有机硅改性聚丙烯酸酯乳液的细乳液合成及应用

浙江理工大学材料与纺织学院毕业设计(论文)诚信声明我谨在此保证：本人所写的毕业设计(论文)，凡引用他人的研究成果均已在参考文献或注释中列出。设计(论文)主体均由本人独立完成，没有抄袭、剽窃他人已经发表或未发表的研究成果行为。如出现以上违反知识产权的情况，本人愿意承担相应的责任。声明人(签名)：年月日i摘要聚丙烯酸酯因成膜性好，粘结性强，耐热等优点而被广泛应用于涂料印花粘合剂，但其存在胶膜硬度大，耐水性差，冷脆热黏等缺点而影响了印花产品的质量。聚硅氧烷疏水性强，链段柔顺，将含有乙烯基的聚硅氧烷对聚丙烯酸进行改性，能有效改善聚丙烯酸酯粘合剂的缺点，提高涂料印花的色牢度与手感。因此本文合成出双端乙烯基聚二甲基硅氧烷（diVi-PDMS），并将其用于改性聚丙烯酸酯，制得一种新型涂料印花粘合剂，使得涂料印花织物兼具良好的耐摩擦牢度和手感。主要研究内容分为两部分：第一部分：双端乙烯基聚二甲基硅氧烷的合成及表征。采用1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷和八甲基环四硅氧烷为原料，以三氟甲基磺酸为催化剂，通过阳离子开环聚合合成双端乙烯基聚硅氧烷（diVi-PDMS）。研究了催化剂用量，反应温度和反应时间对产物转化率和封端率的影响，优化了合成工艺条件并采用红外光谱（FTIR）和核磁共振（1H-NMR）对产物结构进行表征。结果表明：双端乙烯基聚硅氧烷（diVi-PDMS）的优化工艺条件为催化剂用量0.15%，反应温度70℃，反应时间6h，产物转化率达到91%,FTIR和1H-NMR谱图分析表明了产物为双端乙烯基聚硅氧烷（diVi-PDMS)。第二部分：diVi-PDMS改性聚丙烯酸酯细乳液的合成及其性能研究。采用自制的双端乙烯基聚硅氧烷（diVi-PDMS）改性聚丙烯酸酯，通过细乳液聚合制得有机硅改性聚丙烯酸酯乳液。研究了传统乳化剂（SDS:O-10）/可聚合乳化剂（V-20S）配比及用量，有机硅单体分子量对聚合稳定性、乳液性能、胶膜性能及涂料印花性能的影响，并用红外光谱仪（FTIR）、热重分析仪（TG）、差示扫描量热仪（DSC）等对聚合物的结构和性能进行测定和表征。结果表明：乳化剂配比为1.5:1:1、用量为6%时，聚合稳定性及乳液稳定性良好，乳液粒径小，分布窄，且相比传统乳化剂，复配可聚合乳化剂明显提升胶膜的力学性能；随着diVi-PDMS分子量的增大，胶膜交联度降低，耐水性降低，力学性能变差，涂料印花织物耐摩擦牢度变差，当diVi-PDMS分子量为约为1600时，胶膜水接触角为94.9°，吸水率为7.39%，印花织物干、湿摩擦牢度可达4级，手感柔软。红外分析表明产物为有机硅改性聚丙烯酸酯，DSC和TG分析表明经改性后聚合物的玻璃化温度降低，热分解温度提高，耐热稳定性增强。ii论文研究表明，以双端乙烯基聚硅氧烷（diVi-PDMS）为改性单体，采用细乳液聚合，制备有机硅改性聚丙烯酸酯乳液粘合剂，应用于印花涂料，其印花织物耐干、湿摩擦牢度均达到4级，手感柔软，印花织物具有良好的耐摩擦牢度，又具有柔软的手感。关键词：聚丙烯酸酯；双端乙烯基聚硅氧烷；细乳液聚合；涂料印花iiiAbstractPolyacrylatehasbeenwidelyusedaspigmentprintingbinderbecauseofitsadvantages,suchasgoodfilm-formingability,strongadhesion,goodheatresistance,etc.However,thepolyacrylategenerallyexistsmanydefectswhichaffectthequalityoftheprintingproducts,suchashighhardness,poorpropertyofwaterproof,hotsticky-coolbrittleperformanceofthelatexfilm.Therearemanyadvantagesinpolydimethylsiloxane(PDMS),suchasgoodhydrophobicityandflexibility.PDMSwhichcontainsvinylgroupwasappliedinthemodificationofpolyacrylate,inordertoimprovethecolorfastnessandhandleofpigmentprintingfabric.Inthispaper,adoubleVinyl-terminatedpolydimethylsiloxane(diVi-PDMS)wassynthesizedandappliedinthepreparationofsilicone-modifiedpolyacrylateemulsionforpigmentprintingbinder,soastobegoodcolorfastnessandsofterhandleofpigmentprintedfabric.Therearetwopartsinthispaper.Part1:SynthesisandcharacterizationofdiVi-PDMSInthispart,diVi-PDMSwassynthesizedbyring-openingpolymerizationreactionofcationicwith1,3-divinyl-1,1,3,3-tetramethyldisiloxaneandOctamethylcyclotetrasiloxane,usingtrifluoromethanesulfonicacidasacatalyst.Theinfluencesofreactionfactorssuchasamountofcatalyst,reactiontemperatureandtimeontheconversionrateandyieldofterminationwereinvestigated,thenthesynthesisconditionswereoptimizedandthestructureofproductwascharacterizedbyFTIRand1H-NMR.TheresultsshowedthattheoptimalconditionforthepreparationofdiVi-PDMSwasthattheamountsofcatalystwere0.2%,reactiontemperaturewas70℃andreactiontimewas6h.Intheoptimalcondition,theconversionratecanreach91%.TheresultsofFTIRand1H-NMRanalysisindicatedthatthestructureofproductwasdiVi-PDMS.Part2:SynthesisandcharacterizationofdiVi-PDMSmodifiedpolyacrylateminiemulsionInthispart,thediVi-PDMSmodifiedpolyacrylateminiemulsionwaspreparedwithdiVi-PDMSandpolyacrylateviaminiemulsionpolymerization.Theratioandivdosageoftraditionalemulsifier(SDS:O-10)/polymericemulsifier(V-20S),themolecularweightoforganicsiliconmonomeronthepolymerizationstabilityandthepropertiesofsilicone-modifiedpolyacrylateemulsion,latexfilmandpigmentprintingwerestudied.ThepolymerstructureandpropertieswerecharacterizedbyFTIR,TGAandDSC.Theresultsshowedthatwhenthemassratioofpolymerizableemulsifierwas1.5:1:1andtheamountofcompoundemulsifierwas6%,thepolymerizationandlatexhadgoodstability,thelatexhadsmallparticlesizeandnarrowdistribution.Comparedtoconventionalemulsifier,complexpolymericemulsifiercansignificantlyimprovethemechanicalpropertiesofthefilm.WiththeincreaseofmolecularweightofdiVi-PDMS,thecrosslinkingdegreeofthefilm,thewaterresistance,themechanicalpropertiesandtherubbingfastnessofpigmentprintingfabricbecameworse.ItwasfoundthatthemolecularweightofdiVi-PDMSwasabout1600,thewatercontactangleofthefilmwas94.9°,thewaterabsorptionwas7.39%,thedryandwetrubbingfastnessofpigmentprintingfabricreached4grade,andtheprintedfabric’shandlebecamesofter.TheresultsofFTIRanalysisindicatedthattheproductwassilicone-modifiedpolyacrylateminiemulsion,DSCandTGanalysisdisplayedthattheglasstransitiontemperaturesofsilicone-modifiedpolymerwasreduced,thermaldecompositiontemperatureandheat-resistantstabilitywasincreased.TheresultsofprojectshowedthatthediVi-PDMSmodifiedpolyacrylateadhesivelatespreparedbyminiemylsionpolymerizationcanbeusedaspigmentprinting,thecolourfastnesstodryandwetrubbingoftheprintedfabriccouldreachgrade4,anditshandlewassofter,basicallyachievedtheobjectiveunificationofhandleandfastness.keywords：Polyacrylate;diVi-PDMS;Miniemulsionpolymerization;PigmentprintingI目录摘要Abstract第1章绪论.................................................................................................................................11.1引言.......................................................................................................................