1、脂肪族水性聚氨醋的合成及結(jié)構(gòu)與性能關(guān)系的研究摘要本論文以異佛爾酮二異氰酸酷(IPDI)為原料，合成了多種脂肪族水性聚氨酷。整個(gè)工作可以分為3個(gè)主要部分:(1)預(yù)聚體乳化過(guò)程中的相轉(zhuǎn)變行為研究(2)乳液的粒徑大小、分布及穩(wěn)定性研究(3)水性聚氨酷結(jié)構(gòu)與性能的關(guān)系研究。一倩次系統(tǒng)地研究了脂肪族水性聚氨酷預(yù)聚體乳化過(guò)程中的相轉(zhuǎn)變行為。解釋了乳化進(jìn)行的機(jī)理，討論了預(yù)聚體在有機(jī)溶劑中的聚集態(tài)結(jié)構(gòu)。帶有離子基團(tuán)的預(yù)聚體分子可以形成鏈段微離子聚集體。

2、通過(guò)考察預(yù)聚體加水乳化過(guò)程中粘度及電導(dǎo)率的變化，研究了其相轉(zhuǎn)變行為.研究結(jié)果表明:乳化過(guò)程包括鏈段微離子聚集體的解聚集和疏水鏈段的聚集過(guò)程。依據(jù)乳化體系粘度和電導(dǎo)率的變化，可以將乳化過(guò)程劃分為3個(gè)部分.隨著軟段分子量的升高，乳化體系的相轉(zhuǎn)變點(diǎn)后延聚酷體系的相轉(zhuǎn)變比聚醚體系的相轉(zhuǎn)變發(fā)生得早nNCOnox值越接近1，體系的粘度就越高，相轉(zhuǎn)變發(fā)生所需的水含量也越高狡基含量及中和度也對(duì)分散體系的相轉(zhuǎn)變產(chǎn)生影響。研究得出的規(guī)律為水性聚氨醋合成條件

3、的優(yōu)化提供了理論依據(jù)。以均苯四甲酸酚和聚乙二醇600為原料，設(shè)計(jì)合成了一種新型的離子非離子復(fù)合型親水單體(K600)。并以K600、異佛爾酮二異氰酸酷(IPDI)和聚酩二元醇為原料合成了自乳化聚氨醋乳液。考察了K600對(duì)乳液外觀、粒徑大小及分布、粘度、凍融穩(wěn)定性、高溫穩(wěn)定性、抗電解質(zhì)能力、pH值穩(wěn)定性的影響關(guān)系。結(jié)果表明:所得產(chǎn)物具有優(yōu)異的綜合穩(wěn)定性，可以耐受80℃的長(zhǎng)期高溫20C18h凍融5次以上仍然穩(wěn)定可與10%NaCl溶液以任意比

4、例混合可在pH=114的范圍內(nèi)性質(zhì)穩(wěn)定。通過(guò)動(dòng)態(tài)力學(xué)分析(DMA)、應(yīng)力一應(yīng)變行為、紅外光譜(FTIR)等手段研究了脂肪族水性聚氨醋的結(jié)構(gòu)與性能關(guān)系.研究結(jié)果表明:聚酷型軟段和硬段之間的可以形成較強(qiáng)的氫鍵，相容性較好:聚醚型軟段與硬段之間形成的氫鍵較弱，軟硬段相容性較差。當(dāng)軟段的分子量為1000時(shí)，聚酷和聚醚型水性Investigationpolyurethanesonthesynthesisofaliphaticwaterbornea

5、ndtherelationshipsofpropertieswithstructureAbstractThesynthesisofaliphaticwaterbomepolyurethanesandtherelationshipsofpropertieswithstructurewasstudied.Itconsistsofthreemainparts:(1)thestudyonthephaseinversionbehaviorsdur

6、ingemulsificationprocess(2)thestudyonparticlesizedistributionandstabilityofwaterbomepolyurethanes(3)theinvestigationontherelationshipsbetweenmorphologyandpropertiesSeveralaliphaticwaterbornepolyurethaneprepolymersareprep

7、aredfromisophoronediisocyanate(IPDI)dimethylolpropanicacid(DMPA)poly(butyleneadipate)(PBA)andpolypropyleneglycol(PPG).Theprepolymersareblockedwith2methoxyethanolfollowedbyneutralizationpendantcarboxylbytriethylamine(TEA)

8、thendilutedto50wt%withmethylethylketone(MEK)，emulsifiedbyaddingdeionizedwaterunderconstantagitation.Theprincipleofemulsificationisexplained.TheaggregatedstructureofprepolymersinorganicsolventisdiscussedTheprepolymermolec

9、uleswithionicgroupscanformsegmentsmicroioniclaticesTheemulsificationprocessandphaseinversionarecharacterizedbyusingthevariationofviscosityandconductivity.Theemulsificationprocessincludesthedissociationofthesegmentsmicroi

10、oniclaticesandtheaggregationofthehydrophobicsegments.Theinversionprocesscanbeclearlydividedintothreeregionsdependinguponthevariationofviscosityandconductivity.Theexperimentalresultsshowthatseveralfactorscanafectthephasei

11、nversionheavilyincludingthemolecularweightandtypeofsoftsegmentsthenrrconoeratiocarboxylcontentandneutralizationdegree.Withtheincreasingofthemolecularweightofsoftsegmentthephaseinversiondelay.Inadditionthephaseinversionof

12、PBAbasedprepolymeroccursearlythanthatofPPGbasedprepolymerwhiletheirsoftsegmentmolecularweightareequal.Highnriconoxrationotonlydecreasetheviscosityofbothprepolymersolutionandemulsificationsystembutalsomakephaseinversionoc

13、curearly.Withtheincreasingofcarboxylcontentthephaseinversionoccursearly.Inthemeantimeappropriatecarboxylcontentcandecreasetheviscosityofphaseinversionpointandleadtoeasyphaseinversion.Thedecreaseofneutralizationdegreecanc

14、ontributetolowviscosityandearlyphaseinversion.Selectingappropriateconditionscanoptimizetheemulsificationprocess.Anewtypeofhydrophilicmonomer(K600)withbothionicgroupsandnonionicsegmentswassynthesizedfrompolyethyleneoxide(

15、Mn=600)and1245benzenetetracarboxylicdianhydride(BTDA).ThesynthesisprocesswasmonitoredwithFTIR.SeveralselfemulsifiablepolyurethaneemulsionswerepreparedfromIPDIPBAandK600inaprepolymermixingprocessusingsubstantialamountsolv

16、ent.TheacidgroupsareneutralizedwithTEA.TheemulsionbasedonDMPAwaspreparedbythesameprocedureforcomparison.TheefectofK600contentonthecharacteristicsofemulsionssuchasvisualappearanceparticlesizeanddistributionviscositydurabi