PE-g-PMMA的结晶驱动溶液自组装行为——侧链对片晶形貌的调控
PDF下载 (130)龚 宁,韩 鑫,司晓雯,姜晨曦,穆景山.PE-g-PMMA的结晶驱动溶液自组装行为——侧链对片晶形貌的调控[J].宁波大学学报(理工版),2024,37(3):113-120.DOI:10.20098/j.cnki.1001-5132.2023.0314
GONG Ning,HAN Xin,SI Xiaowen,JIANG Chenxi,MU Jingshan.Crystal-driven solution self-assembly behavior of PE-g-PMMA: regulation of side chains[J].Journal of Ningbo University(Natural Science & Engineering Edition),2024,37(3):113-120.DOI:10.20098/j.cnki.1001-5132.2023.0314
| Title: | Crystal-driven solution self-assembly behavior of PE-g-PMMA: regulation of side chains |
| 作者: | 龚 宁, 韩 鑫, 司晓雯, 姜晨曦, 穆景山 |
| Author(s): | GONG Ning, HAN Xin, SI Xiaowen, JIANG Chenxi, MU Jingshan |
| 关键词: | 聚乙烯; 接枝聚合物; 溶液自组装; 结晶驱动 |
| Keywords: | polyethylene; graft copolymer; solution self-assembly; crystallization-driven |
| 分类号: | TQ328.9 |
| DOI: | 10.20098/j.cnki.1001-5132.2023.0314 |
| 文献标识码: | A |
| 摘要: | 以多羟基功能化的聚乙烯(PE214-g-OH4)为初始聚合物, 通过原子转移自由基聚合(ATRP)方法合成了一系列以聚乙烯为主链, 以聚甲基丙烯酸甲酯(PMMA)为侧链的无规接枝聚合物(PE214-g-PMMA60、PE214-g-PMMA120、PE214-g-PMMA300), 并借助FTIR、DSC、TGA对其结构进行表征. 溶液自组装研究表明, 在甲苯中, 聚合物PE214-g-PMMA120在聚乙烯结晶驱动下先形成厚度约为8nm的单层小片晶, 随后融合成厚度不变、直径约为2μm的椭圆形单层片晶; 若缩短PMMA侧链长度, 依然会形成单核片晶结构, 但其厚度增大至10nm; 若增加PMMA侧链长度, 片晶结构则由单核变为多核, 与此同时, 其厚度减小至5nm. 在上述多核片晶的甲苯溶液中加入不良溶剂(二甲基甲酰胺DMF), 片晶的壳层收缩会导致其结构由多核重新转变为单核. |
| Abstract: | Using PE214-g-OH4 as the macro-initiator, a series of grafted copolymers (PE214-g-PMMA60, PE214-g-PMMA120, PE214-g-PMMA300) with polyethylene as the main chain and polymethyl methacrylate as the side chains are synthesized by atom transfer radical polymerization (ATRP) method. Their structures are characterized by FTIR, DSC and TGA. The self-assembly behavior of copolymers in toluene is studied. The results show that, driven by crystallization of polyethylene, PE214-g-PMMA120 first forms lamella structure with a thickness of 8nm. And then larger oval lamellae with a diameter of about 2μm are formed by fusion of the small lamellae. If the length of PMMA side chains is shortened, the lamellae still have single-core structure, but the thickness increases to 10nm. On the contrary, if the length of PMMA branch chain increases, the thickness of lamellae decreases to 5nm at the same time, and the lamellar changes single-core to multi-core structure. If N, N-dimethylformamide (DMF/toluene=1:1) is added to the toluene solution, the structure of the multicore lamellae is to be transformed from multicore to mononuclear. |
| 参考文献 /References: | [1].SCHACHER F H, RUPAR P A, MANNERS I. Functional block copolymers: nanostructured materials with emerging applications[J]. Angewandte Chemie, 2012, 51(32):7898-7921. [2].O’REILLY R K. Spherical polymer micelles: nanosized reaction vessels?[J]. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2007, 365(1861):2863-2878. [3].SAVIC R, LUO L, EISENBERG A, et al. Micellar nanocontainers distribute to defined cytoplasmic organelles[J]. Science, 2003, 300(5619):615-618. [4].HAMLEY I W. Nanotechnology with soft materials[J]. Angewandte Chemie International Edition, 2003, 42(15): 1692-1712. [5].SIMONYAN A, GITSOV I. Linear-dendritic supramo- lecular complexes as nano-scale reaction vessels for “green” chemistry: Diels Alder reactions between fullerene C60 and polycyclic aromatic hydrocarbons in aqueous medium[J]. Langmuir, 2008, 24(20):11431- 11441. [6].NISHIYAMA N, KATAOKA K. Current state, achievements, and future prospects of polymeric micelles as nanocarriers for drug and gene delivery[J]. Pharmacology & Therapeutics, 2006, 112(3):630-648. [7].GILLIES E R, FRÉCHET J M J. Designing macro- molecules for therapeutic applications: polyester dendrimer poly (ethylene oxide) “bow-tie” hybrids with tunable molecular weight and architecture[J]. Journal of the American Chemical Society, 2002, 124(47):14137- 14146. [8].LIM Y, MOON K S, LEE M. Rod-coil block molecules: their aqueous self-assembly and biomaterials applica- tions[J]. Journal of Materials Chemistry, 2008, 18(25): 2909-2918. [9].MIAO Y L, NIU X S, WU A J, et al. Metallic oxide-induced self-assembly of block copolymers to form polymeric hybrid micelles with tunable stability for tumor microenvironment-responsive drug delivery[J]. ACS Applied Materials & Interfaces, 2021, 13(28):32753- 32762. [10].LOTZ B, KOVACS A J, BASSETT G A, et al. Properties of copolymers composed of one poly-ethylene-oxide and one polystyrene block[J]. Kolloid-Zeitschrift und Zeitschrift für Polymere, 1966, 209(2):115-128. [11].HSIAO M S, YUSOFF S F M, WINNIK M A, et al. Crystallization-driven self-assembly of block copolymers with a short crystallizable core-forming segment: controlling micelle morphology through the influence of molar mass and solvent selectivity[J]. Macromolecules, 2014, 47(7):2361-2372. [12].LYU X L, XIAO A Q, ZHANG W, et al. Head-tail asymmetry as the determining factor in the formation of polymer cubosomes or hexasomes in a rod-coil amphiphilic block copolymer[J]. Angewandte Chemie International Edition, 2018, 57(32):10132-10136. [13].WANG Y Z, CHEN J Y, LI S J, et al. Semiconductor- insulator-semiconductor sandwiched lozenge crystals of poly (3-butylthiophene)-block-polyethylene copolymer[J]. Macromolecules, 2011, 44(7):1737-1741. [14].WANG H F, WU C, XIA G M, et al. Semi-crystalline polymethylene-b-poly (acrylic acid) diblock copolymers: aggregation behavior, confined crystallization and controlled growth of semicrystalline micelles from dilute DMF solution[J]. Soft Matter, 2015, 11(9):1778-1787. [15].DJALALI R, HUGENBERG N, FISCHER K, et al. Amphipolar core-shell cylindrical brushes[J]. Macro- molecular Rapid Communications, 1999, 20(8):444-449. [16].MCGRATH N, SCHACHER F H, QIU H, et al. Synthesis and crystallization-driven solution self-assembly of polyferrocenylsilane diblock copolymers with polymetha- crylate corona-forming blocks[J]. Polymer Chemistry, 2014, 5(6):1923-1929. [17].TAO D L, FENG C, CUI Y N, et al. Monodisperse fiber-like micelles of controlled length and composition with an oligo (p-phenylenevinylene) core via “living” crystallization-driven self-assembly[J]. Journal of the American Chemical Society, 2017, 139(21):7136-7139. [18].GONZALEZ-ALVAREZ M J, JIA L, GUERIN G, et al. How a small modification of the corona-forming block redirects the self-assembly of crystalline-coil block copolymers in solution?[J]. Macromolecules, 2016, 49(20):7975-7984. [19].NAZEMI A, BOOTT C E, LUNN D J, et al. Monodisperse cylindrical micelles and block comicelles of controlled length in aqueous media[J]. Journal of the American Chemical Society, 2016, 138(13):4484-4493. [20].JIA L, PETRETIC A, MOLEV G, et al. Hierarchical Polymer-carbon nanotube hybrid mesostructures by crystallization-driven self-assembly[J]. ACS Nano, 2015, 9(11):10673-10685. [21].SCHMELZ J, SCHEDL A E, STEINLEIN C, et al. Length control and block-type architectures in worm-like micelles with polyethylene cores[J]. Journal of the American Chemical Society, 2012, 134(34):14217-14225. [22].LU Y Q, LIN J P, WANG L Q, et al. Self-assembly of copolymer micelles: higher-level assembly for constructing hierarchical structure[J]. Chemical Reviews, 2020, 120(9): 4111-4140. [23].CHENG H X, WANG S G, YANG J T, et al. Synthesis and self-assembly of amphiphilic hyperbranched polygly- cerols modified with palmitoyl chloride[J]. Journal of Colloid and Interface Science, 2009, 337(1):278-284. [24].杨纤, 冯纯, 陆国林, 等. 结晶驱动自组装的研究进展[J]. 功能高分子学报, 2017, 30(1):15-33. [25].GÄDT T, SCHACHER F H, MCGRATH N, et al. Probing the scope of crystallization-driven living self-assembly: studies of diblock copolymer micelles with a polyisoprene corona and a crystalline poly (ferrocenyldiethylsilane) core-forming metalloblock[J]. Macromolecules, 2011, 44(10):3777-3786. [26].LOTZ B, KOVACS A J, BASSETT G A, et al. Properties of copolymers composed of one poly-ethylene-oxide and one polystyrene block: II. morphology of single crystals [J]. Kolloid-Zeitschrift und Zeitschrift für Polymere, 1966, 209:115-128. [27].徐玉赐. 复杂多嵌段共聚物在本体及几何受限下的自组装[D]. 上海: 复旦大学, 2012. [28].KELLER A. Solution grown polymer crystals: a survey of some problematic issues[J]. Kolloid-Zeitschrift und Zeitschrift für Polymere, 1969, 231:386-421. [29].戚美微, 黄卫, 肖谷雨, 等. 超支化聚合物的合成和自组装研究[J]. 高分子学报, 2017(2):214-228. [30].SCHMARSOW R N, CEOLÍN M, ZUCCHI I A, et al. Core-crystalline nanoribbons of controlled length via diffusion-limited colloid aggregation[J]. Soft Matter, 2019, 15(23):4751-4760. [31].MU J S, YANG F, LI W, et al. Synthesis of amphiphilic linear-hyperbranched graft-copolymers via grafting based on linear polyethylene backbone[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2014, 52(15):2146- 2154. [32].ORGAN S J, KELLER A. Solution crystallization of polyethylene at high temperatures: part 1 lateral crystal habits[J]. Journal of Materials Science, 1985, 20:1571- 1585. [33].MANSFIELD M L. Solution of the growth equations of a sector of a polymer crystal including consideration of the changing size of the crystal[J]. Polymer, 1988, 29(10): 1755-1760. [34].MILLER R L, HOFFMAN J D. Nucleation theory applied to polymer crystals with curved edges[J]. Polymer, 1991, 32(6):963-978. [35].FAN B L, LIU L, LI J H, et al. Crystallization-driven one-dimensional self-assembly of polyethylene-b-poly (tert-butylacrylate) diblock copolymers in DMF: effects of crystallization temperature and the corona-forming block[J]. Soft Matter, 2016, 12(1):67-76. |
| 备注/Memo: | 收稿日期: 2023−03−15. 宁波大学学报（理工版）网址: http://journallg.nbu.edu.cn/ 基金项目: 宁波市自然科学基金（2019A610149）. 第一作者: 龚宁, 硕士研究生, 主要研究方向: 聚乙烯基嵌段聚合物的溶液自组装. E-mail: gningly@163.com *通信作者: 穆景山, 博士, 主要研究方向: 嵌段聚合物的自组装. E-mail: mujingshan@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
