含荧光基团的丙烯酸丙烯酰胺共聚物的合成

2006352PETROCHEMICALTECHNOLOGY[]2005-09-08;[]2005-11-05[](1971),,,,,025-84315190,[e-mail]:,025-84315190-1,1,1,1,1,2,1(1.,210094;2.,226007)[]4--1,8-3-4--N-(2-N,N-)(4-MNDMAPN-AQ),(AA)(AM),AA/AM/4-MNDMAPN-AQ,,,0.9950,0.48mg/L,(750.2)[Ca2+]=5mmol/L[HCO-3]=10mmol/L10hAA/AM/4-MNDMAPN-AQ2.5mg/L,70.78%,2--1,2,4-,,[];;;;;;[]1000-8144(2006)02-0145-06[]TQ085.412[]ASynthesisofAcrylicAcid2AcrylamideCopolymerContainingFluorescentGroupLeiWu1,PingChunxia1,WangFenghe1,XiaMingzhu1,ZhangYuehua1,2,WangFengyun1(1.IndustrialChemistryInstitute,NanjingUniversityofScience&Technology,NanjingJiangsu210094,China;2.CollegeofChemistryandChemicalEngineering,NantongUniversity,NantongJiangsu226007,China)[Abstract]Anovelwatersolublefluorescentmonomer,42methoxy2N2(32dimethylaminopropyl)naphthalimideallylchloridequaternaryammoniumsalt(42MNDMAPN2AQ),wassynthesizedfrom42chloro21,82naphthalicanhydrideand32dimethylaminopropylamine.Theoptimalreactionconditionswereobtained,andstructureoftheproductwascharacterizedbymeansofIR,1HNMRandMS.ThecopolymerAA/AM/42MNDMAPN2AQfromacrylicacid(AA),acrylamide(AM)and42MNDMAPN2AQwasprepared.Thefluorescentpropertiesandscaleinhibitionperformanceofthecopolymerwerestudiedindetail.Relationshipbetweenfluorescentintensityandconcentrationofcopolymerwaslinearinconcentrationrangeof18mg/L.Thecorrelationcoefficient(R)was0.9950.Underoptimalconditions:[Ca2+]=5mmol/L,[HCO23]=10mmol/L,t=(750.2)for10handcopolymermassconcentration2.5mg/L,thescaleinhibitionratecouldreach70.78%bymeansofhardscaledetermination.Besidepossessingfluorescence,thecopolymerAA/AM/42MNDMAPN2AQ,asahighperformancescaleinhibitor,wascomparablewith22phosphono2butane21,2,42tricarboxylicacidwhichwasknownasthebestscaleinhibitor.[Keywords]fluorescentmonomer;quaternaryammoniumsalt;synthesis;copolymer;acrylicacid;acrylamide;scaleinhibitor,,[17],,,[818],,[18][19,20],4--1,541PETROCHEMICALTECHNOLOGY2006358-3-,34--N-(2-N,N-)(4-MNDMAPN-AQ),(AA)(AM),(AA/AM/4-MNDMAPN-AQ),CaCO311.14-MNDMAPN-AQ(1);AA/AM/4-MNDMAPN-AQ(2)1.2MB154S-FTIR(IR)(KBr):Nicolet;BrukerDRX300MHz(1HNMR)():Bruker;FinniganTSQ(MS):Varian;GBC-918:GBC;RF5301PC:4--1,8-3-AAAM;N,N-(DMF)1.31.3.14-MNDMAPN-AQ3(1)4--1,8-4.65g,50mL,3-2.05g,3-,,1h5h,,,50%pH89,DMF,4--N-(2-N,N-)()(2)4.84g,50mL,1.7g,N2,6h,,-6412.-,4--N-(2-N,N-)()(3)4.5g,50mL,2.30g,6h,,,-,4-MNDMAPN-AQ()1.3.2AA/AM/4-MNDMAPN-AQ133.7g0.47g4-MNDMAPN-AQ,85,85(3.50g19.59g)(10.48g30.30g),2h;5min13.57g95.43g193.23g50%,2h,1.5h,AA/AM/4-MNDMAPN-AQ()22.12,Cl-CON,,;Cl-,,,SNAr,(3)3,4--N-(2-N,N-)21,,CCl,CCl,,,,SN2[21,22],(4)2.2:IR(KBr,/cm-1),1697.071652.56(CO),573.53(CCl);1HNMR(CH3OH,),7.14(d,1H,ArH),7.04(d,1H,ArH),6.67(d,1H,ArH),6.10(t,1H,ArH),4.69(d,1H,ArH),3.35(t,2H,NCH2CH2CH2N(CH3)2),2.50(t,2H,NCH2CH2CH2N(CH3)2),4.42(s,6H,N(CH3)2);MS(m/z),317([M]+):IR(KBr,/cm-1),1270.37(COC);1HNMR(CH3OH,),3.54(s,3H,OCH3);MS(m/z),312([M]+):IR(KBr,/cm-1),1697.071652.56(CO),1643(CC),1384.8(CN);1HNMR(D2O,),5.926.04(m,1H,CHCH2),5.175.40(d,2H,CHCH2),741PETROCHEMICALTECHNOLOGY2006354.11(d,2H,NCH2CHCH2);MS(m/z),353([M]+)2.3,(),82.0%,()(),2.3.12.3.1.14--1,8-3-11,,,;5h,,78.5%,5h2.3.1.25h,(4--1,8-3-),,;4--1,8-3-21,,79.8%3-,,3-(5),,,4--1,8-3-212.3.24.5g,(1)(2)(3)3,3,1.15,2.30,3.45g;50,60,70;4,6,8h,1,3,2,:2.30g,6h,60,74.8%2.42.4.12.4.1.1,190800nm-1(1)1,,194,240,378nm-12.4.1.210mg/L,450nm,,,,378,450nm1Fig.1Ultravioletspectrumofcopolymer.378,450nm,22,,0.99503/k(,k)0.48mg/L2.4.2,[23][24]HH,8412.-HH0(),()XX=(HH0-HH)/HH0100%2Fig.2Relationshipoffluorescentintensitywithmassconcentrationofcopolymer.33,,12mg/L3,,2--1,2,4-(PBTCA)(DTPMP),-(T-225)[23],PBTCA,T-225,3()Fig.3Relationshipofmassconcentrationofscaleinhibitorswithscaleinhibitionrate(staticmethod).Reactionconditionsreferredtoliterature[23].Copolymer;Acrylicacid2hydroxypropylacrylatecopolymers(T2225);Diethylenetriaminepentamethylenephosponicacid(DTPMP);22Phosphono2butane21,2,42tricarboxylicacid(PBTCA)44,-(AA-MA)PBTCAT-225,,[23][25][26]pH[27][28],,4()Fig.4Relationshipofmassconcentrationofscaleinhibitorswithscaleinhibitionrate(hardscaledetermination).Reactionconditions:temperature(750.2),[Ca2+]=5mmol/L,[HCO23]=10mmol/L,constanttemperature,10h.PBTCA;T2225;Acrylicacid2acrylamide;Copolymer3(1)4--1,8-3-4--N-(2-N,N-)(4-MNDMAPN-AQ),(AA)(AM),(AA/AM/4-MNDMAPN-AQ)(2)AA/AM/4-MNDMAPN-AQ,-,2--1,2,4-(3)AA/AM/4-MNDMAPN-AQ,1,,..,2003,20(4):397399941PETROCHEMICALTECHNOLOGY2006352,,..,2000,17(4):4054083,,..,2001,18(9):7467484,,.Pb2+.,2004,33(12):116811725,..,2004,33(12):117311766,.ZU-101.,2002,31(6):4474497,,./,,2004,24(2):1481508MoriartyBE,WeiMingli,HootsJE,etal.FluorescentMonomersandPolymersContailingSameforUseinIndustrialWaterSystems.USPatAppl,US6312644.20019MoriartyBE,HootsJE,WeiMingli,etal.FluroscentMonomerandPolymersContainingSameforUseIndustryWater2System.PCTIntAppl,WO01/44403A1.200110HootJE.MonitorandDosageControlofTtaggedPolymersinCoolingWaterSystems.USPatAppl,US5171450.199211HootsJE,GodfreyMR.MonitoringWaterTreatmentAgentin2SystemConcentrationandRegulatingDosage.USPatAppl,US5435969.199412SivakumarA,AnanthasubraJ,ShahNM,etal.FluorescentTracerinaWaterTreat