新型共聚砜超濾膜及季銨化聚醚砜酮納濾膜.pdf

1、新型共聚礬超濾膜及季餒化聚醚硯酮納濾膜摘要含二氮雜蔡酮結(jié)構(gòu)的系列共聚Il(PPESB)是本研究組開(kāi)發(fā)的新材料。它是由本組自制的二氮雜蔡酮聯(lián)苯酚(DHPZ)、商用雙酚A(BPA)和44一二氯二苯K(DCS)共聚得到。它具有良好的耐熱性、耐酸堿性、耐氧化性、耐氯性和機(jī)械性能。為了將其制備成非對(duì)稱(chēng)超濾膜，本文采用溶解度參數(shù)差、聚合物一非溶劑相互作用參數(shù)X13特性粘度和PPESB溶劑非溶劑三元相圖四種方法，確定了PPESB與七種非溶劑的相溶性順

2、序，初步選擇了膜材料及制膜用添加劑和凝膠劑，為鑄膜液配制提供了理論依據(jù)。以PPESB(1:1)PPESB(1:3)為膜材料(1:11:3指聚合物中BPA與DHPZ兩種結(jié)構(gòu)單元的比例)，N一甲基一2P咯烷酮(NMP)為溶劑，分別選用丁酮(BO)、乙醚(EE)、乙二醇甲醚(EGME)、一縮二乙二醇(DEGC)和聚乙二醇400(PEG400)為添加劑，制得了一系列超濾膜。詳細(xì)考察了聚合物濃度、添加劑種類(lèi)和用量、凝膠浴溫度以及熱處理對(duì)膜J勝能及

3、結(jié)構(gòu)的影響。所制得的超濾膜，在OAMPa的壓力下，可截留不同分子量的PEG(PEG200。一~PEG10000)，水通量介于192578kg(m2h)。將PPESB膜用于2000mgL硫化黑染料水溶液的截留，當(dāng)操作溫度由18℃升高到95℃時(shí)，膜的滲透通量提高了1.4倍，對(duì)染料的截留率變化不大。以Elias方法為理論依據(jù)，PPESBNMP非溶劑三相體系的相分離曲線為數(shù)據(jù)基礎(chǔ)，分別計(jì)算了PPESB(1:1)和PPESB(1:3)的?；旌先軇?/p>

4、(非溶劑NMP)的組成，結(jié)果發(fā)現(xiàn)此組成與PPESB膜性能突變(或變差)時(shí)鑄膜液中混合溶劑(添加劑NMP)的組成接近。含二氮雜蔡酮結(jié)構(gòu)的聚醚颯酮(PPESK)是本研究組研制開(kāi)發(fā)的，目前耐熱等級(jí)最高的可溶性聚芳醚樹(shù)脂，它具有良好的化學(xué)穩(wěn)定性、機(jī)械性能和成膜性。本文以98%濃硫酸為溶劑和催化劑，氯甲基丁醚為氯甲基化試劑，對(duì)PPESK進(jìn)行氯甲基化改性，制得了氯甲基化程度為02.1的氯甲基化聚醚ix酮(CMPPESK)(其中氯甲基化程度指高分子的

5、每個(gè)重復(fù)單元中一CH2Cl的個(gè)數(shù))。并通過(guò)’HNMR3CNMR對(duì)分子結(jié)構(gòu)進(jìn)行表征。詳細(xì)考察了反應(yīng)溫度、時(shí)間、濃硫酸用量、氯甲基丁醚用量等因素對(duì)反應(yīng)的影響，確定了不同氯甲基化程度CMPPESK的反應(yīng)工藝條件。計(jì)算了不同反應(yīng)溫度下反應(yīng)的表觀速率常數(shù)以及反應(yīng)的活化能。并測(cè)試了CMPPESK的溶解性和5%熱失重溫度(5%TG)，發(fā)現(xiàn)CMPPESK在NMPDMAcDMF等極性有機(jī)溶劑中具有良好的溶解性隨氯甲基化程度的升高，CMPPESK的5%TG

6、下降。將CMPPESK與三甲胺反應(yīng)，制得了季按化程度為0.3mmo雌0.8mmo魄的季按化聚醚諷酮(QAPPESK)?？疾炝巳装窛舛取⒎磻?yīng)溫度、時(shí)間對(duì)季餒化反應(yīng)的影響。新型共聚礬超濾膜及季鉸化聚醚楓酮納濾膜AbstractAseriesofnovelpolymerspoly(phthalazinoneethersulfone)bisphenois(PPESB)sweresynthesizedfromthephthalazinonemo

7、nomer(DHPZ)commercialbisphenolA(BPA)and44dichiclordiphenalsulfone(DCS)whichexhibitexcellentthermostabilityacidresistancealkalineresistanceoxideresistancechlorideresistanceandmechanicalproperties.Topreparenonsymmetricmemb

8、ranebasedonthesematerialsfourmethodsincludingsolubilityparameterspolymernonsolventinteractionparameterintrinsicviscositiesandPPESBNMPnonsolventternaryphasediagramswereusedtodeterminetheconsistenciesbetweenpolymerandseven

9、nonsolvents.Thustheinitialtheoreticalbasiswasprovidedtooptimizethematchingofpolymersolventandadditivesprimarily.Theseriesofultrafrltration(UF)membraneswerepreparedwithPPESB(1:1)andPPESB(1:3)asmembranematerialsNmethyl2pyr

10、rolidinone(NMP)assolventandfivenonsovIents(includingbutanoneethyletherethyleneglycolmonomethyletherdiethyleneglycolandpolyethyleneglycol400)asadditives.Theinfluencesofpolymerconcentrationtypeandamountofadditivescoagulati

11、onbathtemperatureheattreatmenttechnicsonmembraneperformanceandstructurewerestudiedindetail.At0.1MPaOFmembraneswithrejectioncapacityofPEG2000PEG10000andpurewaterfluxof192578kg(mzh)wereobtained.FurtherthermostabilityofPPES

12、Bmembranewasinvestigated.Whenoperatingtemperaturewasraisedfrom180Cto950CfluxofPPESBmembraneincreased1.4timesandtherejectionforsulfurizedbluedyehadnoobviouschange.AccordingtothePPESBNMPnonsolventsternaryphasediagramstheth

13、etacompositionsofmixedsolvent(nonsolventNMP)forPPESB(1:1)andPPESB(1:3)werecalculatedbyEilasmethod.Itisfoundthatthetacompositionisclosetothecompositionofmixedsolvent(additiveNMP)inthecastingsolutionatthemutation(orworseni

14、ng)ofOFmembraneperformance.Poly(phthalazinoneethersulfoneketone)(PPESK)synthesizedinourlabhasperfectthermostabilitychemicalstabilityandmechanicalpropertiesandiseasytobepreparedintomembrane.InthispaperPPESKwasmodifiedbych

15、loromethylationwith98%concentratedsulfuricacidassolventandcatalystchloromethylbutylether(CMBE)aschloromethylationagent.ChloromethylatedPPESKs(CMPPESKs)withadegreeofchloromethylation(DCM)rangingfrom0to2.1(numbersofCHCIper