Cobalt-mediated Radical Polymerization(CMRP) of Chloroprene by CoⅡ(salen*)†

doi:10.7503/cjcu20160496

Abstract

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

CLC Number:

O631

TrendMD:

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

Figures/Tables 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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