College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha, Hunan 410004, China.
College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha, Hunan 410004, China.
Int J Biol Macromol. 2023 Jun 30;241:124458. doi: 10.1016/j.ijbiomac.2023.124458. Epub 2023 Apr 17.
It is a promising idea to graft zwitterionic polymers onto lignin and prepare lignin-grafted-poly [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (Lignin-g-PDMAPS) thermosensitive polymer with the upper critical solution temperature (UCST). In this paper, an electrochemically mediated atom transfer radical polymerization (eATRP) method was used to prepare Lignin-g-PDMAPS. The structure and property of the Lignin-g-PDMAPS polymer were characterized by the fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC). Furthermore, the effect of catalyst structure, applied potential, amount of Lignin-Br, Lignin-g-PDMAPS concentration, NaCl concentration on UCST of Lignin-g-PDMAPS were investigated. It was worth noting that polymerization was well controlled when the ligand was tris (2-aminoethyl) amine (MeTREN), applied potential was -0.38 V and the amount of Lignin-Br was 100 mg. And the UCST of the Lignin-g-PDMAPS aqueous solution (1 mg/ml) was 51.47 °C, the molecular weight was 8987 g/mol, and the particle size was 318 nm. It was also found that the UCST increased and the particle size decreased with the Lignin-g-PDMAPS polymer concentration increased, and the UCST decreased and the particle size increased with the NaCl concentration increases. This work investigated UCST-thermoresponsive polymer which possessed lignin main chain combining the zwitterionic side chain, and provided a new way for development of lignin based UCST-thermoresponsive materials and medical carrier materials, in addition to expand the scope of eATRP.
将两性离子聚合物接枝到木质素上,并制备具有上临界溶解温度(UCST)的木质素接枝聚[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)铵氢氧化物(Lignin-g-PDMAPS)温敏聚合物是一个很有前途的想法。在本文中,采用电化学介导原子转移自由基聚合(eATRP)法制备 Lignin-g-PDMAPS。通过傅里叶变换红外光谱(FT-IR)、核磁共振(NMR)、X 射线光电子能谱(XPS)、动态光散射(DLS)、差示扫描量热仪(DSC)对 Lignin-g-PDMAPS 聚合物的结构和性能进行了表征。此外,还考察了催化剂结构、施加电位、木质素-Br 的用量、Lignin-g-PDMAPS 浓度、NaCl 浓度对 Lignin-g-PDMAPS 的 UCST 的影响。值得注意的是,当配体为三(2-氨基乙基)胺(MeTREN)、施加电位为-0.38 V 且木质素-Br 的用量为 100 mg 时,聚合得到了很好的控制。Lignin-g-PDMAPS 水溶液(1 mg/ml)的 UCST 为 51.47°C,分子量为 8987 g/mol,粒径为 318 nm。还发现,随着 Lignin-g-PDMAPS 聚合物浓度的增加,UCST 升高,粒径减小,随着 NaCl 浓度的增加,UCST 降低,粒径增大。这项工作研究了具有木质素主链和两性离子侧链的 UCST-温敏聚合物,为开发基于木质素的 UCST-温敏材料和医用载体材料提供了新途径,此外还扩展了 eATRP 的应用范围。