聚脲微球粒径与形态结构控制研究
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摘要
通过沉淀聚合制备聚脲微球,主要研究反应时间、反应温度及单体添加量对聚脲微球粒径、粒径分布及形态结构的影响。结果表明,在其他条件不变,反应时间在80～110 min时,聚脲微球的粒径分布呈现双粒径分布,120min时体系为单粒径分布,微球平均粒径由2. 1μm增加到5. 9μm;其他条件不变,反应温度在30～45℃时,粒径由5. 9μm增加到7. 0μm,粒径变异系数(CV)控制在5%以内。当温度到达50℃时,微球CV大于5%;其他条件不变,单体投入量在2%～5%时,微球粒径由5. 8μm逐步增加到8. 4μm,CV小于10%,当质量分数为7%时,CV为52%。通过对反应时间、反应温度及单体添加量的研究,得到了一系列制备粒径及形态可控聚脲微球的规律,为制备出粒径及形态可控的聚脲微球奠定实验和理论基础。
The polyurea microspheres were prepared by precipitation polymerization. The effects of reaction time,reaction temperature and monomer concentration on the particle size,size distribution and morphology of polyurea microspheres were studied. The results show when the reaction time is between 80 min and 120 min with other conditions unchanged,the size distribution of the polyurea microspheres indicates double size distribution. And when the reaction time is 120 min, the size distribution shows single size distribution,the average particle size of microspheres increases from 2. 1 μm to 5. 9 μm. When the temperature is between 30 ℃ and 45 ℃ with other conditions unchanged,the size of microspheres increases from 5. 9 μm to 7. 0 μm and the variable coefficient value( CV) is controlled within 5%. When the temperature is 50 ℃,the CV is greater than 5%. When the monomer concentration is between 2% and 5%with other conditions unchanged,the particle size gradually increases from 5. 8 μm to 8. 4 μm,and the CV is less than 10%. When the monomer concentration is 7%,the CV is 52%. By studying the reaction time,reaction temperature and monomer addition amount, a series of rules for preparing particle size and morphology of polyurea microspheres are obtained, which establishes the experimental and theoretical foundation for the preparation.
The polyurea microspheres were prepared by precipitation polymerization. The effects of reaction time,reaction temperature and monomer concentration on the particle size,size distribution and morphology of polyurea microspheres were studied. The results show when the reaction time is between 80 min and 120 min with other conditions unchanged,the size distribution of the polyurea microspheres indicates double size distribution. And when the reaction time is 120 min, the size distribution shows single size distribution,the average particle size of microspheres increases from 2. 1 μm to 5. 9 μm. When the temperature is between 30 ℃ and 45 ℃ with other conditions unchanged,the size of microspheres increases from 5. 9 μm to 7. 0 μm and the variable coefficient value( CV) is controlled within 5%. When the temperature is 50 ℃,the CV is greater than 5%. When the monomer concentration is between 2% and 5%with other conditions unchanged,the particle size gradually increases from 5. 8 μm to 8. 4 μm,and the CV is less than 10%. When the monomer concentration is 7%,the CV is 52%. By studying the reaction time,reaction temperature and monomer addition amount, a series of rules for preparing particle size and morphology of polyurea microspheres are obtained, which establishes the experimental and theoretical foundation for the preparation.
引文
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[14]宋洪榕,李世彦,杨亚囡,等.Si O2用量对单分散聚脲多孔微球的影响[J].山东化工,2015(4):3-5.
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[2]朱效杰,刘峰,潘肇琦,等.含甲基丙烯酸的高温发泡微球的合成及其发泡性能研究[J].塑料工业,2013,41(4):14-18.
[3]WANG J,CORMACK P A G,SHERRINGTON D C,et al.Monodisperse,molecularly imprinted polymer microspheres prepared by precipitation polymerization for affinity separation applications[J].Angewandte Chemie Int Edition,2003,42(43):5336-5338.
[4]SHIVE M S,ANDERSON J M.Biodegradation and biocompatibility of PLA and PLGA microspheres[J].Adv Drug Deliv Rev,2012,64(1):72-82.
[5]TANG T T,FAN H,AI S Y,et al.Hemoglobin(Hb)immobilized on amino-modified magnetic nanoparticles for the catalytic removal of bisphenol A[J].Chemosphere,2011,83(3):255-264.
[6]HAN H,ZHOU Y M,LI S S,et al.Immobilization of lipase from pseudomonas fluorescens on porous polyurea and its application in kinetic resolution of racemic 1-phenylethanol[J].Acs Appl Mater Interfaces,2016,8(39):25714-25724.
[7]JIANG X B,ZHU X L,KONG X Z.A facile route to preparation of uniform polymer microspheres by quiescent polymerization with reactor standing still without any stirring[J].Chem Eng J,2012,213(12):214-217.
[8]ZHANG F L,JIANG X B,ZHU X L,et al.Preparation of uniform and porous polyurea microspheres of large size through interfacial polymerization of toluene diisocyanate in water solution of ethylene diamine[J].Chem Eng J,2016,303:48-55.
[9]王为强,张秋禹,刘燕燕,等.单分散大粒径交联聚苯乙烯微球的制备及功能化改性的研究进展[J].化工进展,2009(1):93-98.
[10]褚良银,汪伟,巨晓洁,等.微流控法构建微尺度相界面及制备新型功能材料研究进展[J].化工进展,2014,33(9):2229-2234.
[11]姚伟,高志贤,房彦军,等.沉淀聚合法制备咖啡因分子印迹聚合物微球[J].化工进展,2007,26(6):869-872.
[12]YAN Q,ZHAO T Y,BAI Y W,et al.Precipitation polymerization in acetic acid:Study of the solvent effect on the morphology of poly(divinylbenzene)[J].J Phys Chem B,2009,113(10):3008-3014.
[13]黄芳婷.多粒径单分散聚苯乙烯微球的制备及其受控组装[D].扬州:扬州大学,2011.
[14]宋洪榕,李世彦,杨亚囡,等.Si O2用量对单分散聚脲多孔微球的影响[J].山东化工,2015(4):3-5.
[15]LIU Z J,CHEN D,ZHANG J F,et al.Self-stabilized precipitation polymerization and its application[J].Research,2018,2018:1-12.
[16]JIANG X B,YU Y T,LI X M,et al.High yield preparation of uniform polyurea microspheres through precipitation polymerization and their application as laccase immobilization support[J].Chem Eng J,2017,328:1043-1050.