环氧植物油基增塑剂的合成工艺进展

(，，100081)(EPO)。，EPO。，，、、，EPO。AdvanceonSynthesisTechnologyofPlasticizersBasedontheEpoxidizedPlantOilCaiShuang-feiWangLi-sheng(BeijingInstituteofTechnology,Beijing,100081)Abstract:Theepoxidizedplantoil(EPO)isenvironmentalfriendlyasplasticizer.BasedonthemethodsforEPOsynthesisandcatalystsused,progressesinthesynthesisofplasticizerbasedonEPOinrecentyearshavebeenreviewed.Meanwhile,thepresentcatalyticsystemsandsynthetictechnologiesusedforsynthesisofEPOhavebeenanalyzedbriefly.Also,ithasbeenpointedoutthatdevelopingnew,efficient,greenaswellasinexpensivecatalyticsystems,willcontinuetobefutureresearchorientationintheEPOsynthesisfield.Keywords:plantoil;epoxidation;plasticizer;synthesis：2010-03-17，。，(EPO)，PVC[1]。，，、、(DOP、DBP)[2]。EPO、、，。，EPO。，、、、、、、、。，(ESBO)EPO70%，200kt[3]。EPO，，。1()EPO，EPO“Prileschajew”[4](1)，：()，，()H2O2。，（）[5]。，EPO，[4](2)。，EPO，。、，20105（83）1、、，，。，()H2O2，。()，，，。，，，。，EPO。1.1H2SO4，，、。EPO：、、H2O2、、。Goud[6]H2SO4HNO3（mahuaoil)，H2SO4，10-6L/(mol·s)14.5kcal/mol，、：13.8kcal/mol，-51.1cal/(mol·K）30.6kcal/mol。Dinda[7]，4，：H2SO4H3PO4HNO3HCl，。H2SO4(0.39~5.4)×10-6L/(mol·s)，11.7kcal/mol，、：11.0kcal/mol,-51.4cal/（mol·K）28.1kcal/mol。1.2(AIER)，EPO，[8]。，、。Goud[3]，、H2O2、、AIER，12.0kcal/mol。（ESBO），Petrovic[9]。，，，。，Sinadinoric-Fiser[10]，ESBO，ESBO。，。1.3[11]ESBO，，，。Fe2+，，Fe2+H2O2，，。EPO、，[12]ESBO。，，。1.4，，。[13]，ESBO。3，，、。，Campanella[14]。，60℃、30%2EPO[4]Fig.2Acid-catalyzedcleavagereactionofEPO[4]R1CHCHR2OCH3COOHR1CHCHR2OHOCOCH3R1CHCHR2OHOHR1CCH2R2OR1CHR2CHOHOCOOCH3R1CHR2CHOHOOHH2OCH3COOOHH2O2H+1()EPO[4]Fig.1SynthesisofEPObyperoxyformicorperoxyaceticacidoxidationmethod[4]RCOOH+H2O2H+RCOOOH+H2ORCOOOH+R1CHCHR2R1CHCHR2+RCOOHO20105（83）2H2O2，40℃、60%H2O2，。2EPO，、。，EPO，。，、、、、。2.1（W）H2O2，(POMs)。EPO，Q3+{PO4[WO(O2)2]4}3-。Kozhevnikov[15]。，95%，84%()，800~1200。，Poli[16]，96.9%，94%。[17]ESBO，，ESBO0.04g/g，6%，，5。2.2（Ti）Guidotti[18]（TBHP）、，4-。，-（Ti-MCM-41）-。，Rios[19]Ti-MCM-41Ti-SiO2。，Ti、。，Ti-MCM-41，Ti-SiO2，4。2.3（Re）H2O2，(VII)(MTO)。H2O2：(85%)，A；(≤30%)，B(3)[20]。Gerbase[21]MTO/CH2Cl2/H2O2ESBO。，2h，95%，35℃6h91%83%。MTO，。Bouh[22]MTONb2O5。，-H2O2，50℃30min，。2.4(Al)，H2O2。、，H2O260%。Sepulveda[23]，-。，70%H2O2，-，4。Suarez[24]Al2O3、(Al2O3)0.8-(SnO)0.1(ZnO)0.1、(Al2O3)0.8(TiO2)0.1(ZrO2)0.1(Al2O3)0.8-(TiO2)0.2。，，；，，LewisH2O2，。，，。2.5（Mo）3MTO/H2O2[20]Fig.3ReactionmechanismofalkeneepoxidationusingMTO/H2O2system[20]ReOOOH3COOCH2CH2OH2OReOOOOH3CH2OH2O2ReOOH3COOHHOOReOOOCH2CH2OCH3OH2OReCH3OOOcycleAcycleB，.53Mo(VI)/TBHP。，EPO。Sobczak[25][Mo(O)2(SAP)(EtOH)]/TBHP(4)，86.8%，TBHP67%。[Mo(O)2(SAP)(EtOH)]TBHP1.00±0.050.51±0.05，（99±4）kJ/mol△H=(96±4)kJ/mol。3EPOEPO，、EPO、。，、。3.1，Novozym435[26]。EPO。Warwel[27]Novozym435，，。，1H2O22；“”3(5)。、、，90%[28]。，1575%[27]。，Orellana-Coca[29]，。，，。T觟rnvall[30]，，H2O2，。3.2。Piazza[31]，TBHP，80%，H2O233%。，[32]。，，。4EPO4.1/EPO，。、，EPO[33-35]。，K觟ckritz1[36]，(AIBN)，/。，，(6)，。5“”[27]Fig.5Lipase-catalzedreactionmechanismofoleicacid‘self’-epoxidation[27]H3C77OOH+H2O21H3C77OOOH+H2OH3C77OOOH231214TBHP[Mo(O)2(SAP)(EtOH)][25]Fig.4ReactionmechanismofoleicacidepoxidationwithTBHPcatalysedby[Mo(O)2(SAP)(EtOH)][25]2[Me(O)2(SAP)(EtOH)]-2EtOH+2EtOH[Mo(O)(μ-O)SAP)]2Me3COOHMoOOOONOHOMe3CMoOOONOMe3COHMe3COOHMe3COHMe(CH2)7CH=CH(CH2)7COOHMoOOONOHOHOMe3CCCH(CH2)7COOCH3H3C(H2C)79,10-20105（83）44.2。KHSO5，，[37]。EPO[38]。96%，5%~20%（），。。4.3EPO，。LieKenJie[39]，(m-CPBA)(MMPP)。，MMPPm-CPBA，。，。，，。，，，。5，EPO，、。：；，H2SO4，，。H2SO4，AIER，，；AIER，Fe2+，，；，。W、Ti、Re，W，，。，，，，。，，、、，EPO。[1]BenanibaaMT,Belhaneche-BensemrabN,GelbardcG.KineticsofTungsten-catalyzedSunflowerOilEpoxidationStudiedby1HNMR[J].Eur.J.LipidSci.Technol.,2007,109(12):1186-1193[2],,.[J].,2008,33(6):36-39[3]GoudVV,PatwardhanAV,PradhanNC.KineticsofinSituEpoxidationofNaturalUnsaturatedTriglyceridesCatalyzedbyAcidicIonExchangeResin[J].Ind.Eng.Chem.Res.,2007,46(10):3078-3085[4]GoudVV,PatwardhanAV,DindaS,etal.KineticsofEpoxidationofJatrophaOilwithPeroxyaceticandPeroxyformicAcidCatalysedbyAcidicIonExchangeResin[J].Chem.Eng.Sci.2007,62(15):4065-4076[5]GanLH,GohSH,OoiKS.KineticStudiesofEpoxidationandOxiraneCleavageofPalmOleinMethylEsters[J].Am.Oil.Chem.Soc.,1992,69(4):347-351[6]GoudVV,PatwardhanAV,PradhanNC.StudiesontheEpoxidationofMahuaOil(MadhumicaIndica)byHydrogenPeroxide[J].Bioresour.Technol.,2006,97(12):1365-1371[7]DindaS,PatwardhanAV,GoudVV,etal.EpoxidationofCottonseedOilbyAqueousHydrogenPeroxideCatalysedbyLiquidInorganicAcids[J].Bioresour.Technol.,2008,99(9):3737-3744[8]KirkRE,OthmerDF,MarkHF,etal.Kirk-OthmerEncyclopediaofChemicalTechnology[M].Wiley:NewYork,1965[9]Petrovic＇ZS,Zlatanic＇A,LavaCC,etal.EpoxidationofSoybeanOilinTolueneWithPeroxoaceticand6、[36]Fig.6Reactionmechanismofmethyloleateepoxidationusingmolecularoxygenasoxidantandaldehydeascooxidant[36]RCHORCO·ROOO·O2ROOOH+RCO·RCHOH3C(CH2)7(CH2)7COOCH3H3C(CH2)7(CH2)7COOCH3ROOO(CH2)7CH3(CH2)7COOCH3H3C(CH2)7(CH2)7COOCH3OH3C(CH2)7(CH2)7COOCH3O+RCOOHH3C(CH2)7(CH2)7COOCH3O++ROO·CO2+R·，.55PeroxoformicAcidskineticsandSideReactions[J].Eur.J.LipidSci.Technol.,2002,104(5):293-299[10]Sinadinovic＇-Fi觢erS,Jankovic＇M,Petrovic＇ZS.KineticsofinSituEpoxidationofSoybeanOilinBulkCatalyzedbyIonexchangeResin[J].Am.Oil.Chem.Soc.,2