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*21009724。*、。E-mailzhihuizhen@163．comBK20113692013-06-132013-10-31TPPＲDP、、ESI-MS。、、。L934。TPP2.1∶1.0BmimOH0.010wt%120～130℃4hＲDP90.7%。。SynthesisofOligomericPhosphateFlameＲetardantＲDPCaoYangYangXufengZhangWeiweiYangJinfeiZhiHuizhen*SchoolofChemistryandMaterialsScienceNanjingNormalUniversityNanjing210097AbstractWithtriphenylphosphateTPPandresorcinolastherawmaterialstheoligomericphosphateflameretardanttetraphenylm-phenylenebisphosphateＲDPwassynthesizedbyone-stepmethod．ItsstructurewascharacterizedbyIＲNMＲandESI-MS．Effectsoftherawmaterialratiothereactiontemperatureandthereactiontimeonthesynthesiswereinvestigated．ThereactionprocesswasmonitoredbyHPLC．BytheorthogonaltestL934andsinglefactorexperimentthereactionconditionswereoptimizedthatisTPPandresorcinolasmolarratioof2.1∶1.0wereputinundercatalyzingof0.010wt%BmimOHat120～130℃for4h．TheyieldofＲDPcanreach90.7%．TGanalysisshowedthatthethermalstabilityofas-synthesizedＲDＲcanmeetthedemandsofengineeringplasticsprocessing．KeywordsFlameretardantPhosphateＲesorcinoltetraphenylm-phenylenebisphosphateＲDPSynthesis、ＲDP、ABDP、HDP1～4/--PC/ABS5～9、。ＲDP1ＲDP10～122ＲDP13～163、。、、、3ＲDP29.5%17。ＲDP。7ＲDPTPPTPPＲDP。18～21ＲDP·85·2014771http//．hxtb．orgDOI:10.14159/j.cnki.0441-3776.2014.01.011TPPＲDP。“”ＲDP、TPP、、、。11.1TPP。STA449CAgilent1100Tensor27BrukerAvancedIII400MHzAgilent1100LC/MSD-。1.268.5g、11.0g0.010wt%120～130℃4h。IＲν/cm－1766C—H1190960P—O—Ph1305P=O1457148915903060C—H1HNMＲ400MHzDMSO-d6δ7.11～7.30m16H7.33～7.54m8H31PNMＲ400MHzDMSO-d6δ－17.7s2PESI-MSm/z575.3592.0597.5601.9613.1。ＲDP1Na+597.5ＲDP574.5。IＲ、NMＲ、ESI-MSＲDP。1ＲDPScheme1SyntheticroutesofＲDP2TPP。TPP。。TPP。2.1A/%、BnTPP∶n、CT/℃、Dt/h1L9342ＲDP。2ＲDP、、、A3B2C2D21Tab．1FactorsinorthogonalexperimentaldesignABCD10.0041.5∶1.0100～110320.0082.0∶1.0120～130430.0122.5∶1.0140～15052Tab．2ＲesultsoforthogonaltestABCDＲDP/%1111143.22122288.33133371.54212363.35223181.76231252.07313266.88321367.49332174.3K1203173.3162.6199.2K2197237.4225.9207.1K3208.5197.8220202.2Ｒ3.821.421.12.6·95·http//．hxtb．org2014771nTPP∶n=2.0∶1.00.012wt%120～130℃4h。、、、。2.2ＲDP。NaOH、NaHCO3、CH3ONa、KF、1--3-BmimOH、--3-BmimHCO36。22nTPP∶n=2.0∶1.00.012wt%120～130℃4h。ＲDP3。3Tab．3EffectofdifferentcatalystsonthecontentofproductsＲDP/%ＲDP/%ＲDP/%TPP/%NaOH62.122.37.96.5NaHCO357.310.24.417.3CH3ONa67.84.51.614.8KF26.50.70.142.1BmimOH87.34.51.03.6BmimHCO376.33.70.49.63ＲDP。。BmimOH。BmimOHnTPP∶n=2.0∶1.0120～130℃4h4。4Tab．4Effectofcatalysesdosageoncontentofproducts/%ＲDP/%ＲDP/%ＲDP/%TPP/%0.00772.53.30.49.70.00877.33.90.68.90.00981.64.51.15.20.01090.75.01.22.50.01190.64.91.52.50.01290.05.11.62.04ＲDP0.010wt%90.7%。0.010wt%。2.3BmimOH0.010wt%120～130℃4hＲDP。5。5Tab．5EffectofreactantproportiononcontentsofproductsnTPP∶nＲDP/%ＲDP/%ＲDP/%TPP/%1.7∶1.057.22.60.316.91.8∶1.073.24.40.79.11.9∶1.079.94.60.76.12.0∶1.087.34.91.12.72.1∶1.090.75.01.22.52.2∶1.086.25.21.23.73.0∶1.062.12.60.417.64.0∶1.041.72.50.233.35TPPＲDPTPP2.1∶1.0ＲDP90.7%。TPP2.1∶1.0。TPP2.1∶1.0。2.4BmimOHnTPP∶n=2.1∶1.00.010wt%4hＲDP6。6Tab．6Effectoftemperatureonthecontentofproducts/℃ＲDP/%ＲDP/%ＲDP/%TPP/%100～11069.12.60.413.5110～12077.53.50.89.9120～13090.75.01.22.5130～14082.511.41.92.5140～15071.315.32.33.4150～16062.920.43.03.7·06·2014771http//．hxtb．org。6120～130℃ＲDP。ＲDP。140℃。。120～130℃。2.5BmimOHnTPP∶n=2.1∶1.00.010wt%120～130℃ＲDP7。7Tab．7Effectoftimeoncontentofproducts/hＲDP/%ＲDP/%ＲDP/%TPP/%136.52.00.337.7272.93.70.79.4381.55.01.16.1490.75.01.22.5576.010.14.33.5673.511.36.24.27ＲDP。4hＲDP。4h。3ＲDPHPLC3.18Tab．8AnalysisconditionsofHPLC25℃1.0mL/min30μL15min3.2ＲDP9。9ＲDPTab．9ThecomparisonofＲDPperformanceＲDPＲDP25℃/mPa·s360～800400～7501.293～1.3151.299～1.3113.3ＲDPN280mL/min5℃/min～500℃。TG1。ＲDP1%281.32℃5%320.57℃。ＲDP25～27。1ＲDPFig．1TGcurveofＲDP4ＲDP。TPP2.1∶1.00.010wt%BmimOH120～130℃4hＲDP90.7%。。1MDespinasseBSchartel．Polym．Degr．Stab．201297122571～2580.2SYXuanXWangLSongetal．Polym．Int．201160101541～1547.3DGuoQWangSBBai．Polym．Adv．Technol．2013243339～347.4DVParikh．FireandMaterials201337146～57.5SVLevchikEDWeil．Polym．Int．2005547981～998.·16·http//．hxtb．org20147716SVLevchikEDWeil．J．FireSci．2006242137～151.7SVLevchikEDWeil．J．FireSci．2006245345～364.8SMLiuLJiangZJJiangetal．Polym．Adv．Technol．201122122392～2402.9HDLuLSongYHu．Polym．Adv．Technol．2011224379～394.10HJVincentKCHoward．EP05216281992.11DABrightＲLPirrelli．USP57507561998.12DABrightＲLPirrelli．USP61369972000.13AMAaronsonDABright．USP51839051993.14．2011397123～125.15．201119524～28.16．20055180～82.17JSHill．EP07751471999.18JSHill．USP60751582000.19MCombeyＲNBirrell．USP38695261975.20PFischerWHaese．USP78146262010.21KOhtsukiHTsuji．USP201102637672011.22BCＲunuSBanerjee．Org．Lett．200573049～3052.23KSAnnakuttyKKishore．Polymer19882971273～1276.24BLMiller．NMＲinBiomedicine19914247～52.25．201240242～46.26HVahabiOEterradossiLFerryetal．Eur．Polym．J．2013492319～327.27EFeyzYJahaniMEsfandeh．Macromol．Symp．20102981130～137.2014《》80。。。。1。“”、“”“”。。“《》”。2《ChemistryHuaxueTongbao》。320141。20132014。2013、E-mail。4、。“”。5“”。6①*。②、/。XXXXX。③。。④。⑤3。。《》2013－12－15·26·2014771http//．hxtb．org