Citation: Yan-An Wang, Xiao-Tao Zhang, Yan Shi, Zhi-Feng Fu, Wan-tai Yang. Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts[J]. Acta Polymerica Sinica, ;2018, 0(10): 1287-1296. doi: 10.11777/j.issn1000-3304.2018.18046 shu

Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Yan Shi, shiyan@mail.buct.edu.cn
Received Date: 5 February 2018
Revised Date: 9 March 2018
Available Online: 24 May 2018

The reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) was carried out utilizing an alkyl iodide in situ formed as initiator and dicyclohexylcarbodiimide (DCC) or N,N′-diisopropylcarbodiimide (DIC) as highly efficient organic catalysts for the first time. Firstly, the catalytic activity of the two catalysts was demonstrated and compared. The control of the polymerization by DCC was better than that by DIC under the same experimental conditions. Then the influence of the amount of catalyst DCC, the amount of traditional initiators and the type of solvents on the polymerization was investigated in detail. The results show that the addition of DCC or DIC catalyst can effectively reduce the polydispersity index (PDI = M_w/M_n), as compared with the reverse iodine chain transfer polymerization (RITP). The catalytic performance is excellent with the ratio of [MMA]₀:[I₂]₀:[ABVN]₀:[DCC]₀ = 200:1:1.7:4. The measured molecular weight by GPC is consistent with the theoretical molecular weight, and the molecular weight increases linearly with the increase in conversion rate. The molecular weight polydispersity index is small (PDI < 1.26). The polymerizations of MMA in different solvents were carried out. The induction period is shortened and the polymerization rate is increased with the increase of catalyst or initiator amount. The polymerizations have good control effect in toluene, benzene, tetrahydrofuran (THF), anisole. The structure and the iodine-end-capped structure of the obtained PMMA was demonstrated by ¹H-NMR spectrum. The calculated M_n,NMR was in good agreement with M_n,GPC, and the fraction of iodine chain end of the PMMA chains was up to 97.5%, and the iodine terminus could be efficiently reactivated for chain extension. Last, the mechanism of the polymerization mediated by carbodiimide is discussed based on free radical trapping experiments and ultraviolet absorption. The high conversion of CP-I to CPo radical catalyzed by DIC and the complexation peak of I₂/carbodiimide detected by ultraviolet absorption spectroscopy demonstrate that the polymerization catalyzed by carbodiimide proceeds according to the reversible complexation mediated polymerization mechanism.
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沈阳化工大学材料科学与工程学院沈阳 110142

Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com