水性環(huán)氧合成方法

PreparationofanIsolatedAdductbasedonTETAandEpon828.TM.Toa3liter(公升)，4neckedroundbottomflask,equippedwithamechanicalstirrer,thermocouple,nitrogenspargeanddroppingfunnelwascharged1700g(11.65mols)oftriethylenetetramine(TETA).Thecontentsoftheflaskwasheatedto95.degree.C.atwhichpoint737g(1.95mols)ofEpon828diglycidyletherofbisphenolA(ShellChemicalCo.)wasaddedovera2hourperiod.Aftertheadditionwascompletethebatchwasheldatthistemperatureforafurther2hoursandthentransferredtoawipedfilmstill.RemovaloftheexcessTETAwasachievedbypassingtheadductthroughthestillat150.degree.C./2-4mmHg.Rotorbladesweresetat400rpmandthebatchintroducedatafeedrateofapproximately150g/hr.Aftervacuumstrip,asamplewasanalyzedbygaschromatographyandfoundtocontain<0.5%freeTETA.RecoveryoftheE828/TETAadductwasequivalentto98.5%ofthetheoreticalyield.EXAMPLE2PreparationofEndCappedAdductbasedonPhenylGlycidylEther(苯基縮水甘油醚)andCashewNutOilGlycidylEther(腰果油糖醇)Toa500ml,4neckedroundbottomflask,equippedwithamechanicalstirrer,thermocouple,condenser,nitrogenspargeandadroppingfunnelwasplaced168g(0.25mols)oftheisolatedadductoftriethylenetetramine(TETA)andEpon828epoxideaspreparedinExample1.Anitrogenspargewasbegunandthematerialheatedto95.degree.C.followedbytheadditionof80.0gof1-methoxy-2-propanol(丙二醇甲醚)(Dowanol.TM.PM).Whilemaintainingthistemperature,49.0g(0.05mols)ofaDER671resin(EEW490)in49.0gofDowanolPM(丙二醇甲醚)solutionwerechargedtothereactorovera2hourperiod.Aftertheadditionwascomplete,themixturewasallowedtoreactattheabovetemperatureforafurtheronehour.Toa500mldroppingfunnelwerecharged66.0g(0.4mols)ofphenylglycidyletherand49.0g(0.1mols)ofcashewnutoilglycidylether(CardoliteNC513).Themixturewaschargedtothepolyamine/epoxyadductsolutionoveraperiodofaboutonehour,whilemaintainingareactiontemperatureof95.degree.-105.degree.C.Themixturewasheldat95.degree.C.foranadditional60minutes,atwhichpointamixtureof79.0gwaterand13.3gglacialaceticacid(冰醋酸)wasthenadded.Afterthoroughmixing(30minutes),thebatchwascooledto70.degree.C.andthenfiltered.Theresultinghomogeneousproducthadanon-volatilecontentof60.3%,viscosity11,700cps@25.degree.C.andacolorofGardner8.Thetheoreticalhydrogenequivalentweight[HEW]fortheaminecuringagentwasapproximately174basedonsolids.(EpoxyResinFormation)Toakettlereactorwerecharged362.7gramsofdiglycidyletherofBPAhavinganepoxideequivalentweightof188,EPON.RTM.Resin828manufacturedbyShellChemicalCompany.and127.7gramsofBPA,BPA-157manufacturedbyShellChemicalCompany.Thismixturewasheatedandstirredatabout177.degree.F.untiltheBPAdissolvedintheliquidepoxyresin.18gramsofdeionizedwaterand1.3gramsoftriphenylphosphinecatalystwerethenaddedtothismixture.Themixturewasallowedtoreactat177.degree.F.fortwohours.Theepoxideequivalentweightofthereactionproductwas620.EXAMPLE2(One-PackFormation)Tothereactionproductofexample1inwaterwasadded107.2gramsofareactivesurfactant,preparedbyreacting2molesofpolyoxyethyleneglycoland1moleofaglycidylpolyetherofBPAhavinganepoxyequivalentweightof468.Thesurfactantwasaddedtothereactionmassasa32.5%wsolutioninwaterslowlysoastomaintainthetemperatureofthereactionmassat177.degree.F.Anadditional33.2gramsofdeionizedwaterwasthenaddedtothismixture.Apredispersedepoxyresinwasthusformed.20.3gramsofmicronizedDICYhavinganaverageparticlesizeof8micronswasaddedtothepredispersedepoxyresin.Aftera30minuteholdat177.degree.F.,themasswasafluffywhiteliquidpredispersedresinousmass.A2gramsampleofthepredispersed,resinousmasseasilydispersedinavialofwater.Thewaterphasewasthecontinuousphase.Theaverageparticlesizeofthedispersedphase(organic)wasdeterminedtobeabout1-2micronsbyvisualinspection.Thepredispersedresinousmasswasagitatedandheldat177.degree.F.foranadditionalthreehours.241gramsofadditionaldeionizedwaterwasaddedtothemasstoyielda60%wtsolidssolution,basedontotalresinoussolidsinwater.Thispredispersedresinousmasswasthencooled.Theresultantdispersionhadanumberaverageparticlesizeof1.19asdeterminedbydisccentrifugephotosedimentometry.Thefinalweightperepoxideonasolidsbasiswas685.Theviscosityofthedispersionwas8000cP.Theresultantdispersiondisplayedanonsetofcureat175.degree.C.,determinedbydifferentialscanningcalorimetry.Theresultantdispersionwasthenagedatroomtemperatureforthreemonths.Thenumberaverageparticlesizewasthendeterminedtobe0.95,theweightperperoxidewas680andtheviscositywas7900cP.Onsetofcurewasagaindeterminedtobe175.degree.C.bydifferentialscanningcalorimetry.Thisexampleillustratestheformationofastablewaterborneone-packdispersionofasolidepoxyresinandDICY.EXAMPLE3(One-packFormation)Areactivesurfactantpreparedbyreacting2molsofpolyoxyethyleneglycoland1molofaglycidylpolyetherofBPAhavinganepoxyequivalentweightof468waschargedtoafourneckglassreactionflask.105gramsofthissurfactantinwater(32.5%wsolidsinwater)wasadded.Anadditional110gramsofDIwaterwasaddedandthesolutionwasthenagitatedandheatedto140.degree.F.565.8gramsofwarmed,100.degree.F.,diglycidyletherofBPAhavinganepoxideequivalentweightof188(commerciallyavailablefromShellChemicalCompanyunderthetradenameEPON.RTM.Resin828)wereaddedtothereactoroverthecourseof90minutestoformapredispersedresin.34gramsofDICYmicronizedtoanaverageparticlesizeof8micronswasthenaddedtothereactionmass.Afluffywhiteliquidpredispersedresinousmasswasformedaftera30minuteholdwithagitationbutnoadditionalheat.A2gramsampleofthepredispersedresinousmasseasilydispersedinavialofwater.Vacuumwasappliedtothepredispersedresinousmassasitwasagitatedat95.degree.F.for60minutes.219gramsofdeionizedwaterwasthenaddedtobringthemixturetoa60%wtsolidsdispersion.Thisresultedintheformationofastableepoxyresindispersionwithanumberaverageparticlesizeof0.56,aweightperepoxideonasolidsbasisof200,aviscosityof1800cP,withanonsetofcureoccurringat172.degree.C.,measuredbydifferentialscanningcalorimetry.Thestableepoxyresindispersionwasagedatroomtemperaturefor3months.Afteraging,thedispersionwasfoundtohaveanumberaverageparticlesizeof0.60,weightperepoxideof200,viscosity1850cP,andonsetofcureoccurringat170.degree.C.,bydifferentialscanningcalorimetry.Thisexampleillustratesthatastableone-packdispersionofaliquidepoxyandDICYinanaqueousmediumisformedfromtheprocessofthisinvention.EXAMPLE4(One-PackFormation)Areactivesurfactantpreparedbyreacting2molsofpolyoxyethyleneglycoland1molofaglycidylpolyetherofBPAhavinganepoxyequivalentweightof468waschargedtoafourneckglassreactionflask.105gramsofthissurfactantinwater(32.5%wsolidsinwater)wasadded.Anadditional110gramsofDIwaterwasaddedandthesolutionwasthenagitatedandheatedto140.degree.F.351gramsofwarmed,100.degree.F.,tetraglycidyletherofphenolicnovolachavinganepoxideequivalentweightof205(commerciallyavailablefromShellChemicalCompanyunderthetradenameEPON.RTM.Resin155)and40gramsofDICYmicronizedtoanaverageparticlesizeof8micronsweremixedtogethertoformasoliddispersedinliquidresinmass.Thismasswasaddedtothereactorcontainingsurfactantoverthecourseof90minutes.Afluffywhiteaqueousliquidpredispersedresinousmasswasformed.A2gramsampleofthepredispersedresinousmasseasilydispersedinavialofwater.Thepredispersedresinousmasswasshearedforanadditional30minutes.1.32gramsofdeionizedwaterwasthenaddedtobringthemixturetoa70%wtsolidsdispersion.Thisresultedintheformationofastableepoxyresindispersionwithanumberaverageparticlesizeof0.62,aweightperepoxideonasolidsbasisof230,aviscosityof57,360cP,withanonsetofcureoccurringat175.degree.C.,measuredusingdifferentialscanningcalofimetry.Thestableepoxyresindispersionwasagedatroomtemperaturefor3months.Afteragingthedispersionwasfoundtohaveanumberaverageparticlesizeof0.60,weightperepoxideof235,viscosity59,520cP,andonsetofcureoccurringat174.degree.C.,measuredbydifferentialscanningcalofimetry.Thisexamplesillustratestheformationofastablemultifunctionalepoxysystembytheprocessofthisinvention.ItalsoillustratesthattheDICYcanbeaddedsimultaneouslywiththeliquidepoxyresin.EXAMPLE5(AcceleratorAddition)A10%wtsolutionof2-methylimidazolesolutionwasprepared.1.5gramswasaddedtothestableepoxyresindispersionofexample3.1.0gramwasaddedtothestableepoxyresindispersionofexample4.Filmswereeastfrombothacceleratedformulationswitha2milmeteringbar.Thefilmswerecuredat350.degree.F.for20minutes.Bothfilmsshowedahighdegreeofcureasevidencebygreaterthan100methylethylketonedoublerubswithweightedcheesecloth.Fullcurewasalsoevidencedbynoexothermpresentinatemperaturesweepfrom50to300degreesCat20degreesCperminuteusingdifferentialscanningcalorimetry.EXAMPLE6(Comparative)Anepoxyresinsolutionofexample1(withoutofadditionofDICY)waspreparedhavinga60%wtsolidepoxyinwatercontent,aweightperperoxideof650,aviscosityof9,500cP,andanumberaverageparticlesizeof1.2(commerciallyavailablefromShellChemicalCompanyunderthetradenameEPI-REZ.RTM.Resin3522-W-60).Eachofthesepropertieswasdeterminedassetforthabove.20.3gramsofDICYwasdissolvedin182.7gramsofhotwater.ThisDICYsolutionwasthenadde