收稿日期: 2019-03-11
网络出版日期: 2019-07-05
Preparation of PDMAs-PSx block copolymer nanoparticles by RAFT dispersion PISA
Received date: 2019-03-11
Online published: 2019-07-05
可逆加成-断裂-链转移(reversible addition-fragmentation-chain transfer, RAFT)聚合诱导自组装(polymerization-induced self-assembly, PISA)是制备具有特定形貌嵌段共聚物纳米颗粒的高效手段. 以苯乙烯(styrene, St)为分散聚合的单体, PDMA$_{23}$ 和 PDMA$_{38}$ 为大分子链转移剂(chain transfer agent, CTA), 乙醇为溶剂, 在 70 $^{\circ}$C 下探究了纳米颗粒的形貌随不同聚合度(degree of ploymerizations, DPs)的转变情况. 由实验结果可知: 以 PDMA$_{23}$ 为链转移剂, 可调控苯乙烯的聚合度, 得到球、虫、囊泡、复合囊泡等形貌; 以 PDMA$_{38}$ 为链转移剂, 可在较宽的聚合度范围内得到均匀的球形纳米颗粒.
梁海洋, 杨永启, 张玲 . RAFT 分散聚合诱导自组装制备 PDMAs-PSx 嵌段共聚物纳米颗粒[J]. 上海大学学报(自然科学版), 2021 , 27(4) : 741 -748 . DOI: 10.12066/j.issn.1007-2861.2166
Reversible addition-fragmentation-chain transfer (RAFT) polymerization-induced self-assembly (PISA) is a versatile and powerful strategy for preparing block copolymer nanoparticles with specific morphologies. Ethanol was used for the RAFT dispersion polymerisation of styrene (St) at 70 $^\circ$C. PDMA$_{23}$ and PDMA$_{38}$ were chosen as macromolecular chain transfer agents (CTAs). The transformation of the morphologies was altered by varying the degree of polymerizations (DPs). The experimental results showed that spheres, worms, vesicles, and compound vesicles were obtained using PDMA$_{23 }$ as the CTA. However, only well-distributed spherical nanoparticles were obtained when PDMA$_{38 }$was employed as the CTA.
| [1] | Huo M, Yuan J Y, Tao L, et al. Redox-responsive polymers for drug delivery: from molecular design to applications[J]. Polymer Chemistry, 2014, 5(5):1519-1528. |
| [2] | Huo M, Ye Q, Che H, et al. Polymer assemblies with nanostructure-correlated aggregation-induced emission[J]. Macromolecules, 2017, 50(3):1126-1133. |
| [3] | Blackman L D, Varlas S, Arno M C, et al. Permeable protein-loaded polymersome cascade nanoreactors by polymerization-induced self-assembly[J]. ACS Macro Letters, 2011, 6(11):1263-1267. |
| [4] | Shen L L, Guo H Z, Zheng J W, et al. RAFT polymerization-induced self-assembly as a strategy for versatile synjournal of semifluorinated liquid-crystalline block copolymer nano-objects[J]. ACS Macro Letters, 2018, 7(3):287-292. |
| [5] | Ratcliffe L P D, Couchon C, Armes S P, et al. Inducing an order-order morphological transition via chemical degradation of amphiphilic diblock copolymer nano-objects[J]. Biomacromolecules, 2016, 17(6):2277-2283. |
| [6] | Szwarc M, Levy M, Milkovich R. Polymerization initiated by electron transfer to monomer. A new method of formation of block polymers[J]. Journal of the American Chemical Society, 1956, 78(11):2656-2657. |
| [7] | Chiefari J, Chong Y K, Ercole F, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process[J]. Macromolecules, 1998, 31(16):5559-5562. |
| [8] | Georges M K, Veregin R P N, Kazmaier P M, et al. Narrow molecular weight resins by a free-radical polymerization process[J]. Macromolecules, 1993, 26(11):2987-2988. |
| [9] | Percec V, Barboiu B. “Living” radical polymerization of styrene initiated by arenesulfonyl chlorides and CuI(bpy)nCl[J]. Macromolecules, 1995, 28(23):7970-7972. |
| [10] | Boyer C, Bulmus V, Davis T P, et al. Bioapplications of RAFT polymerization[J]. Chemical Reviews, 2009, 109(11):5402-5436. |
| [11] | Climie I E, White E F T. The aggregation of random and block copolymers containing acrylonitrile in mixed solvents[J]. Journal of Polymer Science, 1960, 47(149):149-156. |
| [12] | Gao Z, Varshney S K, Wong S, et al. Block copolymer “Crew-Cut” micelles in water[J]. Macromolecules, 1994, 27(26):7923-7927. |
| [13] | Zhang L, Eisenberg A. Multiple morphologies of “Crew-Cut” aggregates of polystyrene-b-poly (acrylic acid) block copolymers[J]. Science, 1995, 268(5218):1728-1731. |
| [14] | Zhang L, Eisenberg A. Multiple morphologies and characteristics of “Crew-Cut” micelle-like aggregates of polystyrene-b-poly (acrylic acid) diblock copolymers in aqueous solutions[J]. Journal of the American Chemical Society, 1996, 118(13):3168-3181. |
| [15] | Canning S L, Smith G N, Armes S P. A critical appraisal of RAFT-mediated polymerization-induced self-assembly[J]. Macromolecules, 2016, 49(6):1985-2001. |
| [16] | Derry M J, Fielding L A, Armes S P. Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization[J]. Progress in Polymer Science, 2016, 52:1-18. |
| [17] | Yeow J, Boyer C. Photoinitiated polymerization-induced self-assembly (Photo-PISA): new insights and opportunities[J]. Advanced Science, 2017, 4(7):1-14. |
| [18] | Wang X, Shen L L, An Z S. Dispersion polymerization in environmentally benign solvents via reversible deactivation radical polymerization[J]. Progress in Polymer Science, 2018, 83:1-27. |
| [19] | Ferguson C J, Hughes R J, Nguyen D, et al. Ab initio emulsion polymerization by RAFT-controlled self-assembly[J]. Macromolecules, 2005, 38(6):2191-2204. |
| [20] | Wan W M, Sun X L, Pan C Y. Morphology transition in RAFT polymerization for formation of vesicular morphologies in one pot[J]. Macromolecules, 2009, 42(14):4950-4952. |
| [21] | Wan W M, Hong C Y, Pan C Y. One-pot synjournal of nanomaterials via RAFT polymerization induced self-assembly and morphology transition[J]. Chemical Communications, 2009, 45(39):5883-5885. |
| [22] | Wan W M, Pan C Y. Formation of polymeric yolk/shell nanomaterial by polymerization-induced self-assembly and reorganization[J]. Macromolecules, 2010, 43(6):2672-2675. |
| [23] | 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. |
| [24] | Cai W M, Wan W M, Hong C Y, et al. Morphology transitions in RAFT polymerization[J]. Soft Matter, 2010, 6(21):5554-5561. |
| [25] | He W D, Sun X L, Wan W M, 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. |
| [26] | Ji W, Yan J, Chen E, et al. In situ and online monitoring polymerization-induced micellization[J]. Macromolecules, 2008, 41(13):4914-4919. |
| [27] | Zhang W J, Hong C Y, Pan C Y. formation of hexagonally packed hollow hoops and morphology transition in RAFT ethanol dispersion polymerization[J]. Macromolecular Rapid Communications, 2015, 36(15):1428-1436. |
| [28] | Zhou W, Qu Q W. Aqueous polymerization-induced self-assembly for the synjournal of ketone-functionalized nano-objects with low polydispersity[J]. ACS Macro Letters, 2015, 4(5):495-499. |
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