高分子量聚丙烯酰胺的合成

1、Synthesisofacationicpolyacrylamidewithhighmolecularweightandhighpurity背景：阳离子聚丙烯酰胺絮凝剂作为有机高分子絮凝剂已被广泛应用于污泥脱水工业废水及市政污水的处理。目前，阳离子聚丙烯酰胺系列产品絮凝剂在美国日本欧洲各国的用量已占有机絮凝剂总量的75%-80%近年来，国内对阳离子聚丙烯酰胺系列絮凝剂的市场需求在不断增加，但在应用方面，大多局限于污水及污泥处理，用于饮用水源处理的研究较少；在使用过程中，存在价格昂贵缺乏成品的质检和有效的卫生监控等问题，使得絮凝剂的卫生安全存在较大隐患。在一些情况下和一定范围内，阳离子聚丙烯酰胺

2、的分子量越大，处理效果越好阳离子聚丙烯酰胺对原水处理中部分常规处理工艺难以去除的有机污染物有较好的去除效果，但由于聚丙烯酰胺产物中存在未聚合的丙烯酰胺单体，丙烯酰胺是一种水溶性具有神经毒性和遗传毒性的致癌物，极大的限制了其在原水处理中的应用目前，国内对聚丙烯酰胺的研究大多仅停留在如何提高聚合物的相对分子质量，对如何降低聚合物中残留单体含量的研究较少因此，为了满足国内市场对高纯度高分子量絮凝剂的需求研究降低阳离子聚丙烯酰胺中残留丙烯酰胺含量同时又保证合成高分子量的聚合物合成适用于饮用水源水处理的有机高分子絮凝剂具有重要的意义。高分子量聚丙烯酰胺的定义聚丙烯酰胺（Polyacrylamide,PA

3、M是丙烯酰胺及其衍生的均聚物和共聚物的统称。聚丙烯酰胺的分子量有低、中、高和超高之分，一般来说，100万以下为低分子量、100万-1000万为中低分子量、1000万以上高分子量。所以高分子量聚丙烯酰胺是分子量在1000万以上有机高分子聚合物。高分子量聚丙烯酰胺的分子结构高分子量聚丙烯酰胺的分子结构为：CHCHnIJnCONH结构式中丙烯酰胺分子量为，n值为2X1049X105,故聚丙烯酰胺分子量一般为X1066X107。高分子量聚丙烯酰胺的分类根据PAM大分子链上官能团在水溶液中的离解性质，可划分成阴离子型（CPAM、阳离子型（APAM、非离子型（NPAM及两性离子型几个品种。阳离子型一般都含

4、有微量毒性，不适宜在给排水工程中使用，所以我们接触到的水处理剂聚丙烯酰胺均属阴离子型或非离子型。根据高分子量聚丙烯酰胺的纯度产品来分，有粉剂和胶体两种，粉剂产品为白色或微黄色颗粒或粉末，固含量一般在90%乂上，胶体产品为无色微黄色透胶体，固含量为8%9%。高分子量聚丙烯酰胺的特点高分子量聚丙烯酰胺因其结构单元中含有酰胺基、易形成氢键，使其具有良好的水溶性和很高的化学活性，可通过接枝、交联等反应得到多种衍生物。高分子量聚丙烯酰胺是由丙烯酰胺单体聚合而成的有机高分子聚合物，无色无味、无臭、易溶于水，没有腐蚀性。高分子量聚丙烯酰胺在常温下比较稳定，高温、冰冻时易降解，故其贮存与配制投加时，温度应控制

5、在2c55c时。高分子量PAM勺合成方法简介目前，PAM的合成方法根据聚合是否加入其他单体，又可分为均聚和共聚2种，PAM产品形态有水溶液、乳剂和粉剂等。国内外常用的AM聚合方法有水溶液聚合法，反相乳液聚合法，悬浮聚合法等，其基本原理都是基于AM在引发剂的作用下，进行自由基引发聚合生成聚丙烯酰胺，反应式如下：由上式可知AM聚合过程中链增长，链引发及链终止反应符合自由基引发聚合的一般规律，故AM的聚合反应为自由基引发聚合反应。水溶液聚合法水溶液聚合法是将单体AMffi引发剂溶解在水中的聚合反应，是目前应用较广泛和成熟的技术。所得PAM产品有胶状和粉状2种，其胶体采用质量分数为8%-10喊20%-

6、30%AM勺水溶液在引发剂作用下直接聚合而得，产物经脱水干燥后可得粉状产品。产物相对分子质量为7万-700万。该法优点为安全、工艺设备简单、环境污染小，缺点是产物固含量低，仅为8%-15%且易发生酰亚胺化反应，生成凝胶。在PAM的水溶液聚合中，引发剂在很大程度上决定了聚合反应后得到产物的相对分子质量、产率，因而新型引发体系的开发是AM水溶液聚合研究的关键。反相乳液聚合法丙烯酰胺单体配制成浓度为30%60%的水溶液作为分散相，其中加有少量的二乙胺四乙酸和Na2SO及氧化一还原引发剂和适量水溶性表面活性剂，其HLB值应较低。用芳炫或饱和脂肪炫作为连续相，其中加有油溶性表面活性剂，其HLB值应较高，

7、如脱水山梨醇油酸酯。Na2SO4M有防止胶乳粒子粘结的作用。分散相与连续相的比例通常为3:7。聚合所得分散相胶乳粒子直径为10区m与表面活性剂用量有关。反应温度一般为40C6h转化率可达98%。此法的优点是反应热易导出，物料体系粘度低，便于操作，产品可不经干燥直接应用。缺点是使用有机溶剂，易燃、有效生产能力低于溶液聚合法。反相悬浮聚合法反相悬浮聚合是近几年发展起来的新方法。反相悬浮聚合法生产土艺简单、成木低，易十实现土业化，产品相对分子质量可达千万以上，溶解性能比水溶液聚合产品好，可直接得到粉状或粒状产品，包装和运输方便。新的聚合方法近年来对PAM合成中自由基引发方式的研究有了新进展，采用更为

8、节能环保的引发体系，如光引发聚合、热引发聚合、辐射聚合、等离子体引发聚合、沉淀聚合、胶束聚合等。SynthesisofacationicpolyacrylamidewithhighmolecularweightandhighpurityBackground:cationicpolyacrylamideflocculantasanorganicpolymerflocculanthasbeenwidelyappliedintheprocessingofindustrialwastewaterandmunicipalsewagesludgedewatering.Atpresent,thecation

9、icpolyacrylamideflocculantseriesproductsintheUnitedStatesJapanthedosageoftheEuropeancountrieshaveaccountedfor75%80%ofthetotalorganicflocculant.Inrecentyears,thedomesticmarketdemandofcationicpolyacrylamideflocculantseriesareontheincrease,butintermsofapplication,aremostlylimitedtosewageandsludgetreatm

10、ent,andlessresearchfordrinkingwatertreatment;Inuseprocess,thereisexpensivelackoffinishedproductqualityandeffectivehealthmonitoring,etc.,makesflocculanthealthsecuritythereisabighiddentrouble.Insomecases,andacertainrange,thehigherthemolecularweightofthecationicpolyacrylamide,thebetterthetreatmenteffec

11、tcationicpolyacrylamideinrawwatertreatmentispartoftheconventionaltreatmentprocessisdifficulttoremovetheorganicpollutantshasbetterremovaleffect,butasaresultofpolyacrylamideproducts,didnotexistinthepolymerizationofacrylamidemonomeracrylamideisakindofwater-solublecarcinogenswithneuraltoxicityandgenetic

12、toxicity,greatlylimitsitsapplicationintherawwatertreatmentatpresent,thedomesticstudyofpolyacrylamidearemostlyjuststayonhowtoimprovethepolymerrelativemolecularmass,thestudyofhowtoreducetheresidualmonomercontentinpolymersless,therefore,inordertomeetdomesticmarketdemandforhighpurityhighmolecularweightf

13、locculantsresearchtoreduceresidualacrylamidecontentincationicpolyacrylamideagainatthesametimetoensurethatthesynthesisofhighmolecularweightpolymersynthesisissuitablefordrinkingwatersupplyinwatertreatmentoforganicpolymerflocculanthasthevitalsignificance.thedefinitionofhighmolecularweightpolyacrylamide

14、PAM(Polyacrylamide,PAM)acrylamideanditsderivativesofhomopolymerandcopolymer.Molecularweightofpolyacrylamidewithlow,medium,highandultra-high,ingeneral,forlowmolecularweightbelow1million,1million-10millionasthelowmolecularweight,highmolecularweightmorethan10million.Sothehighmolecularweightpolyacrylami

15、deisover10millionorganicpolymermolecularweight.themolecularstructureofthehighmolecularweightpolyacrylamideThemolecularstructureofthehighmolecularweightpolyacrylamideCHCH上|JnCONHis:Structuralformulaofacrylamidemolecularweightis,thevalueofnforthe2x1049x105,sothepolyacrylamidemolecularweightaverageofx1

16、066x107.theclassificationofhighmolecularweightpolyacrylamideAccordingtoPAMdissociationpropertiesoffunctionalgroupinaqueoussolution,macromolecularchaincanbedividedintoioniccolorful(CPAM),cationic(APAM),nonionic(NPAM)andamphotericionicseveralvarieties.Cationicgenerallycontaintracesoftoxicity,notsuitab

17、leforuseinwatersupplyanddrainageengineering,sowecomeintocontactwiththewatertreatmentagentbelongtotheanionicandnonionicpolyacrylamide.Accordingtothepurityofhighmolecularweightpolyacrylamideproducts,hastwokindsofpowderandcolloid,powderproductiswhiteorlightyellowgranularorpowder,solidcontentisincommonl

18、y90%,colloidalgelproductisacolorless,yellowish,solidcontentis8%9%.thecharacteristicsofhighmolecularweightpolyacrylamideHighmolecularweightpolyacrylamidebecauseofitsstructuralunitcontainingamide,easytoformhydrogenbonding,makeithasgoodwatersolubilityandhighchemicalactivity,canbeobtainedbygraftingandcr

19、osslinkingreactionssuchasavarietyofderivatives.Highmolecularweightpolyacrylamideiscomposedofacrylamidemonomerpolymerizationoforganicpolymer,colorless,tasteless,odourless,solubleinwater,nocorrosion.Highmolecularweightpolyacrylamideisstableatroomtemperature,hightemperature,easydegradation,whenfrozenso

20、itsstorageandpreparationforovertime,temperatureshouldbecontrolledwithin2c55C.thesynthesisofhighmolecularweightPAMAtpresent,thesynthesismethodsofPAMaccordingtowhetheraggregationwilljoinothermonomer,candivideagainhomopolymerizationandcopolymerization,PAMproductformaaqueoussolution,emulsion,andpowder,e

21、tc.AMpolymerizationmethodscommonlyusedathomeandabroadwithaqueoussolutionpolymerization,inverseemulsionpolymerization,suspensionpolymerizationandsoon,ofthegenerateitsbasicprincipleisbasedonAMinundertheactioninitiator,carriesonthefreeradicalpolymerization,polyacrylamide,equationisasfollows:Bytypeknown

22、AMchainpolymerizationprocess,thechaininitiationandterminationreactionaccordswiththegenerallawoffreeradicalpolymerization,thepolymerizationreactionoffreeradicalpolymerizationreactionofreasonAM.aqueoussolutionpolymerizationAqueoussolutionpolymerizationmonomerAMandinitiatorofpolymerization,dissolvedint

23、hewateriswidelyusedandmaturetechnology.ThePAMgelandpowderproducts,thecolloidbymassfractionis8%-10%or10%-30%aqueoussolutionofAMdirectpolymerizationundertheactionofainitiatorand,afterdryingcanbepowderproduct.Productmolecularweightis70000-7million.Theadvantagesofsafety,simpleprocessequipment,environmen

24、talpollutionissmall,thedisadvantageisthattheproductsolidcontentislow,only8%-8%,andpronetoimidereaction,generategel.InthePAMaqueoussolutionpolymerization,theinitiatortoagreatextent,determinestherelativemolecularmassoftheproductresultingfromthepolymerizationreaction,yield,andthedevelopmentofthenewinit

25、iatorsystemisthekeytoAMaqueoussolutionpolymerizationresearch.inverseemulsionpolymerizationAcrylamidemonomermixtureconcentrationis30%60%aqueoussolutionasthedispersedphase,whichaddasmallamountofdiethylaminetetraaceticacidandNa2SO4andoxidation-reductioninitiatorandrightamountwatersolublesurfactant,theH

26、LBvalueshouldbelower.Witharomatichydrocarbonsorsaturatedhydrocarbonsascontinuousphase,whichisoilsolublesurfactant,theHLBvalueshouldbehigher,suchasdehydration,sorbitanoleate.Na2SO4havepreventthelatexparticlebondingeffects.Theproportionofthedispersedphaseandcontinuousphaseisusually3:7.Aggregateincomedispersedphaselatexparticleswas10micronsindiameter,relatedtothedosageofsurfaceactiveagent.Reactiontemperatureiscommonly40C6hconversionratecouldreach98%.Thismethodhastheadvantageofheatofreactionisderived,andthematerialsystem