基于PDMA的星状和嵌段聚合物的合成、表征及溶液行为研究
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摘要
本论文主要研究基于PDMA的星状和嵌段聚合物的合成,表征及溶液行为。实验中使用的单体包括甲基丙烯酸-2-(N, N-二甲氨基)乙酯(DMAEMA或DMA)、甲基丙烯酸叔丁酯(tert-BMA或tBMA)、以及甲基丙烯酸-(2, 2, 3, 3, 4, 4, 5, 5-八氟)戊酯(2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl methacrylate, OFMA)。
第一部分聚阳离子与聚阴离子通过超分子作用构建微凝胶
通过原子转移自由基聚合方法(ATRP)制备星状聚合物β-CD-g-PDMA;通过氧阴离子聚合方法制备嵌段聚阴离子PMAA30-b-PEG-b-PMAA30。1H NMR,GPC,FT-IR和TGA的结果证实了聚合物的组成及化学结构。通过TEM及DLS方法研究聚阴、阳离子电解质在水溶液中的自组装行为及pH响应性。由上述带有相反电荷的聚电解质在PBS缓冲溶液中混合后可形成微凝胶。SEM,TEM,DLS和流变仪测试结果证实了微凝胶的成功制备。结果表明,微凝胶的形态和大小依赖于聚电解质的结构、浓度以及聚阳离子和聚阴离子电解质的比例。
第二部分含氟两性电解质聚合物的制备及溶液行为研究
通过氧阴离子聚合的方法,制备了含氟嵌段聚合物BzO-PDMA30-b-PtBMA10-b-POFPMA6,将其水解,则得到了含氟两性电解质聚合物BzO-PDMA30-b-PtBMA10-b-POFPMA6。1H NMR、19F NMR和GPC的结果证实了这两种聚合物的组成及化学结构。通过一系列方法研究含氟嵌段共聚物的水溶液行为。表面张力测试结果表明水解后的含氟嵌段聚合物具有相对较高的表面活性。此外DLS和TEM测试结果证明这两种含氟嵌段聚合物都具有很好的pH响应性。
This paper is focused on the synthesis and characterization of star and block copolymers based on poly[2-(N, N-dimethylamino)ethyl methacrylate] (PDMAEMA or PDMA in short) and their solution behaviors. The monomers used in this work include DMA, tert-butyl methacrylate (tert-BMA or tBMA) and 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl methacrylate (OFPMA).
(1) Fabrication of Microgels via Supramolecular Assembly of Polycation and Polyanion
Star polymersβ-CD-g-PDMA was prepared by atom transfer radical polymerization (ATRP), while PMAA30-b-PEG-b-PMAA30 was synthesized by oxyanion-initiated polymerization. The composition and chemical structures of star polymer and block copolymer were confirmed by the measurements of 1H NMR spectroscopy, gel permeation chromatography (GPC), fourier transform infrared spectroscopy (FTIR) and thermogravity analysis (TGA). The self-aggregating morphologies of polyanion and polycation in aqueous solution were investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). It was found that the polycation and polyanion in phosphate buffer solution (PBS) formed microgel immediately as soon as they were mixed. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) and rheological test confirmed the formation of polyion complex microgels. It was found that both the morphologies and particle size resulted from the microgels depended on the variation of concentrations, the structures of polyanion and the ratios of polycation to polyanion.
(2) Preparation and Solution Behavior of Fluorinated Amphiphilic Polyelectrolyte
Well-defined polyampholyte BzO-PDMA30-b-PMAA10-b-POFPMA6 was prepared successfully by the hydrolysis of fluorinated amphiphilic triblock copolymer BzO-PDMA30-b-PtBMA10-b-POFPMA6, which was synthesized by oxyanion-initiated polymerization. The composition and chemical structure of these fluorinated copolymers were confirmed by 1H NMR, 19F NMR spectroscopy and gel permeation chromatography (GPC) techniques. The solution behaviors of these fluorinated copolymers were investigated by the measurements of surface tension, dynamic light scattering (DLS), Zeta-potential (ξ-potential) and transmission electron microscopy (TEM). The results indicate that the BzO-PDMA30-b-PMAA10-b-POFPMA6 possess relatively high surface activity than BzO-PDMA30-b-PtBMA10-b-POFPMA6. Moreover, the DLS andξ-potential measurements showed that these two kinds of fluorinated triblock copolymers possess distinct pH-responsive properties.
第一部分聚阳离子与聚阴离子通过超分子作用构建微凝胶
通过原子转移自由基聚合方法(ATRP)制备星状聚合物β-CD-g-PDMA;通过氧阴离子聚合方法制备嵌段聚阴离子PMAA30-b-PEG-b-PMAA30。1H NMR,GPC,FT-IR和TGA的结果证实了聚合物的组成及化学结构。通过TEM及DLS方法研究聚阴、阳离子电解质在水溶液中的自组装行为及pH响应性。由上述带有相反电荷的聚电解质在PBS缓冲溶液中混合后可形成微凝胶。SEM,TEM,DLS和流变仪测试结果证实了微凝胶的成功制备。结果表明,微凝胶的形态和大小依赖于聚电解质的结构、浓度以及聚阳离子和聚阴离子电解质的比例。
第二部分含氟两性电解质聚合物的制备及溶液行为研究
通过氧阴离子聚合的方法,制备了含氟嵌段聚合物BzO-PDMA30-b-PtBMA10-b-POFPMA6,将其水解,则得到了含氟两性电解质聚合物BzO-PDMA30-b-PtBMA10-b-POFPMA6。1H NMR、19F NMR和GPC的结果证实了这两种聚合物的组成及化学结构。通过一系列方法研究含氟嵌段共聚物的水溶液行为。表面张力测试结果表明水解后的含氟嵌段聚合物具有相对较高的表面活性。此外DLS和TEM测试结果证明这两种含氟嵌段聚合物都具有很好的pH响应性。
This paper is focused on the synthesis and characterization of star and block copolymers based on poly[2-(N, N-dimethylamino)ethyl methacrylate] (PDMAEMA or PDMA in short) and their solution behaviors. The monomers used in this work include DMA, tert-butyl methacrylate (tert-BMA or tBMA) and 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl methacrylate (OFPMA).
(1) Fabrication of Microgels via Supramolecular Assembly of Polycation and Polyanion
Star polymersβ-CD-g-PDMA was prepared by atom transfer radical polymerization (ATRP), while PMAA30-b-PEG-b-PMAA30 was synthesized by oxyanion-initiated polymerization. The composition and chemical structures of star polymer and block copolymer were confirmed by the measurements of 1H NMR spectroscopy, gel permeation chromatography (GPC), fourier transform infrared spectroscopy (FTIR) and thermogravity analysis (TGA). The self-aggregating morphologies of polyanion and polycation in aqueous solution were investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). It was found that the polycation and polyanion in phosphate buffer solution (PBS) formed microgel immediately as soon as they were mixed. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) and rheological test confirmed the formation of polyion complex microgels. It was found that both the morphologies and particle size resulted from the microgels depended on the variation of concentrations, the structures of polyanion and the ratios of polycation to polyanion.
(2) Preparation and Solution Behavior of Fluorinated Amphiphilic Polyelectrolyte
Well-defined polyampholyte BzO-PDMA30-b-PMAA10-b-POFPMA6 was prepared successfully by the hydrolysis of fluorinated amphiphilic triblock copolymer BzO-PDMA30-b-PtBMA10-b-POFPMA6, which was synthesized by oxyanion-initiated polymerization. The composition and chemical structure of these fluorinated copolymers were confirmed by 1H NMR, 19F NMR spectroscopy and gel permeation chromatography (GPC) techniques. The solution behaviors of these fluorinated copolymers were investigated by the measurements of surface tension, dynamic light scattering (DLS), Zeta-potential (ξ-potential) and transmission electron microscopy (TEM). The results indicate that the BzO-PDMA30-b-PMAA10-b-POFPMA6 possess relatively high surface activity than BzO-PDMA30-b-PtBMA10-b-POFPMA6. Moreover, the DLS andξ-potential measurements showed that these two kinds of fluorinated triblock copolymers possess distinct pH-responsive properties.
引文
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