泡沫相相分离制备多孔聚合物微球连续化工艺
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摘要
采用在泡沫相进行溶剂挥发的方法,连续、高效制备聚甲基丙烯酸甲酯-丙烯酸丁酯[P (MMA-BA)]共聚物多孔微球。采用自制的连续化反应装置,在一定搅拌速率和反应温度下,向反应器连续加料,在出口处连续收集溢出的泡沫并进行消泡、分散,再经洗涤、过滤、干燥得到多孔聚合物微球。重点研究了油相进料速率、反应温度、搅拌速率、聚乙烯醇用量(PVA浓度)对平均泡沫溢出速率、微球收率、微球粒径以及多孔形态的影响规律。结果表明:在反应温度为45℃,搅拌速率为500 r/min,油相溶液进料速率为30 g/min,PVA浓度为1.0%(质量),油相溶液中P (MMA-BA)∶二氯甲烷(DCM)∶正庚烷(HT)=10:53:6 (质量比)的工艺条件下,聚合物微球的收率高达92%,平均粒径为130μm,P (MMA-BA)微球球形饱满,呈多孔结构。
Porous polymeric mirospheres have been widely used since their characteristics in the structure.However, the reported methods are less efficient, especially no continuous process was reported to prepare porous polymeric microspheres. Therefore, there is a need to develop a time-saving method with high yield for producing porous polymeric microspheres. This paper reports a continuous process to prepare porous polymeric microspheres via the solvent evaporation method in foam phase, being efficient and of high yield. Preparation of porous poly(methyl methacrylate-co-butyl acrylate) [P(MMA-BA)] microspheres was carried out in a customized continuous reaction device. At a certain stirring rate and reaction temperature, the oil phase and the aqueous phase were pumped continuously into the reactor. Foam phase gradually generated and flowed out from the outlet of the reactor.Porous P(MMA-BA) microspheres were obtained after collecting the bubble phase followed by defoaming, washing,filtration and drying. The average foam flow rate,the microspheres' yield, the average particle size and the pore structure were investigated as a function of the experimental conditions including the feed rate of the oil phase, the reaction temperature, the stirring rate and the concentration of PVA. The results showed that the reaction temperature was 45℃, the stirring rate was 500 r/min, the oil phase solution feed rate was 30 g/min, the PVA concentration was 1.0%(mass), and the oil phase solution P(MMA-BA): DCM :HT is 10 : 53 :6 respectively, the yield of the porous P(MMA-BA) rnicrospheres was up to 92% and the average particle size is 130 μm. The temperature and the residual amount of the aqueous phase left in the customized continuous reaction device are critical for the foam behavior and the yield of the porous P(MMA-BA) microspheres. This work validates that the customized continuous reaction device is capable to produce porous polymeric microspheres continuously, based on the method to prepare porous polymeric microspheres via solvent evaporation method in foam phase, with improved efficiency and yield. In addition, the method reported in this work is able to use continuously on an industrial scale potentially.
Porous polymeric mirospheres have been widely used since their characteristics in the structure.However, the reported methods are less efficient, especially no continuous process was reported to prepare porous polymeric microspheres. Therefore, there is a need to develop a time-saving method with high yield for producing porous polymeric microspheres. This paper reports a continuous process to prepare porous polymeric microspheres via the solvent evaporation method in foam phase, being efficient and of high yield. Preparation of porous poly(methyl methacrylate-co-butyl acrylate) [P(MMA-BA)] microspheres was carried out in a customized continuous reaction device. At a certain stirring rate and reaction temperature, the oil phase and the aqueous phase were pumped continuously into the reactor. Foam phase gradually generated and flowed out from the outlet of the reactor.Porous P(MMA-BA) microspheres were obtained after collecting the bubble phase followed by defoaming, washing,filtration and drying. The average foam flow rate,the microspheres' yield, the average particle size and the pore structure were investigated as a function of the experimental conditions including the feed rate of the oil phase, the reaction temperature, the stirring rate and the concentration of PVA. The results showed that the reaction temperature was 45℃, the stirring rate was 500 r/min, the oil phase solution feed rate was 30 g/min, the PVA concentration was 1.0%(mass), and the oil phase solution P(MMA-BA): DCM :HT is 10 : 53 :6 respectively, the yield of the porous P(MMA-BA) rnicrospheres was up to 92% and the average particle size is 130 μm. The temperature and the residual amount of the aqueous phase left in the customized continuous reaction device are critical for the foam behavior and the yield of the porous P(MMA-BA) microspheres. This work validates that the customized continuous reaction device is capable to produce porous polymeric microspheres continuously, based on the method to prepare porous polymeric microspheres via solvent evaporation method in foam phase, with improved efficiency and yield. In addition, the method reported in this work is able to use continuously on an industrial scale potentially.
引文
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[31]姚顺治,单梦醒,朱天赐,等.泡沫分离法制备聚苯乙烯多孔微球[J].化工进展,2018,37(7):2753-2758.Yao S Z,Shan M X,Zhu T C,et al.Preparation of porous polystyrene microspheres by using foam phase separation[J].Chemical Industry and Engineering Progress,2018,37(7):2753-2758.
[32]何艳萍,郭文峰,孙彦琳,等.一种聚合物多孔微球的制备方法:201610223725.6[P].2016-07-13.He Y P,Guo W F,Sun Y L,et al.A method to prepare polymer porous microspheres:201610223725.6[P].2016-07-13.
[33]德鲁·迈尔斯.表面、界面和胶体--原理及应用[M].北京:化学工业出版社,2005:225-227.Drew M.Surfaces,Interface,and Colloids:Principles and Applications[M].Beijing:Chemical Industry Press,2005:225-227.
[2]马光辉,苏志国.微球材料尺寸和结构控制的过程工程[J].化工学报,2014,65(7):2574-2587.Ma G H,Su Z G.Process engineering for size and structure control of microspheres[J].CIESC Journal,2014,65(7):2574-2587.
[3]郭新东,章莉娟,钱宇,等.聚乳酸载药微球形成机理的模拟分析与实验研究[J].化工学报,2007,58(9):2321-2328.Guo X D,Zhang L J,Qian Y,et al.Mechanism analysis of polylactic acid microspheres formation by dissipative particle dynamics simulation and experimental study[J].Journal of Chemical Industry and Engineering(China),2007,58(9):2321-2328.
[4]Wei D X,Dao J W,Chen G Q.A micro-ark for cells:highly open porous polyhydroxyalkanoate microspheres as injectable scaffolds for tissue regeneration[J].Advanced Materials,2018,30(31):1802273.
[5]Lu J,Toy P H.Organic polymer supports for synthesis and for reagent and catalyst immobilization[J].Chemical Reviews,2009,109(2):815-838.
[6]Benaglia M,Puglisi A,Cozzi F.Polymer-supported organic catalysts[J].Chemical Reviews,2003,103(9):3401-3430.
[7]Buchmeiser M R.Polymer-supported well-defined metathesis catalysts[J].Chemical Reviews,2009,109(2):303-321.
[8]Slater M,Snauko M,Svec F,et al.“Click Chemistry”in the preparation of porous polymer-based particulate stationary phases forμ-HPLC separation of peptides and proteins[J].Analytical Chemistry,2006,78(14):4969-4975.
[9]Wood C D,Tan B E,Trewin A,et al.Microporous organic polymers for methane storage[J].Advanced Materials,2008,20(10):1916-1921.
[10]Wu D C,Xu F,Sun B,et al.Design and preparation of porous polymers[J].Chemical Reviews,2012,112(7):3959-4015.
[11]Barbaro P,Liguori F.Ion exchange resins:catalyst recovery and recycle[J].Chemical Reviews,2009,109(2):515-529.
[12]Gelbard G.Organic synthesis by catalysis with ion-exchange resins[J].Industrial&Engineering Chemistry Research,2005,44(23):8468-8498.
[13]Tang Q,Wang K T,Yaseen M,et al.Synthesis of highly efficient porous inorganic polymer microspheres for the adsorptive removal of Pb2+from wastewater[J].Journal of Cleaner Production,2018,193:351-362.
[14]Xu Z Y,Zhang Q X,Fang H H P.Applications of porous resin sorbents in industrial wastewater treatment and resource recovery[J].Critical Reviews in Environmental Science and Technology,2003,33(4):363-389.
[15]Schmidt W,Roessling G.Novel manufacturing process of hollow polymer microspheres[J].Chemical Engineering Science,2006,61(15):4973-4981.
[16]Dubinsky S,Parf J I,Gourevich I,et al.Toward controlling the surface morphology of macroporous copolymer particles[J].Macromolecules,2009,42(6):1990-1994.
[17]Du K F,Dong X Y,Sun Y.Fabrication of bimodal porous CaTiO3microspheres using composite agarose/CaCO3beads as template CaCO3beads as template[J].Industrial&Engineering Chemistry Research,2010,49(24):12560-12566.
[18]Hao D X,Gong F L,Hu G H,et al.The relationship between heterogeneous structures and phase separation in synthesis of uniform microns PolyDVB microspheres[J].Polymer,2009,14:3188-3195.
[19]马光辉,苏志国.高分子微球材料[M].北京:化学工业出版社,2005:51-58.Ma G H,Su Z G.Polymeric Microsphere Materials[M].Beijing:Chemical Industry Press,2005:51-58.
[20]Gokmen M T,Du Prez F E.Porous polymer particles-a comprehensive guide to synthesis,characterization,functionalization and applications[J].Progress in Polymer Science,2012,37(3):365-405.
[21]Kim T K,Yoon J J,Lee D S,et al.Gas foamed open porous biodegradable polymeric microspheres[J].Biomaterials,2006,27(2):152-159.
[22]Yang Y Y,Chung T S,Ng N P.Morphology,drug distribution,and in vitro release profiles of biodegradable polymeric microspheres containing protein fabricated by double-emulsion solvent extraction/evaporation method[J].Biomaterials,2001,22(3):231-241.
[23]Hong Y,Gao C Y,Shi Y C,et al.Preparation of porous polylactide microspheres by emulsion-solvent evaporation based on solution induced phase separation[J].Polymers for Advanced Technologies,2005,16(8):622-627.
[24]Dastidar D G,Saha S,Chowdhury M.Porous microspheres:synthesis,characterisation and applications in pharmaceutical&medical fields[J].International Journal of Pharmaceutics,2018,548(1):34-48.
[25]Yu Q B,Tao Y L,Huang Y P,et al.Preparation of porous polysulfone microspheres and their application in removal of oil from water[J].Industrial&Engineering Chemistry Research,2012,51(23):8117-8122.
[26]Watanabe T,Ono T,Kimura Y.Continuous fabrication of monodisperse polylactide microspheres by droplet-to-particle technology using microfluidic emulsification and emulsionsolvent diffusion[J].Soft Matter,2011,7(21):9894-9897.
[27]Hong Y,Gao C Y,Shi Y C,et al.Preparation of porous polylactide microspheres by emulsion-solvent evaporation based on solution induced phase separation[J].Polymers for Advanced Technologies,2005,16(8):622-627.
[28]Liu S Q,Cai M L,Deng R H,et al.Fabrication of porous polymer microparticles with tunable pore size and density through the combination of phase separation and emulsion-solvent evaporation approach[J].Korea-Australia Rheology Journal,2014,26(1):63-71.
[29]He Y P,Guo W F,Shan M X,et al.Technical improvement for producing porous polymer microspheres in foam phase[J].Materials Letters,2017,201:54-57.
[30]He Y P,Li X,Zhu T C,et al.Controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent[J].Polymers,2018,10(7):789.
[31]姚顺治,单梦醒,朱天赐,等.泡沫分离法制备聚苯乙烯多孔微球[J].化工进展,2018,37(7):2753-2758.Yao S Z,Shan M X,Zhu T C,et al.Preparation of porous polystyrene microspheres by using foam phase separation[J].Chemical Industry and Engineering Progress,2018,37(7):2753-2758.
[32]何艳萍,郭文峰,孙彦琳,等.一种聚合物多孔微球的制备方法:201610223725.6[P].2016-07-13.He Y P,Guo W F,Sun Y L,et al.A method to prepare polymer porous microspheres:201610223725.6[P].2016-07-13.
[33]德鲁·迈尔斯.表面、界面和胶体--原理及应用[M].北京:化学工业出版社,2005:225-227.Drew M.Surfaces,Interface,and Colloids:Principles and Applications[M].Beijing:Chemical Industry Press,2005:225-227.