RAFT光引发分散聚合制备单分散PMMA微球

doi:10.12052/gdutxb.160029

摘要/Abstract

摘要：

在乙醇/水的反应介质中，通过RAFT光分散聚合制备了聚甲基丙烯酸甲酯（PMMA）微球.探究了RAFT光分散聚合机理，研究了反应条件对微球粒径及粒径分布的影响.结果表明：RAFT光分散聚合的成核期为60 min左右.光引发剂浓度和稳定剂浓度对微球均匀性影响不大；RAFT试剂质量浓度为0.25%~0.75%，能够获得单分散微球；微球粒径随单体浓度增加或者反应介质中乙醇含量的增加而增大.

关键词: 光引发, RAFT聚合, 分散聚合, 单分散微球

Abstract:

In this study, poly (methyl methacrylate) (PMMA) microspheres were synthesized by photoinitiated RAFT dispersion polymerization in an ethanol/water mixture. The mechanism of photoinitiated RAFT dispersion polymerization was investigated, and the effects of reaction conditions on microspheres size and size distribution studied. The results showed that the nucleation of photoinitiated RAFT dispersion polymerization was at around 60 min. The concentrations of photoinitiator and stabilizer had a little influence on the particle uniformity. Monodisperse microspheres were obtained at RAFT agent concentrations ranging from 0.25% to 0.75%. It was found that the diameter of microspheres became larger as the monomer concentration or the content of ethanol in the medium increased.

Key words: photoinitiation, RAFT polymerization, dispersion polymerization, monodisperse microspheres

中图分类号:

TQ323.8

付黎黎, 柏宇豪, 张雪超, 谭剑波, 张力. RAFT光引发分散聚合制备单分散PMMA微球[J]. 广东工业大学学报, 2017, 34(02): 34-39.

Fu Li-li, Bai Yu-hao, Zhang Xue-chao, Tan Jian-bo, Zhang Li. Synthesis of Monodisperse PMMA Microspheres by Photoinitiated RAFT Dispersion Polymerization[J]. Journal of Guangdong University of Technology, 2017, 34(02): 34-39.

参考文献

[1] 乔红梅. 单分散多孔聚合物微球的制备及反相色谱应用[J]. 精细化工, 2015, 32(7):721-725.QIAO H M. Preparation of monodisperse porous polymer microspheres and their antiphase chromatographic application[J]. Fine Chemicals, 2015, 32(7):721-725.
[2] CHEN Z K, CAI M X, YANG J, et al. Chemotherapy with PLGA microspheres containing docetaxel decreases angiogenesis in human hepatoma xenograft[J]. Medical Oncology, 2012, 29(1):62-69.
[3] 周晓英, 张光华, 朱军峰, 等. 液晶显示器衬垫用大粒径单分散性交联聚苯乙烯微球的制备[J]. 石油化工, 2009, 38(4):432-437.ZHOU X Y, ZHANG G H, ZHU J F, et al. Preparation of large-sized monodispersed crosslinked polystyrene microspheres used as liquid crystal displayer spacer[J]. Petrochemical Technology, 2009, 38(4):432-437.
[4] OH J S, DANG L N, YOON S W, et al. Amine-functionalized polyglycidyl methacrylate microsphere as a unified template for the synthesis of gold nanoparticles and single-crystal gold plates[J]. Macromolecular Rapid Communications, 2013, 34(6):504-510.
[5] 赖子尼, 崔英德, 梁灿强, 等. PVA-SA-PLA复合水凝胶的制备及铵离子扩散性能[J]. 广东工业大学学报, 2009, 26(3):1-4.LAI Z N, CUI Y D, LIANG C Q, et al. Preparation of PVA-SA-PLA composite hydrogels and the diffusibility performance for NH₄⁺[J]. Journal of Guangdong University of Technology, 2009, 26(3):1-4.
[6] LI X, GUO Y, ZHANG J, et al. Preparation of polysulfone microspheres with a hollow core/porous shell structure and their application for oil spill cleanup[J]. Journal of Applied Polymer Science, 2013, 128(5):2994-2999.
[7] QU Q, MIN Y, ZHANG L, et al. Silica microspheres with fibrous shells:synthesis and application in HPLC[J]. Analytical Chemistry, 2015, 87(19):9631-9638.
[8] 徐祖顺, 胡晓熙. 乳液聚合制备聚合物纳米微球的研究进展[J]. 石油化工, 2011, 40(2):125-132.XU Z S, HU X X. Progress in preparation of polymeric nanospheres by emulsion polymerization[J]. Petrochemical Technology, 2011, 40(2):125-132.
[9] SHAHIDUL I M, HYUN Y J, KUMAR D A. Synthesis of poly (vinyl acetate-methyl methacrylate) copolymer microspheres using suspension polymerization[J]. Journal of Colloid and Interface Science, 2011, 368(1):400-405.
[10] 党高飞, 付志峰. 分散聚合技术及其研究进展[J]. 高分子通报, 2008(10):41-46.DANG G F, FU Z F. Progress on research and technology of dispersion polymerization[J]. Polymer Bulletin, 2008(10):41-46.
[11] RICHEZ A P, YOW H N, BIGGS S, et al. Dispersion polymerization in non-polar solvent:Evolution toward emerging applications[J]. Progress in Polymer Science, 2013, 38(6):897-931.
[12] SONG J S, WINNIK M A. Monodisperse, micrometer-sized low molar mass polystyrene particles by two-stage dispersion polymerization[J]. Polymer, 2006, 47(13):4557-4563.
[13] HONG J, HONG C K, SHIM S E. Synthesis of polystyrene microspheres by dispersion polymerization using poly (vinyl alcohol) as a steric stabilizer in aqueous alcohol media[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2007, 302(1):225-233.
[14] LIANG Y, ABDELRAHMAN A I, BARANOVV, et al. The synthesis and characterization of lanthanide encoded poly (styrene-co-methacrylic acid) microspheres[J]. Polymer, 2011, 52(22):5040-5052.
[15] PENG G, WANG B, MENG X, et al. Different dispersion polymerization strategies influence the quality of fluorescent poly(St-co-GMA) microspheres[J]. Journal of Applied Polymer Science, 2015, 132(18):41927-41936.
[16] 熊圣东, 郭小丽, 张凌飞, 等. 微波辐射分散聚合制备单分散聚甲基丙烯酸甲酯微球[J]. 高分子材料科学与工程, 2010(2):8-11.XIONG S D, GUO X L, ZHANG L F, et al. Preparation of monodisperse poly (methyl methacrylate) microspheres by dispersion polymerization under microwave irradiation[J]. Polymer Materials Science and Engineering, 2010(2):8-11.
[17] 程艳玲, 邱俊英, 易昌凤, 等. 超声辐照分散聚合制备聚苯乙烯纳米微球[J]. 应用化学, 2008, 25(10):1217-1220.CHENG Y L, QIU J Y, YI C F, et al. Polystyrene nanoparticles prepared by dispersion polymerization under ultrasonic irradiation[J]. Chinese Journal of Applied Chemistry, 2008, 25(10):1217-1220.
[18] ZHANG G, ZHANG Z, XU C, et al. Preparation of monodisperse polystyrene particles by radiation-induced dispersion polymerization using waterborne polyurethane as a stabilizer[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2006, 276(1):72-77.
[19] 马江雅, 付坤, 张源林, 等. 紫外光引发聚合的研究与应用[J]. 化学研究与应用, 2015, 27(10):1574-1580.MA J Y, FU K, ZHANG Y L, et al. Researches and applications of UV-initiated polymerization[J]. Chemical Research and Application, 2015, 27(10):1574-1580.
[20] YAGCI Y, JOCKUSCH S, TURRO N J. Photoinitiated polymerization:advances, challenges, and opportunities[J]. Macromolecules, 2010, 43(15):6245-6260.
[21] 周传玉, 崔艳艳, 董智贤, 等. 紫外光固化氨酯型油墨保护树脂的合成及应用性能的研究[J]. 广东工业大学学报, 2011, 28(3):66-69.ZHOU C Y, CUI Y Y, DONG Z X, et al. Synthesis and application of UV-curable polyurethane for ink protection[J]. Journal of Guangdong University of Technology, 2011, 28(3):66-69.
[22] 何岷洪, 宋坤, 莫宏斌, 等. 3D打印光敏树脂的研究进展[J]. 功能高分子学报, 2015, 28(1):102-108.HE M H, SONG K, MO H B, et al. Progress on photosensitive resins for 3D printing[J]. Journal of Functional Polymers, 2015, 28(1):102-108.
[23] CHEN J, ZENG Z, YANG J, et al. Photoinitiated dispersion polymerization of methyl methacrylate:A quick approach to prepare polymer microspheres with narrow size distribution[J]. Journal of Polymer Science:Part A:Polymer Chemistry, 2008, 46(4):1329-1338.
[24] RIZZARDO E. Living radical polymerization by the RAFT process-a third update[J]. Australian Journal of Chemistry, 2012, 65(8):985-1076.
[25] SANG E S, JUNG H, LEE H, et al. Living radical dispersion photopolymerization of styrene by a reversible addition-fragmentation chain transfer (RAFT) agent[J]. Polymer, 2003, 44(19):5563-5572.
[26] HUANG C Q, Pan C Y. Direct preparation of vesicles from one-pot RAFT dispersion polymerization[J]. Polymer, 2010, 51(22):5115-5121.
[27] ZHANG W J, Hong C Y, Pan C Y. Fabrication of Spaced Concentric Vesicles and Polymerizations in RAFT Dispersion Polymerization[J]. Macromolecules, 2014, 47(5):1664-1671.
[28] JONES E R, SEMSARILAR M, BLANAZS A, et al. Efficient Synthesis of Amine-Functional Diblock Copolymer Nanoparticles via RAFT Dispersion Polymerization of Benzyl Methacrylate in Alcoholic Media[J]. Macromolecules, 2012, 45(12):5091-5098.
[29] HUO F, WANG X, ZHANG Y, et al. RAFT dispersion polymerization of styrene in water/alcohol:the solvent effect on polymer particle growth during polymer chain propagation[J]. Macromolecular Chemistry and Physics, 2013, 214(8):902-911.
[30] 张瑶瑶, 王小辉, 霍菲, 等. 可逆加成-断裂链转移(RAFT)分散聚合[J]. 高分子通报, 2013(1):174-180.ZHANG Y Y, WANG X H, HUO F, et al. Reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization[J]. Polymer Bulletin, 2013(1):174-180.
[31] RIEGER J. Guidelines for the synthesis of block copolymer particles of various morphologies by RAFT dispersion polymerization[J]. Macromolecular Rapid Communications, 2015, 36(16):1458-1471.
[32] JOHN T L, DEBBY F, RONALD S. Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents[J]. Macromolecules, 2002, 35(18):6754-6756.

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