羟丙基纤维素接枝改性研究（study on graft modification of hydroxypropyl cellulose）

羟丙基纤维素接枝改性研究（STUDYONGRAFTMODIFICATIONOFHYDROXYPROPYLCELLULOSE）ARTICLENUMBER10044736200004000604STUDYONGRAFTMODIFICATIONOFHYDROXYPROPYLCELLULOSEYANGJIAMO,LISHIRONG,YUFAQUAN,BIYAFAN,CHENXIAOYANDEPARTMENTOFCHEMICALENGINEERING,WUHANINSTITUTEOFCHEMISTRY,HUBEI,WUHAN430073,CHINAABSTRACTTHEGRAFTCOPOLYMERIZATIONOFHYDROXYPROPYLCELLULOSEWITHMETHYLMETHACRYLATEWASCARRIEDOUTBYUSINGUVANDCERIUMSALTSASTWOINITIATORSTHEEFFECTSOFREACTIONTIME,TEMPERATURE,MONOMERCONCENTRATION,PHOTOSENSITIZERORINITIATORDOSAGEONTHEVISCOSITYOFTHEPRODUCTWEREINVESTIGATEDTWOKINDSOFINITIATIONWERECOMPAREDTHEOPTIMUMOPERATIONCONDITIONOFTHEREACTIONISOBTAINEDKEYWORDSHYDROXYPROPYLCELLULOSEGRAFTCOPOLYMERIZATIONMODIFICATIONVISCOSITYCLCNUMBERTQ3616,DOCUMENTIDENTIFIERCODEARECEIVEDDATE20000509BIOGRAPHYYANGJIAMO1949,MALE,PROFESSOROFZHANGSHUCITY,JIANGXILONGTERMTEACHINGANDRESEARCHWORKINCHEMICALENGINEERINGANDCHEMICALTECHNOLOGY0INTRODUCTIONTHEMOLECULARFORMULAFORCOTTONCELLULOSEISC6H10O5N,WHICHISFORMEDTHECHIEFCONSTITUENTOFTHEPLANTCELLMEMBRANECELLULOSEINTHEMACROMOLECULARSTRUCTURECONSISTINGOFREPEATEDGLUCOSEUNITSLINKEDTOTHE1,4BETAGLYCOSIDICBONDTHEREACTIONCHARACTERISTICOFCELLULOSEISMAINLYTHATITSPRODUCTISINHOMOGENEOUSSEXANDCOMPLEXITY,THEMOLECULARSTRUCTUREOFTHERAWMATERIALHASANIMPACTONTHEREACTIONPROCESSTHEREACTIONACTIVITYISAFFECTEDBYTHENEIGHBORINGFUNCTIONALGROUPANDTHEREACTIONSTRIPATTHESAMETIMETHETYPEOFREACTIONISRELATEDTOTHEREACTIONSTEPPROCESSINGPRODUCTSTOMEETTHEQUALITYREQUIREMENTSOFUSERSMOREDIFFICULT,BIGMANYOFTHEMNEEDTOBEREMODIFIEDTOIMPROVETHEIRPERFORMANCEGRAFTCOPOLYMERIZATIONISONEOFTHEMOSTCOMMONANDHASBEENPROVEDBYPRACTICETHEMODIFICATIONMETHODWITHREMARKABLEEFFECTISTHROUGHTWOKINDSOFMACROMOLECULARBACKBONECHEMICALLYLINKEDWITHABRANCHEDCHAINTOPRODUCEAPRODUCTWITHTHECOMPREHENSIVEPROPERTIESOFTHESETWOMOLECULES,IDEALRESULTSCANBEOBTAINEDIMPROVEITSPHYSICALANDCHEMICALPROPERTIESORUSEPERFORMANCETHENEWPRODUCTCANBESYNTHESIZEDBYTHEFOLLOWINGWAYSTHEPURPOSEOFIMPROVINGITSQUALITYORPERFORMANCE1INTRODUCINGACTIVEGROUPSONMACROMOLECULARBACKBONETHEINITIATIONOFAMONOMER,COPOLYMERIZATION,ANDGROWTHOFAPOLYMERBRANCHEDCHAIN2BYMEANSOF“GRAFTING“CHEMICALCOMBINATION,AKINDOFTHEMOLECULARCHAINOFTHEADDUCTACTSASABRANCHEDCHAINATTACHEDTOTHEPARENTMACROMOLECULARBACKBONE3INTHEPROCESSOFPREPARINGAPOLYMER,MAKEANOTHERKINDPOLYMERSAREFORMEDSIMULTANEOUSLYANDAREUSEDASBRANCHEDCHAINSWITHTHEFIRSTPOLYMERTOOBTAINMACROMOLECULARPRODUCTSTHEABOVEREACTIONSCANBEPERFORMEDINDIFFERENTWAYS,SUCHASCHAINTRANSFERANDACTIVITYGROUPMETHOD,RADIATIONMETHOD,ADDITIONPOLYMERIZATIONMETHODANDRINGOPENINGPOLYMERIZATIONMETHOD,ETCETC,THISWORKISTOUSEHYDROXYPROPYLCELLULOSE,METHYLMETHACRYLATETHELIPIDWASTHEMAINRAWMATERIAL,WHICHWASCAUSEDBYCERICAMMONIUMNITRATEANDULTRAVIOLETLIGHTRESPECTIVELY,GRAFTCOPOLYMERIZATIONWASCARRIEDOUTTOIMPROVECELLULOSEVISCOSITYOBJECTIVEANDCOMPARETHEADVANTAGESANDDISADVANTAGESOFTWODIFFERENTMETHODSOPTIMUMOPERATINGCONDITIONS1MAINRAWMATERIALS,DRUGSANDINSTRUMENTSHYDROXYPROPYLCELLULOSEHECWHITEPOWDER,HUBEIBELLCHEUNGCELLULOSECOMPANYPRODUCESANAQUEOUSSOLUTIONOFW2WITHAVISCOSITYOF20000MPAS20DEGCDRY24HBEFOREUSEMETHYLMETHACRYLATEC5H8O2MOLECULARWEIGHT10012ANALYTICAL,PURE,HUBEIUNIVERSITYCHEMICALPLANTPRODUCTIONCERICAMMONIUMNITRATENH42CENO36REFERREDTOASCERIUMSALTTHEMOLECULARWEIGHTIS54832,PURITYANALYSIS,SHANGHAIYUELONGDAYENONFERROUSMETALSCOSTUDENTSPRODUCTIONPYROGALLICACIDC6H3OH3AMOLECULARWEIGHTOF12611,THEANALYSISOFPURE,GUIZHOU,ZUNYISECONDCHEMICALPLANTPRODUCTIONROTARYVISCOSIMETERMODELNDJ1,SHANGHAIBALANCEINSTRUMENTFACTORYPRODUCTIONUVINITIATEDGRAFTCOPOLYMERIZATIONDEVICEHOMEMADE2EXPERIMENTPROCEDUREANDEXPERIMENTSCHEME21EXPERIMENTALSTEPSINORDERNOTTOOXIDIZETHEREACTIONPROCESS,NITROGENISNEEDEDPROTECTIONFIRST,ANITROGENPURGEUNITISASSEMBLEDTODISSOLVEITTHROUGHCOPPERAMMONIALIQUID,PYROGALLICACIDSOLUTIONANDPHOSPHATESOLUTION,ANDCHECKTHESEALSACERTAINAMOUNTOFDRIEDHYDROXYPROPYLCELLULOSEISPLACEDINTHEREACTOR,ADDPROPERAMOUNTOFDISTILLEDWATERANDMIXWITH2HFORCONSISTENCYAFTERTHEENTRY,THENITROGENISINJECTED30MIN,ANDTHEMIXTUREISSTIRREDATTHESAMETIMETHESALTHEATSORTURNSONTHEULTRAVIOLETLIGHTWHENTHETEMPERATUREISREACHED,THEMETERISADDEDTHEAMOUNTOFMONOMERMETHYLMETHACRYLATE,STIRRINGUNTILAPREDETERMINEDREACTIONTIMETHEPRODUCTISREMOVEDANDCOOLEDTOROOMTEMPERATUREDETERMINATIONOFVISCOSITYOFTHEPRODUCTTWENTYSECONDVOLUMEFOURTHJOURNALOFWUHANINSTITUTEOFCHEMICALTECHNOLOGYVOL22NO4DECEMBER2000JWUHANINSTCHEMTECHDEC200022EXPERIMENTALPROGRAMBECAUSEOFTHEINFLUENCEFACTORSOFGRAFTCOPOLYMERIZATION,MORETHEORTHOGONALEXPERIMENTWASUSEDTOANALYZETHEEFFECTSOFVARIOUSFACTORSONTHEPROPERTIESOFTHEPRODUCTSTHEOPTIMUMREACTIONCONDITIONSWEREOBTAINEDANDTHELEVELOFORTHOGONALEXPERIMENTWASINVESTIGATEDSEETABLE1,TABLE2TABLE1TABLE1LEVELFACTOROFCERIUMSALTTABLE1,LEVELS,AND,FACTORS,OF,REACTION,INITIATED,BY,CE4FACTORFACTORSHORIZONTALLEVELS123REACTIONTIME/HREACTIONTIME123INITIATORDOSAGE/MLLLINITIATORAMOUNT123MONOMERDOSAGE/MLLLMONOMERAMOUNT101520REACTIONTEMPERATURE/TEMPERATUREREACTIONTEMPERATURE405060TABLE2HORIZONTALFACTORTABLESOFULTRAVIOLETLIGHTTABLE2,LEVELS,AND,FACTORS,OFREACTION,INITIATED,BY,UV,LIGHTFACTORFACTORSHORIZONTALLEVELS123REACTIONTIME/HREACTIONTIME123PHOTOSENSITIZERDOSAGE/MLLLPHOTOSONSITICERAMOUNT304050MONOMERDOSAGE/MLLLMONOMERAMOUNT579REACTIONTEMPERATURE/TEMPERATUREREACTIONTEMPERATURE405060AFTERTHEORTHOGONALEXPERIMENT,INORDERTOINVESTIGATETHEINFLUENCEOFVARIOUSFACTORSONTHEVISCOSITYOFTHEPRODUCTTHEINFLUENCEOFDEGREEWASANALYZEDBYSINGLEFACTOR3EXPERIMENTALRESULTSANDDISCUSSIONANALYSISOFTHERESULTSOF31ORTHOGONALEXPERIMENTSACCORDINGTOTHETABLEOFLEVELFACTORSSHOWNINTABLE1ANDTABLE2,ACCORDINGTOTHEORTHOGONALREALTHERULEOFEXPERIMENTISTOTAKETHEORTHOGONALEXPERIMENTOFEACHFACTORINDEPENDENTOFEACHOTHERL934THERESULTSOFTHETWOSETSOFEXPERIMENTSARELISTEDINTABLES3AND4ITCANBESEENFROMTABLE3ANDTABLE4THATUVINDUCEDGRAFTREACTIONTHEMOSTINFLUENTIALFACTORWASTHEREACTIONTIME,WHEREASCERIUMSALTSWERETHEMOSTINFLUENTIALTHEBIGFACTORISTHEAMOUNTOFINITIATOR,WHICHISTHESAMEASBEFORETHERESULTSOFTHESTUDYAREIDENTICALTHEOPTIMUMREACTIONOFCERICSALTWASOBTAINEDBYORTHOGONALEXPERIMENTTHECONDITIONISA3B2C3D2,THATIS,THEREACTIONTIMEIS3H,ANDTHEINITIATORISUSEDTHEAMOUNTIS2ML/L,THEMONOMERDOSAGEIS20ML/L,ANDTHEREACTIONTEMPERATUREISTABLE3SCHEMEANDRESULTOFORTHOGONALEXPERIMENTINITIATEDBYCERIUMSALTTABLE3,ORTHOGONAL,EXPERIMENT,PLAN,AND,EFFECT,OFREACTIONINITIATEDBYCE4EXPERIMENTSERIALNUMBERTESTNOITEMITEMABCDVISCOSITYMPASVISCOSITY111104026500212155048200313206046500421156032000522204047200623105044500731205043600832106042800933154046600YI1404000340333,379333,40100/YI2412333460667,422667,454333/YI3443333458667,457667,404333/RANGELIMITERREUR39333,120334,78333,53333/TABLE4SCHEMEANDRESULTOFUVINDUCEDORTHOGONALDESIGNTABLE4,ORTHOGONAL,EXPERIMENT,PLAN,AND,EFFECT,OFREACTION,INITIATED,BG,UV,LIGHEEXPERIMENTSERIALNUMBERTESTNOITEMITEMABCDVISCOSITYMPASVISCOSITY113054028600214075051500315096046300423076046500524094060600625055058400733095051600834056052200935074055600YI1421333422333,464333,482667/YI255166754800,51200,538333/YI3525000534333,528333,483667/RANGELIMITERREUR130333,125667,6400,55666/50THEOPTIMUMOPERATINGCONDITIONSFORUVINDUCEDREACTIONSAREA2B2C3D2,THATIS,THEREACTIONTIMEIS2HANDTHEPHOTOSENSITIZERDOSAGEIS40ML/L,THEAMOUNTOFMONOMERIS9ML/L,THEREACTIONTEMPERATUREIS50DEGCFROMTHERESULTSOFTHEVISCOSITYOFTWOSETSOFREACTIONPRODUCTS,THEEFFECTOFUVIRRADIATIONWASOBSERVEDTHEEFFECTISCLEARLYSUPERIORTOTHATCAUSEDBYCERIUMSALTS,IE,UVINDUCEDTHEGRAFTINGRATIOSHOULDBEHIGHERTHANTHERATEOFGRAFTINGINITIATEDBYCERIUMSALTSTHEWORKWASCONSISTENTWITHPREVIOUSSTUDIES7,FOURTH,YANGJIAMOETALSTUDYONGRAFTMODIFICATIONOFHYDROXYPROPYLCELLULOSE32SINGLEFACTORANALYSISASCANBESEENFROMFIGURE1ANDFIGURE2,THEREACTIONTIMEISRELATIVETOTHETWOKINDSOFGRAFTINGFIG1EFFECTOFREACTIONTIMEOFCERIUMSALTONVISCOSITYFIG1,VISCOSITY,OF,GRAFT,COPOLYMER,INITIATED,BY,CE4WAS,INFLUENCED,BY,REACTION,TIMEFIG2EFFECTOFUVIRRADIATIONREACTIONTIMEONVISCOSITYFIG2,VISCOSITY,OF,GRAFT,COPOLYMER,INITIATED,BYUV,LIGHT,WAS,INFLUENCED,BY,REACTION,TIMETHEREISANOPTIMUMVALUEFORTHEPOLYMERIZATIONREACTION,WHENTHEPRODUCTVISCOSITYEXCEEDSTHISVALUEINSTEAD,THISMAYBETHEMAINCHAINATTHEBEGINNINGOFTHEREACTIONTHEINITIATIONANDCHAINCONTINUE,WHILETHEREACTIONTIMEISTOOLONG,WHICHWILLLEADTOGRAFTCOPOLYMERIZATIONTHECHAINTERMINATIONREACTIONACCELERATEDANDTHEGRAFTINGRATEDECREASEDTHEOPTIMUMOPERATIONTIMEOFTHEGRAFTCOPOLYMERIZATIONISGREATERTHANTHATOFCERICSALTSHORT,BECAUSETHELIGHTTIMEISTOOLONG,ITISEASYTODEGRADETHECOPOLYMERASCANBESEENFROMFIGURES3AND4,THEREISATEMPERATUREINBOTHOFTHEMFIG3EFFECTOFREACTIONTEMPERATUREOFCERIUMSALTONVISCOSITYFIG3,VISCOSITY,OF,GRAFT,POLYMER,INITIATED,BY,CE4WAS,INFLUENCED,BY,REACTION,TEMPERATURETHEOPTIMUMVALUEISTHATTHETEMPERATURERANGEOFTHEREACTIONISNOTHIGHUNDERTHEEXPERIMENTALCONDITIONS,THEEXTREMEVALUETRENDISNOTOBVIOUS,ANDTHECURVEISMOREGENTLE,FROMTHEORTHOGONALEXPERIMENTALRESULTS,WECANSEETHERANGEANALYSISANDREACTIONTEMPERATURETHEDEGREEOFINFLUENCEISRELATIVELYSMALL,OFCOURSE,THETEMPERATURECANNOTRISETOOHIGH,THISWILLGUIDETHEVISCOSITYOFTHERESULTINGPRODUCTWILLDECREASEANDTHECOSTWILLINCREASEFIG4EFFECTOFUVINDUCEDREACTIONTEMPERATUREONVISCOSITYFIG4,VISCOSITY,OF,GRAFT,COPOLYMER,INITIATED,BYUV,LIGHT,WAS,INFLUENCED,BY,REACTION,TIMEFIGURES5AND6SHOWTHEEFFECTOFTHEAMOUNTOFMONOMERONTHEVISCOSITYOFTHEPRODUCTFIG5EFFECTOFTHEAMOUNTOFCERIUMSALTONTHEVISCOSITYOFMONOMERFIG5,VISCOSITY,OF,GRAFT,COPOLYMER,INITIATED,BY,CE4WAS,INFLUENCED,BY,PHOTOSENSITIZER,AMOUNTFIG6EFFECTOFUVIRRADIATIONONTHEVISCOSITYOFMONOMERFIG6,VISCOSITY,OF,GRAFT,COPOLYMER,INITIATED,BYUV,LIGHT,WAS,INFLUENCED,BY,PHOTOSENSITIZER,AMOUNTFROMTHEDIAGRAM,WHENTHEAMOUNTOFMONOMERINCREASES,THEVISCOSITYOFTHEPRODUCTINCREASESRAPIDLY,BUTWHENTHEBESTVALUEISREACHED,ITISNOTNECESSARYTOCONTINUETOINCREASETHEAMOUNTOFMONOMERTHEBIGCANONLYRAISETHECOSTOFPRODUCTION4CONCLUSIONAUSESHYDROXYPROPYLSALTASINITIATORANDUVINHYDROXYPROPYLCELLULOSETHEGRAFTCOPOLYMERIZATIONCANINCREASETHEVISCOSITYOFTHEREACTIONPRODUCTSACHIEVETHEPURPOSEOFMODIFICATION,BUTTHEEFFECTOFLIGHTISBETTERTHANTHATOFCERIUMSALTTECHNICALLY,CERIUMSALTSAREEASYTOINITIATEANDCOSTLESSBTHEREACTIONTIMEANDTEMPERATUREOFTHETWOINITIATIONMETHODSAREBOTH8THEREISANOPTIMUMVALUEINTHETWENTYSECONDVOLUMEOFJOURNALOFWUHANINSTITUTEOFCHEMICALTECHNOLOGYMORETHANTHISVALUEWILLLEADTOTHEENDOFTHECHAININTHEREACTIONPROCESSTHE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