Polymerization of acrylonitrile in dimethyl carbonate: A kinetic and mechanistic study

IF 4.1 2区 化学 Q2 POLYMER SCIENCE
Yuhang Jiao , Huijie Yan , Qingxin Meng , Shiling Jia , Shuang Liu , Huixuan Zhang , Zhongyu Fu
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Abstract

For the first time, a new polymerization medium, dimethyl carbonate (DMC), was used for the polymerization of acrylonitrile (AN), and polyacrylonitrile (PAN) powder was obtained successfully. The effects of polymerization factors, including monomer concentrations, temperature and initiator concentrations on the structures and properties of PAN powders were investigated by nuclear magnetic resonance spectroscopy (NMR), total internal reflectance Fourier transform infrared spectrometer (FTIR), wide-angle X-ray diffractometer (WXRD) and thermal gravimetric analyzer (TGA). The polymerization kinetic and mechanistic study of PAN with DMC as the polymerization medium were discussed in details. There are three key achievements in this paper. First, the kinetic equation of PAN polymerization with DMC as a medium was established: Rp = K[ABVN]0.92[AN]6.78. This result shows that the Rp is highly dependent on the AN concentrations. Second, the chain transfer constant of DMC was measured to be 4.57 × 10−4 at 60 °C, and the chain transfer constant increases with polymerization temperature. Lastly, the structures and properties of PAN powders prepared with H2O, tetrahydrofuran (THF) and DMC as media were compared. The results showed that the PAN prepared with DMC as a medium by free radical polymerization had a higher conversion, molecular weight and better crystalline property compared to THF. These findings indicate that DMC is a promising medium for manufacturing high quality PAN powder by free radical polymerization.

Abstract Image

Abstract Image

丙烯腈在碳酸二甲酯中的聚合:动力学和机理研究
首次将新型聚合介质碳酸二甲酯(DMC)用于丙烯腈(AN)的聚合,并成功获得了聚丙烯腈(PAN)粉末。利用核磁共振光谱仪(NMR)、全内反射傅立叶变换红外光谱仪(FTIR)、广角 X 射线衍射仪(WXRD)和热重分析仪(TGA)研究了单体浓度、温度和引发剂浓度等聚合因素对 PAN 粉末结构和性质的影响。详细讨论了以 DMC 为聚合介质的 PAN 的聚合动力学和机理研究。本文取得了三项重要成果。首先,建立了以 DMC 为介质的 PAN 聚合动力学方程:Rp = K[ABVN]0.92[AN]6.78 。这一结果表明 Rp 与 AN 浓度有很大关系。其次,在 60°C 时,测得 DMC 的链转移常数为 4.57 × 10-4,链转移常数随聚合温度的升高而增大。最后,比较了以 H2O、四氢呋喃(THF)和 DMC 为介质制备的 PAN 粉末的结构和性质。结果表明,与 THF 相比,以 DMC 为介质通过自由基聚合制备的 PAN 具有更高的转化率、分子量和更好的结晶特性。这些结果表明,DMC 是通过自由基聚合法制造高质量 PAN 粉末的理想介质。
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来源期刊
Polymer
Polymer 化学-高分子科学
CiteScore
7.90
自引率
8.70%
发文量
959
审稿时长
32 days
期刊介绍: Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.
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