脂肪肥皂：天然动植物的油脂与碱的水汽液加热发生皂化反应制得，其反应方程式为：4NRRRR23+1.X-RCOOCH2RCOOCHRCOOCH2CH2OHCHOHCH2OH+3NaOH3RCOOMe+硬脂酸皂：C17H35COONa月桂酸皂：C11H23COONa油酸皂：C17H33COONa7-2阳离子表面活性剂一、阳离子表面活性剂的分类1.胺盐类伯胺盐RNH2.HClC18H37NH2.HCl十八烷基胺（硬脂胺）盐酸盐仲胺盐RNHR.HCl(C18H37)2NH.HCl12双十八烷基胺盐酸盐叔胺盐RNR(R).HClC18H37N(CH3)2.HCl123N，N－二甲基十八胺盐酸盐2.季铵盐型如缓染剂DC十八烷基二甲基苄基氯化铵CH2CH3CH3C18H37N+.Cl-3.杂环型吗啡型C16H33CH2CH2CH2CH2CH2CH2CH2CH2NONORR12.X-+RN+.Cl-CH2CH2CH2CH212CNRNRR+.X-CNRNR'吡啶型咪唑型哌嗪型CH2CH2CH2CH2NNHRR12.X-+.噁啉型NR+.X-4.鎓盐型a.磷盐化合物CH3CH3C12H25BrC12H25CH3CH3P+3h乙醇.-BrP+110℃b.硫盐化合物通式：3RR12.X-+.SRC16H33SC2H5CH3XC2H5H33C16H3C+.X-+.Sc.碘鎓化合物RR2.X-+.I1[]HSO4I+.-联苯碘磷酸盐d.鉮盐化合物.-+ClRAsRRR1234二、阳离子的表面活性剂的合成1.烷基季铵盐a.高级卤烷与低级叔胺反应RX+N:RRR123.-+RRRR123XN&+&-举例:C12H25Br(CH3)3NC12H25-N(CH3)3C16H33Br(CH3)3NC16H33-N(CH3)31231+水介质+[].Br-1:1.2-1.61631+醇介质回流+[].Br-过量50％60～80℃b.高级烷基胺与低级卤代烷的反应C12H25NH2CH3ClC12H25-NCH3CH3C12H25-NCH3CH3CH2ClC12H25CH2CH3CH3+2+2NaOH+2NaCl+2+加热加压N.-ClH2OC16H37-NCH3CH3CH3ClC16H33CH3CH3CH3+石油醚溶剂N.-Cl加压,80℃,1h2.含杂原子的季胺盐a.含氧原子①含酰胺基的季铵盐如SpamineiusC17H33COClH2N-CH2CH2-NC2H5C2H5C17H33CONHCH2CH2C2H5C2H5(CH3O)2SO4C17H33CONHCH2CH2C2H5C2H5CH3CH3SO4+N-N-.+-C17H35COOHH2NCH2CH2NHCH2CH2NH2N2C17H35CONHCH2CH2NHCH2CH2NHCOC17H35CH2-CHCH2ClC17H35CONHCH2CH2NHCH2CH2NHCH2-CH-CH2COC17H352+140-170-2O110-120O.-ClH2O℃②℃b.含醚基的季铵盐C18H37OCH2N(CH3)3[]+.-ClC18H37OHHCHOC18H37OCH2ClC18H37OCH2ClN(CH3)3C18H37OCH2N(CH3)++HCl5-10+[].-Cl+℃c.含氨季铵盐C10H21-N-CH2CH2BrCH3N(CH3)3C10H21NCH2CH2-N(CH3)3CH3+汽剂300份120℃压力12h[+].Br-d.含硫原子季铵盐C12H25SHHCHOC12H25SCH2ClC12H25SCH2ClN(CH3)3C12H25SCH2N(CH3)3++HCl+苯溶剂310份70-80℃2h[].-Cl+H2O3.含有苯环的季铵盐1227CH3CH3C12H25ClCH2CH3CH3C12H25CH2N+80-903hN.Cl+-℃4.含杂环的季铵盐R-CO-NHCH2CH2HOCH2CH2NHCH2CH2CH2CH2OHCH2CH2NH2CH2CH2OHCH2CH2CH2CH2OH酮式RCOHNNH烯醇式CNOR250-300-H2ORCNN℃7-3.非离子表面活性剂的合成一、非离子表面活性剂的分类a.醚类聚醚类聚乙二醇类b.酯类多元醇型聚乙二醇类脂肪酸酯山梨醇及失水山梨醇的季戊四醇的脂肪酸酯甘油的脂肪酸酯二、非离子表面活性剂的合成（一）醚类1.脂肪醇聚环氧乙烯醚（平平加AEO）(CH2CH2O)ROnHHOCH2CH2OHCH2CH2OnHOHH2C-CH2CH2CH2OROH+O催化RO()nHnR：12－16匀染、乳化R：7－9EO=5,渗透2.壬基苯酚聚氧乙烯醚CH2-CH2(CH2CH2O)+nOnHROHRO3.聚醚CHCH2CH3CH2CH3CHCH2OnCH3HOOH+CHO碱HO开环反应CH2CH2CH2CH2-OHCH2H2CCH2CH2-OHCH2CH2OHOH+CHOH++CHOOH-22O-O-副产物：一般用碱催化剂4.脂肪胺聚氧乙烯醚NH2H