分散聚合制备粒径可控的聚甲基丙烯酸甲酯微球
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摘要
以甲基丙烯酸甲酯为单体,偶氮二异丁腈为引发剂,苯乙烯磺酸钠为离子单体,采用聚乙烯吡咯烷酮为分散剂,在乙醇/水介质中通过自由基分散聚合法合成了平均粒径分布在0.5～0.9μm范围的聚甲基丙烯酸甲酯(PMMA)微球,研究了各因素对微球粒径和分布的影响。结果表明,单体、分散剂和离子单体三者的浓度对PMMA微球尺寸及分布影响显著,微球尺寸随着单体浓度的增加、离子单体和分散剂用量的减少而增加,微球粒径增加的同时尺寸分布变宽。在反应体系中加入0.2%的离子单体可显著提高PMMA微球聚合过程中的稳定性,产物微球不发生粘连和团聚,呈现规则的球形形态,同时分散剂的使用量大幅降低。当单体质量分数、引发剂质量分数、离子单体质量分数依次为11%、1.0%、0.2%,控制乙醇/水体积比为0.8～1.0时,仅使用3%的分散剂,可成功制备出单分散PMMA微球。
With methyl methacrylate as monomer, 2,2'-azobisisobutyronitrile as initiator, poly(N-vinylpyrrolidone) as stabilizer and sodium styrene sulfonate as ionic monomer, a type of poly(methyl methacrylate)(PMMA) microsphere with the average particle size range from 0.5 μm to 0.9 μm were prepared by dispersion polymerization in the ethanol/water mixture medium. The effects of various parameters on particle size and distribution of microspheres were investigated. The results show that the mass fraction of monomer, ionic monomer and dispersant have obvious effects on PMMA particle size and distribution. The size scale of PMMA microspheres increases with increasing the mass fraction of monomer or decreasing the dosage of the ionic monomer and dispersant, whilst the size distribution of microspheres becomes broad. With the addition of ionic monomer into the initial reaction system, the stability of polymerization procedure shows a great improvement, and the microspheres show a clear spherical morphology, no conglutination or agglomeration of microspheres can be observed. Most importantly, the dosage of dispersant is dramatically reduced. The desired monodisperse PMMA microspheres are obtained successfully only using 3% dispersant when the mass fraction of monomer, initiator, ionic monomer is 11%, 1.0%, and 0.2%, respectively, with the volume ratio of ethanol/water in a range of 0.8 to 1.0.
With methyl methacrylate as monomer, 2,2'-azobisisobutyronitrile as initiator, poly(N-vinylpyrrolidone) as stabilizer and sodium styrene sulfonate as ionic monomer, a type of poly(methyl methacrylate)(PMMA) microsphere with the average particle size range from 0.5 μm to 0.9 μm were prepared by dispersion polymerization in the ethanol/water mixture medium. The effects of various parameters on particle size and distribution of microspheres were investigated. The results show that the mass fraction of monomer, ionic monomer and dispersant have obvious effects on PMMA particle size and distribution. The size scale of PMMA microspheres increases with increasing the mass fraction of monomer or decreasing the dosage of the ionic monomer and dispersant, whilst the size distribution of microspheres becomes broad. With the addition of ionic monomer into the initial reaction system, the stability of polymerization procedure shows a great improvement, and the microspheres show a clear spherical morphology, no conglutination or agglomeration of microspheres can be observed. Most importantly, the dosage of dispersant is dramatically reduced. The desired monodisperse PMMA microspheres are obtained successfully only using 3% dispersant when the mass fraction of monomer, initiator, ionic monomer is 11%, 1.0%, and 0.2%, respectively, with the volume ratio of ethanol/water in a range of 0.8 to 1.0.
引文
[1] 王娟, 梁彤祥, 李辰砂. 单分散聚合物微球的合成技术[J]. 材料工程, 2004(11): 61-64.Wang J, Liang T X, Li C S. Preparation technologies of monodisperse polymer microspheres[J].Journal of Materials Engineering, 2004(11): 61-64.
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[3] Song J S, Frédéric Tronc A, Winnik M A. Two-stage dispersion polymerization toward monodisperse, controlled micrometer-sized copolymer particles[J]. J. Am. Chem. Soc. , 2004, 126: 6562-3.
[4] Fan L, Geng C, Yan Q F. Growth kinetics of monodisperse polystyrene microspheres prepared by dispersion polymerization[J]. J. Polym., 2013, 2013: 628-631.
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[6] Kawaguchi S, Ito K. Dispersion polymerization[J].Adv. Polym. Sci., 2005, 175: 299-328.
[7] Watanabe S, Kobayashi T, Sumitomo H, et al. Preparation of monodisperse PMMA particles by dispersion polymerization of MMA using poly(styrene-co-methacrylic acid) copolymer as a steric stabilizer[J].Polym. Bull., 2010, 65: 543-550.
[8] Kim O H, Lee K, Kim K, et al. Optimum conditions for preparing micron-sized PMMA beads in the dispersion polymerization using PVA[J]. Colloid Polym. Sci., 2006,284: 909-915.
[9] Sang E S, Jung H, Lee K, et al. Dispersion polymerization of methyl methacrylate with a novel bifunctional polyurethane macromonomer as a reactive stabilizer[J].J. Colloid Interface Sci.,2004, 279: 464-470.
[10] Nakashima T, Yamada Y, Yoshizawa H. Synthesis of monodisperse polystyrene microspheres by dispersion polymerization using sodium polyaspartate[J]. Colloid Polym. Sci., 2007, 285: 1487-1493.
[11] Bilgin S, Tomovska R, Asua J M. Surfactant-free high solids content polymer dispersions[J]. Polymer, 2017, 117: 64-75.
[12] Tan J B, Zhao G Y, Lu Y J, et al. Synthesis of PMMA microparticles with a narrow size distribution by photoinitiated RAFT dispersion polymerization with a macromonomer as the stabilizer[J].Macromolecules,2014, 47: 6856-6866.
[13] Xu Z S, Deng Z W, Hu X X, et al. Monodisperse polystyrene microspheres prepared by dispersion polymerization with microwave irradiation[J].J. Polym. Sci. Part A: Polym. Chem., 2005, 43: 2368-2376.
[2] Tan J B, Rao X, Jiang D, et al. One-stage photoinitiated RAFT dispersion polymerization-Reaction parameters for achieving high particle size uniformity[J]. Polymer., 2014, 55: 2380-2388.
[3] Song J S, Frédéric Tronc A, Winnik M A. Two-stage dispersion polymerization toward monodisperse, controlled micrometer-sized copolymer particles[J]. J. Am. Chem. Soc. , 2004, 126: 6562-3.
[4] Fan L, Geng C, Yan Q F. Growth kinetics of monodisperse polystyrene microspheres prepared by dispersion polymerization[J]. J. Polym., 2013, 2013: 628-631.
[5] 李光辉,张贵才,葛际江,等. 单分散聚合物微球的合成方法进展[J].材料工程, 2014(8): 97-104.Li G H, Zhang G C, Ge J J, et al. Progress of synthesis method for monodisperse polymer microspheres[J]. Journal of Materials Engineering, 2014(8): 97-104.
[6] Kawaguchi S, Ito K. Dispersion polymerization[J].Adv. Polym. Sci., 2005, 175: 299-328.
[7] Watanabe S, Kobayashi T, Sumitomo H, et al. Preparation of monodisperse PMMA particles by dispersion polymerization of MMA using poly(styrene-co-methacrylic acid) copolymer as a steric stabilizer[J].Polym. Bull., 2010, 65: 543-550.
[8] Kim O H, Lee K, Kim K, et al. Optimum conditions for preparing micron-sized PMMA beads in the dispersion polymerization using PVA[J]. Colloid Polym. Sci., 2006,284: 909-915.
[9] Sang E S, Jung H, Lee K, et al. Dispersion polymerization of methyl methacrylate with a novel bifunctional polyurethane macromonomer as a reactive stabilizer[J].J. Colloid Interface Sci.,2004, 279: 464-470.
[10] Nakashima T, Yamada Y, Yoshizawa H. Synthesis of monodisperse polystyrene microspheres by dispersion polymerization using sodium polyaspartate[J]. Colloid Polym. Sci., 2007, 285: 1487-1493.
[11] Bilgin S, Tomovska R, Asua J M. Surfactant-free high solids content polymer dispersions[J]. Polymer, 2017, 117: 64-75.
[12] Tan J B, Zhao G Y, Lu Y J, et al. Synthesis of PMMA microparticles with a narrow size distribution by photoinitiated RAFT dispersion polymerization with a macromonomer as the stabilizer[J].Macromolecules,2014, 47: 6856-6866.
[13] Xu Z S, Deng Z W, Hu X X, et al. Monodisperse polystyrene microspheres prepared by dispersion polymerization with microwave irradiation[J].J. Polym. Sci. Part A: Polym. Chem., 2005, 43: 2368-2376.