CoⅡ(salen*)存在下的氯丁二烯自由基聚合

doi:10.7503/cjcu20160496

摘要/Abstract

摘要：

研究了N,N'-双(3,5-二叔丁基水杨醛)-1,2-环己二胺钴(Ⅱ)[Co^Ⅱ(salen*)]存在下氯丁二烯(CP)的自由基聚合, 考察了不同溶剂、引发剂用量及配体对聚合反应的影响. 结果表明, 随着引发剂用量的增加, 聚合反应的诱导期缩短, 以[ABVN]₀/[ Co^Ⅱ(salen*)]₀=3/1配比投料, 聚合反应表现出较好的可控聚合特征. 在苯、甲苯、四氢呋喃(THF)和乙酸乙酯(EA) 4种溶剂中按照[CP]₀/[Co^Ⅱ(salen*)]₀/[ABVN]₀=400/1/3的配比投料, 在苯中的可控聚合程度最好: 在低转化率(40%以下)实测聚合物分子量(M_n,GPC)与理论值(M_n,th)吻合, 且分子量随转化率增加呈线性增长. 研究了THF、三乙胺(NEt₃)、吡啶(Py)及水等不同配体对聚合反应的影响, 发现在添加THF时, 低转化率(40%以下)下M_n,GPC与M_n,th相符, 分子量分布(PDI)相对较窄.

关键词: 氯丁二烯, 有机金属控制的自由基聚合, 供电子配体, CoⅡ(salen*), 有机钴控制的自由基聚合

Abstract:

Radical polymerization of chloroprene(CP) in the presence of N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine [Co^Ⅱ(salen*)], as a mediator was investigated. The results show that the induction time is shortened and the polymerization rate is increased with the increase of ABVN concentrations. The linear increase in molecular weight with conversion, and molecular weight close to the theoretical value at low conversion in benzene, demonstrating the living process of CP radical polymerization mediated by [Co^Ⅱ(salen*)]. In order to determine what effect, if any, the solvents had upon the control of the polymerization, various solvents were used in the CMRP of chloroprene, and the process in benzene efficiently controls the molar mass(characterized by size exclusion chromatography, SEC) at low monomer conversion. Then, the effect of electron donors(ED) on the [Co^Ⅱ(Salen*)]-mediated radical polymerization of CP was examined by the addition of electron donors, water, pyridine(Py), NEt₃, tetrahydrofuran(THF) and dimethylsulfoxide(DMSO) to the complex in the molar ratio [CP]/[Co]/[ABVN]/[ED]=400/1/3/25. The induction periods became shorter with the addition of electron donors(ED). Obviously, the control of polymerization increased with the addition of THF, which was demonstrated by molecular weight close to the theoretical value and a relatively narrow molecular weight distribution at low monomer conversion.

Key words: Chloroprene, Organometallic mediated radical polymerization, Electron donor, CoⅡ(salen*), Cobalt-mediated radical polymerization

中图分类号:

O631

TrendMD:

李威威, 石艳, 杨万泰, 付志峰. Co^Ⅱ(salen*)存在下的氯丁二烯自由基聚合. 高等学校化学学报, 2016, 37(11): 2085.

LI Weiwei, SHI Yan, YANG Wantai, FU Zhifeng. Cobalt-mediated Radical Polymerization(CMRP) of Chloroprene by Co^Ⅱ(salen*)^†. Chem. J. Chinese Universities, 2016, 37(11): 2085.

图/表 8

Fig.1 Structures of salen*(A) and CoⅡ(salen*)(B)

Fig.2 First order kinetic plots for polymerization of CP in benzene[V(CP)/V(benzene)=1/2, 50 ℃] with different ABVN concentrationsConditions: [CoⅡ(salen*)]0=9.0×10-3 mol/L, [CP]0=3.6 mol/L, [ABVN]0/[CoⅡ(salen*)]0: a. 2.0; b. 2.5; c. 3.0; d. 3.5; e. 4.0.

Fig.3 Molecular weight distribution(A) and number-average molecular weight(B) for CoⅡ(salen*) mediated CP polymerization in benzene(CP/benzene=1/2, 50 ℃) with different ABVN concentrationsMn,th=([M]0/[CoⅡ(salen*)]0)×MCP×monomer conversion+MCoⅡ(salen*; [M]0=initial monomer concentration; [CoⅡ(salen*)]0=initial CoⅡ(salen*) concentration; MCP=molecular weight of CP=88.54; MCoⅡ(salen*=604. Conditions are the same as those in Fig.2. [CP]∶[CoⅡ(salen*)]∶[ABVN]: 400∶1∶2; 400∶1∶2.5; 400∶1∶3; 400∶1∶3.5; 400∶1∶4.

Fig.4 First order kinetic plots for polymerization of CP in different solutions at 50 ℃ Conditions: [CP]0∶[ABVN]0∶[CoⅡ(salen*)]0= 400∶3∶1; a. benzene; b. THF; c. EA; d. toluene; e. bulk.

Fig.5 Plots of conversion versus molecular weight(Mn)(A) and PDI(B) for polymerization of CP in different solutions at 50 ℃ and typical GPC traces from the synthesis of PCP in benzene at 50 ℃(C)Conditions are the same as those in Fig.4. Toluene; benzene; bulk; THF; EA.

Fig.6 First order kinetic plots for polymerization of CP in benzene at 50 ℃Conditions: [CP]0∶[ABVN]0∶[CoⅡ(salen*)]0=400∶3∶1 and [Co]∶[ED]=1∶25; a. DMSO; b. THF; c. NEt3; d. Py; e. no addition.

Fig.7 Plots of molecular weight(A) and PDI(B) versus conversion for the addition of electron donors to polymerization of CP in benzene at 50 ℃ and typical GPC traces from the synthesis of PCP with addition of THF(C)Conditions are the same as those in Fig.6. DMSO; THF; water; Py; NEt3; no addition.

Fig.8 Time dependent UV-Vis spectra illustrating the transformation of CoⅡ(salen*) to CoⅢ(salen*)-R during the induction period of CP polymerizationConditions: [CP]0∶[ABVN]0∶[CoⅡ(salen*)]0=400∶3∶1 in benzene at 50 ℃. Time/min: a. 0; b. 30; c. 60; d. 90; e. 120.

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