天然松香改性苯丙乳液的制备及性能
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摘要
以苯乙烯(St)、甲基丙烯酸甲酯(MMA)、丙烯酸-2-乙基己酯(2-EHA)、丙烯酸-2-羟基乙酯(HEA)和丙烯酸(AA)为反应单体,利用天然松香乳液作为改性剂,通过乳液聚合的方式制备了松香-苯丙复合乳液。研究了乳化剂用量、引发剂用量、松香乳液用量和单体配比对乳液性能的影响。并通过TGA、DLS、TEM对所制备的复合乳液进行了表征。结果表明:当乳化剂用量为单体质量的5%、引发剂用量为单体质量的0.8%、松香乳液用量为单体质量的30%、m(硬单体)∶m(软单体)=2.5∶1时,制得的乳液呈白色泛蓝光,粒径为131 nm。成膜后,漆膜光滑透明,硬度(1H)、耐水性(接触角97.05°)和附着力(1级)等性能良好。
A styrene acrylic composite emulsion was prepared by using styrene(St), methyl methacrylate(MMA), 2-ethylhexyl acrylate(2-EHA), 2-hydroxyethyl acrylate(HEA) and acrylic acid(AA) as monomers, natural rosin emulsion as modifier. The effects of emulsifier dosage, initiator dosage, rosin emulsion dosage and monomer ratio on the properties of emulsion were discussed. The obtained composite emulsion was characterized by TGA, DLS and TEM. The results showed that the resulting emulsion with a particle size of 131 nm presented white with blue phase when the mass fraction of emulsifier was 5%, mass fraction of initiator was 0.8%, mass fraction of rosin emulsion was 30%, mass ratio of hard monomer to soft monomer was 2.5∶1. In addition, the resulting film was absolutely smooth and transparent with good hardness(1 H), water resistance(contact angle 97.05 °) and adhesion properties(level 1).
A styrene acrylic composite emulsion was prepared by using styrene(St), methyl methacrylate(MMA), 2-ethylhexyl acrylate(2-EHA), 2-hydroxyethyl acrylate(HEA) and acrylic acid(AA) as monomers, natural rosin emulsion as modifier. The effects of emulsifier dosage, initiator dosage, rosin emulsion dosage and monomer ratio on the properties of emulsion were discussed. The obtained composite emulsion was characterized by TGA, DLS and TEM. The results showed that the resulting emulsion with a particle size of 131 nm presented white with blue phase when the mass fraction of emulsifier was 5%, mass fraction of initiator was 0.8%, mass fraction of rosin emulsion was 30%, mass ratio of hard monomer to soft monomer was 2.5∶1. In addition, the resulting film was absolutely smooth and transparent with good hardness(1 H), water resistance(contact angle 97.05 °) and adhesion properties(level 1).
引文
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[2]EL-MollaMM.Synthesisofpolyurethaneacrylateoligomersas aqueous UV-curable binder for inks of ink jet in textile printing and pigment dyeing[J]. Dyes and Pigments, 2007, 74(2):371-379.
[3]HuJ,MaJZ,DengWJ.Propertiesofacrylicresin/nano-SiO2leatherfinishingagentpreparedviaemulsifier-freeemulsion polymerization[J]. Materials Letter, 2008, 62:2931-2934.
[4]AthawaleVD, KulkarniMA.Preparationandpropertiesof urethane/acrylatecompositebyemulsionpolymerizationtechnique[J].Progress in Organic Coatings, 2009, 65(3):392-400.
[5]MaJianzhong(马建中),WangHuajin(王华金),BaoYan(鲍艳).Studyonsynthesisandperformanceofcore/shellsilicon-acrylate compoundinglatex[J].FineChemicials(精细化工),2010,27(2):195-200.
[6]NicolaT,OscarA,UlrichWS.Investigationonthewettability propertiesofthinfilmsofmethacrylicpolymerswithpartially fluorinated side chains[J]. Macromolecular Chemistry and Physics,1998, 199(11):2425-2431.
[7]Wang Xiaowen(王晓雯), He Yufeng(何玉凤), Wang Rongmin(王荣民),etal.Preparationandapplicationoffunctionalacrylate latex[J].ChemicalIndustryandEngineeringProgress(化工进展),2012, 31(9):2011-2018.
[8]Ren Tianrui(任天瑞). The chemistry of rosin and its application(松香化学及其应用)[M]. V1. Beijing:Chemical Industry Press, 2006:1-5.
[9]HayashiS,KimHJ,KajiyamaM,etal.Miscibilityand pressure-sensitiveadhesiveperformancesofacryliccopolymerand hydrogenated rosin systems[J]. Journal of Applied Polymer Science,1999, 71(4):651-663.
[10]ElisabettaC,JeanneM,LeiCH.Acomparisonoftackified,miniemulsioncore-shellacryliclatexfilmswithcorresponding particle-blendfilms:Structure-propertyrelationships[J].Langmuir,2009, 25(18):11021-11031.
[11]Wang Zhenghong(王振洪), Song Zhanqian(宋湛谦). Fine chemical utilizationofrosin(V)——Rosinandrosinesteremulsions[J].JournalofChemicalIndustryof ForestProducts(林产化工通讯),2003, 37(2):33-36.
[12]Wang Jifu(王基夫), Lin Mingtao(林明涛), Wang Chunpeng(王春鹏), et al. Synthesis and characterization of rosin-based UV curing coating[J].AppliedChemicalIndustry(应用化工),2011,40(7):1162-1169.
[13]TobingSD,KleinA.Mechanisticstudiesintackifiedacrylic emulsion pressure sensitive adhesives[J]. Journal of Applied Polymer Science, 2000, 76(13):1965-1976.
[14]TobingSD,KleinA,SperlingLH,etal.Effectofnetwork morphologyonadhesiveperformanceinemulsionblendsofacrylic pressure sensitive adhesives[J]. Journal of Applied Polymer Science,2001, 81(9):2109-2117.
[15]LuYanju(卢言菊).StudyonmultivariatemodificationanditsUV curingbehaviorofallylresinate[D].Beijing:ChineseAcademyof Forestry(中国林产科学院), 2015.
[16]Xu J F, Hu H R. Preparation and characterization of styrene acrylate emulsionsurfacesizingagentmodifiedwithrosin[J].Journalof Applied Polymer Science, 2012, 123(1):611-616.
[17]Liu Wenfang(刘文芳), Li Shucai(李树材). Effects of tackifiers on thepropertiesofacrylicemulsionadhesive[J].Thermosettingresin(热固性树脂), 2000, 15(4):56-58.
[18]KurtF,MarcelS,JohannesF,etal.Stableaqueousdispersionsfor sizing paper:US6380299[P]. 2002-04-30.
[19]Standardization Administration of the P.R.C.(中国国家标准化管理委员会). Paints and varnishes—Cross cut test for films(色漆和清漆漆膜的划格试验):GB/T9286—1998[S]. Beijing:Standards Press of China, 1999.
[20]Standardization Administration of the P.R.C.(中国国家标准化管理委员会).Paintsandvarnishes—Determinationoffilmhardnessby penciltest(色漆和清漆铅笔法测定漆膜硬度):GB/T6739—2006[S]. Beijing:Standards Press of China, 2007.
[21]Cao Yutong(曹同玉), Liu Qingpu(刘庆普), Hu Jinsheng(胡金生).Principle,propertiesandapplicationofpolymeremulsionsynthesis(聚合物乳液合成原理性能及应用)[M].V2.Beijing:Chemical Industry Press, 2007:175-177.
[22]Hu Zhihua(胡智华), Qian Yu(钱宇), Jiang Yanbin(江燕斌). Study onpolymerizationstabilityasfunctionalmonomerforpreparing acrylateemulsion[J].Paint&CoatingsIndustry(涂料工业),2003,33(6):14-18.
[23]Liu Dandan(刘丹丹), Zeng Xingrong(曾幸荣), Li Hongqiang(李红强), et al. Influence of polymerization conditions on particle size and itsdistribution ofacrylatemicro-emulsion[J].Chinaadhesives(中国胶粘剂), 2011, 20(1):22-26.
[24]LiuXiaodan(刘晓丹).Studyonacrylateemulsionandits pressure-sensitiveadhesivemodifiedviaderivativeandphosphate ester[D]. Guangzhou:South China University of Technology(华南理工大学), 2012.
[25]PedrazaEP,SoucekMD.Effectoffunctionalmonomeronthe stabilityandfilmpropertiesofthermosettingcore–shelllatexes[J].Polymer, 2005, 46(24):11174-11185.
[26]Chen P X, Zeng X R, Li H Q, et al. Preparation and characterization ofpolyacrylate/polymerizedrosincompositeemulsionsbyseeded semicontinuousemulsionpolymerization[J].JournalofApplied Polymer Science, 2012, 124(6):4694-4701.
[27]Wu Jing(吴婧). Synthesis of solvent fluoro-acrylate resins and their applications in fluorocarbon coatings[D]. Xi’an:Shanxi University of Science and Technology(陕西科学大学), 2013.