Citation: Xiao-qiang Xue, Feng Qian, Wen-yan Huang, Hong-jun Yang, Qi-min Jiang, Lei Zhou, Bi-biao Jiang. Preparation and Multiple Responsiveness of Copolymers of PNIPAM Containing Azo Pyridine in Side Chain[J]. Acta Polymerica Sinica, ;2018, 0(9): 1175-1183. doi: 10.11777/j.issn1000-3304.2018.18002 shu

Preparation and Multiple Responsiveness of Copolymers of PNIPAM Containing Azo Pyridine in Side Chain

1.
Department of Materials Science and Engineering, Changzhou University, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou 213164
2.
Patent Examination Cooperation Jiangsu Center of the Patent Office, Suzhou 215011
3.
School of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210000

Corresponding author: Bi-biao Jiang, jiangbibiao@cczu.edu.cn
Received Date: 2 January 2018
Revised Date: 26 March 2018
Available Online: 7 May 2018

A novel azopyridine monomer was prepared by diazo coupling: 4-(4-pyridylazo) phenyl methacrylate (PAZO). PAZO was randomly copolymerized with N-isopropylacrylamide (NIPAM) and ethylene glycol methyl ether methacrylate (EGMA) to obtain a multi-response terpolymer (P(NIPAM-co-PAZO-co-EGMA)). The structure of the polymer was characterized by ¹H-NMR and gel permeation chromatography (GPC), and the responsiveness of the polymer to UV spectroscopy was studied. Under the acidic conditions, the trans absorption peak of azo pyridine is stable and the weakness is inhibited. Under alkaline conditions, the trans absorption peak is weak, and the cis absorption peak is enhanced and stable. The lowest phase transition temperature (LCST) of the polymer was 49 °C. The trans structure of azopyridine was changed to the cis structure by ultraviolet light irradiation. Before UV irradiation, the hydrodynamic radius of the polymer was 9.82 nm. After the UV illumination, the value became 11.07 nm, and increased by 1.25 nm, indicating that the polymer size was increased after UV illumination. The size of the polymer increased with the increased size of the azo pyridine structure, making the PNIPAM segment more sensitive to temperature and LCST decreased 2 °C to 47 °C. The LCST of polymer sites before introduction of CO₂ was 49 °C, and that was changed to 62 °C after passing through CO₂. Argon is bubbled through the polymer solution or the solution is left open at 60 °C for a period of time to evacuate the CO₂. The LCST of the solution changes to 49 °C again. Before and after the introduction of CO₂, there was no obvious change in the LCST point of the aqueous solution of PNIPAM, indicating that the carbonic acid did not affect the amine group on the PNIPAM group, but instead was protonated with the azopyridine group. The CO₂ and argon gasses were repeatedly introduced. The LCST of the polymer solution changed reversibly between 49 and 62 °C.
- Isopropyl acrylamide,
- Azo pyridine,
- Random copolymerization,
- Multiple responses
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沈阳化工大学材料科学与工程学院沈阳 110142