聚合诱导自组装制备复杂形貌的聚合物纳米材料

doi:10.12052/gdutxb.170167

摘要/Abstract

摘要： 以聚乙二醇单甲醚（Methoxypolyethylene glycol，mPEG₄₅）为大分子链转移剂、S-正十二烷基-S'-（2-甲基-2-丙酸基）三硫代碳酸酯（S-1-dodecyl-S'-（α，α'-dimethyl-α″-acetic acid）trithiocarbonate，DDMAT）为小分子链转移试剂、苯乙烯（Styrene，St）和4-乙烯基吡啶（4-vinylpyridine，4VP）为单体、偶氮二异丁腈（2，2-Azobisisobutyronitrile，AIBN）为热引发剂，在70 ℃下以甲醇/水作为溶剂通过可逆加成-断裂链转移（Reversible Addition–Fragmentation chain Transfer，RAFT）分散聚合制备一系列mPEG₄₅-P（St-co-4VP）/P（St-co-4VP）不同形貌聚合物纳米材料. 文中探讨了不同[St]₀/[4VP]₀摩尔比、不同成核链段目标聚合度（Degree of Polymer，DP）、不同[mPEG₄₅-DDMAT]/[DDMAT]摩尔比对聚合物形貌的影响，通过透射电子显微镜（Transmission electron microscope，TEM）、扫描电子显微镜（Scanning electron microcopy，SEM）以及核磁共振（¹H NMR spectroscopy）研究其动力学及形貌变化.

关键词: 分散聚合, 聚合诱导自组装, 复杂形貌

Abstract: Styrene (St) and 4-vinylpyridine (4VP) were used as monomers to prepare a series of mPEG₄₅-P(St-co-4VP)/P(St-co-4VP) polymer nano-objects of different morphologies in methanol/water at 70℃, mediated by binary mixture of mPEG₄₅-DDMAT and DDMAT. Effects of[St]₀/[4VP]₀ molar ratio, degree of polymerization (DP) of the core-forming block,[mPEG₄₅-DDMAT]/[DDMAT] molar ratio on the assemblies were investigated by transmission electron microscopy (TEM), scanning electron microcopy (SEM) and ¹H NMR spectroscopy.

Key words: dispersion polymerization, polymerization-induced self-assembly, complex morphologies

中图分类号:

TQ316.31

张宇旋, 黄春东, 谭剑波. 聚合诱导自组装制备复杂形貌的聚合物纳米材料[J]. 广东工业大学学报, 2018, 35(06): 100-106.

Zhang Yu-xuan, Huang Chun-dong, Tan Jian-bo. Synthesis of Polymer Nano-objects with Complex Morphologies via Polymerization-induced Self-assembly[J]. Journal of Guangdong University of Technology, 2018, 35(06): 100-106.

参考文献 41

[1] WANG Z, VAN OERS M C M, RUTJES F P J T, et al. Polymersome colloidosomes for enzyme catalysis in a biphasic system[J]. Angewandte Chemie International Edition, 2012, 51(43):10746-10750
[2] LOUZAO I, VAN HEST J C M. Permeability effects on the efficiency of antioxidant nanoreactors[J]. Biomacromolecules, 2013, 14(7):2364-2372
[3] LIU T, HU J, JIN Z, et al. Two-photon ratiometric fluorescent mapping of intracellular transport pathways of pH-responsive block copolymer micellar nanocarriers[J]. Advanced Healthcare Materials, 2013, 2(12):1576-1581
[4] LEE J S, FEIJEN J. Polymersomes for drug delivery:design, formation and characterization[J]. Journal of Controlled Release, 2012, 161(2):473-483
[5] NING Y, FIELDING L A, ANDREWS T S, et al. Sulfate-based anionic diblock copolymer nanoparticles for efficient occlusion within zinc oxide[J]. Nanoscale, 2015, 7(15):6691-6702
[6] 付黎黎, 柏宇豪, 张雪超, 等. 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(2):34-39 FU L L, BAI Y H, ZHANG X C, et al. Synthesis of monodisperse PMMA microspheres by photoinitiated RAFT dispersion polyneerization[J]. Journal of Guangdong University of Technology, 2017, 34(2):34-39
[7] MAI Y, EISENBERG A. Self-assembly of block copolymers[J]. Chemical Society Reviews, 2012, 41(18):5969-5985
[8] DU J Z, TANG Y Q, LEWIS A L, et al. pH-sensitive vesicles based on a biocompatible zwitterionic diblock copolymer[J]. Journal of the American Chemical Society, 2005, 127(51):17982-17983
[9] KITA-TOKARCZYK K, GRUMELARD J, HAEFELE T, et al. Block copolymer vesicles-using concepts from polymer chemistry to mimic biomembranes[J]. Polymer, 2005, 46(11):3540-3563
[10] BLANAZS A, MASSIGNANI M, BATTAGLIA G, et al. Tailoring macromolecular expression at polymersome Surfaces[J]. Advanced Functional Materials, 2009, 19(18):2906-2914
[11] SUN J, HONG C, PAN C. Recent advances in RAFT dispersion polymerization for preparation of block copolymer aggregates[J]. Polymer Chemistry, 2013, 4(4):873-881
[12] 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
[13] DERRY M J, FIELDING L A, ARMES S P. Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization[J]. Progressin Polymer Science, 2016, 52:1-18
[14] CUNNINGHAM V J, ALSWIELEH A M, THOMPSON K L, et al. Poly(glycerol monomethacrylate)-poly(benzyl methacrylate) diblock copolymer nanoparticles via raft emulsion polymerization:synthesis, characterization, and interfacial activity[J]. Macromolecules, 2014, 47(16):5613-5623
[15] CHARLEUX B, DELAITTRE G, RIEGER J, et al. Polymerization-induced self-assembly:from soluble macromolecules to block copolymer nano-objects in one step[J]. Macromolecules, 2012, 45(17):6753-6765
[16] SUN L, HONG L, WANG C. Facile fabrication of water dispersible latex particles with homogeneous or chain-segregated surface from RAFT polymerization using a mixture of two macromolecular chain transfer agents[J]. Macromolecular Rapid Communications, 2016, 37(8):691-699
[17] RIEGER J, STOFFELBACH F, BUI C, et al. Amphiphilic poly(ethylene oxide) macromolecular RAFT agent as a stabilizer and control agent in ab initio batch emulsion polymerization[J]. Macromolecules, 2008, 41(12):4065-4068
[18] TAN J, LIU D, ZHANG X, et al. Facile preparation of hybrid vesicles loaded with silica nanoparticles via aqueous photoinitiated polymerization-induced self-assembly[J]. RSC Advances, 2017, 7(37):23114-23121
[19] LIU G, QIU Q, SHEN W, et al. Aqueous dispersion polymerization of 2-methoxyethyl acrylate for the synthesis of biocompatible nanoparticles using a hydrophilic RAFT polymer and a redox initiator[J]. Macromolecules, 2011, 44(13):5237-5245
[20] ZHOU W, QU Q, XU Y, et al. Aqueous polymerization-induced self-assembly for the synthesis of ketone-functionalized nano-objects with low polydispersity[J]. ACS Macro Letters, 2015, 4(5):495-499
[21] WAN W, HONG C, PAN C. One-pot synthesis of nanomaterials via RAFT polymerization induced self-assembly and morphology transition[J]. Chemical Communications, 2009(39):5883-5885
[22] HE W, SUN X, WAN W, et al. Multiple morphologies of PAA-b-PSt assemblies throughout RAFT dispersion polymerization of styrene with PAA Macro-CTA[J]. Macromolecules, 2011, 44(9):3358-3365
[23] ZHANG W, HONG C, PAN C. Fabrication of spaced concentric vesicles and polymerizations in RAFT dispersion polymerization[J]. Macromolecules, 2014, 47(5):1664-1671
[24] FIELDING L A, LANE J A, DERRY M J, et al. Thermo-responsive diblock copolymer worm gels in non-polar solvents[J]. Journal of the American Chemical Society, 2014, 136(15):5790-5798
[25] RATCLIFFE L P D, MCKENZIE B E, LE BOUEDEC G M D, et al. Polymerization-induced self-assembly of all-acrylic diblock copolymers via RAFT dispersion polymerization in alkanes[J]. Macromolecules, 2015, 48(23):8594-8607
[26] PEI Y, THURAIRAJAH L, SUGITA O R, et al. RAFT dispersion polymerization in nonpolar media:polymerization of 3-phenylpropyl methacrylate in n-tetradecane with poly(stearyl methacrylate) homopolymers as macro chain transfer agents[J]. Macromolecules, 2015, 48(1):236-244
[27] GAO C, ZHOU H, QU Y, et al. In situ synthesis of block copolymer nanoassemblies via polymerization-induced self-assembly in poly(ethylene glycol)[J]. Macromolecules, 2016, 49(10):3789-3798
[28] TAN J, SUN H, YU M, et al. Photo-PISA:shedding light on polymerization-induced self-assembly[J]. ACS Macro Letters, 2015, 4(11):1249-1253
[29] TAN J, HUANG C, LIU D, et al. Alcoholic photoinitiated polymerization-induced self-assembly (Photo-PISA):a fast route toward poly(isobornyl acrylate)-based diblock copolymer nano-objects[J]. ACS Macro Letters, 2016, 5(8):894-899
[30] TAN J, BAI Y, ZHANG X, et al. Room temperature synthesis of poly(poly(ethylene glycol) methyl ether methacrylate)-based diblock copolymer nano-objects via photoinitiated polymerization-induced self-assembly (Photo-PISA)[J]. Polymer Chemistry, 2016, 7(13):2372-2380
[31] YEOW J, XU J, BOYER C. Polymerization-induced self-assembly using visible light mediated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization[J]. ACS Macro Letters, 2015, 4(9):984-990
[32] TAN J, LIU D, BAI Y, et al. Enzyme-assisted photoinitiated polymerization-induced self-assembly:an oxygen-tolerant method for preparing block copolymer nano-objects in open vessels and multiwell plates[J]. Macromolecules, 2017, 50(15):5798-5806
[33] NG G, YEOW J, XU J, et al. Application of oxygen tolerant PET-RAFT to polymerization-induced self-assembly[J]. Polymer Chemistry, 2017, 8(18):2841-2851
[34] GAO C, WU J, ZHOU H, et al. Self-assembled blends of AB/BAB block copolymers prepared through dispersion RAFT polymerization[J]. Macromolecules, 2016, 49(12):4490-4500
[35] TAN J, HUANG C, LIU D, et al. Polymerization-induced self-assembly of homopolymer and diblock copolymer:a facile approach for preparing polymer nano-objects with higher-order morphologies[J]. ACS Macro Letters, 2017, 6(3):298-303
[36] YUAN B, HE X, QU Y, et al. In situ synthesis of a self-assembled AB/B blend of poly(ethylene glycol)-b-polystyrene/polystyrene by dispersion RAFT polymerization[J]. Polymer Chemistry, 2017, 8(14):2173-2181
[37] ZHU A, LV X, SHEN L, et al. Polymerization-induced cooperative assembly of block copolymer and homopolymer via RAFT dispersion polymerization[J]. ACS Macro Letters, 2017, 6(3):304-309
[38] SHI P, QU Y, LIU C, et al. Redox-responsive multicompartment vesicles of ferrocene-containing triblock terpolymer exhibiting on off switchable pores[J]. ACS Macro Letters, 2016, 5(1):88-93
[39] HE X, QU Y, GAO C, et al. Synthesis of multicompartment nanoparticles of a triblock terpolymer by seeded RAFT polymerization[J]. Polymer Chemistry, 2015, 6(35):6386-6393
[40] SHI P, ZHOU H, GAO C, et al. Macro-RAFT agent mediated dispersion copolymerization:a small amount of solvophilic co-monomer leads to a great change[J]. Polymer Chemistry, 2015, 6(27):4911-4920
[41] LAI J T, FILLA D, SHEA R. Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents[J]. Macromolecules, 2002, 35(18):6754-6756

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed