甲基丙烯酸甲酯的电化学乳液聚合
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摘要
采用可编程的线性直流电源电解铁阳极产生Fe~(2+),以此引发过硫酸铵(APS)产生自由基,催化甲基丙烯酸甲酯(MMA)单体进行乳液聚合。在优化的聚合时间和引发剂浓度条件下,重点研究了电流强度对聚合物相对分子质量及分布的调控作用。结果表明:在0. 10～0. 18 A的电流范围内,随着电流强度的增大,聚合物的平均相对分子质量也有所增加。通过调节电流的大小,可以对聚合物的相对分子质量分布进行调控,当电流从0. 10 A增大至0. 12 A时,聚甲基丙烯酸甲酯(PMMA)相对分子质量分布指数(Mw/Mn)减小为1. 461。
The programmable linear DC power was employed to electrolyze the iron anode to produce Fe~(2+),which could initiate the generation of free radicals by ammonium persulfate(APS),resulting in the catalytic effect on the methyl methacrylate(MMA)monomer for emulsion polymerization. Based on the optimized polymerization time and initiator concentration,the regulating effect of current intensity on the size and distribution of polymer molecular weight was investigated in particular. In the current range of 0. 10～0. 18 A,the average molecular weight of the obtained polymer increased with the increase of the current intensity. The molecular weight distribution of the polymer PMMA could be regulated by adjusting the current. And the PMMA molecular weight distribution index decreased to 1. 461 when the current increased from 0. 1 A to 0. 12 A.
The programmable linear DC power was employed to electrolyze the iron anode to produce Fe~(2+),which could initiate the generation of free radicals by ammonium persulfate(APS),resulting in the catalytic effect on the methyl methacrylate(MMA)monomer for emulsion polymerization. Based on the optimized polymerization time and initiator concentration,the regulating effect of current intensity on the size and distribution of polymer molecular weight was investigated in particular. In the current range of 0. 10～0. 18 A,the average molecular weight of the obtained polymer increased with the increase of the current intensity. The molecular weight distribution of the polymer PMMA could be regulated by adjusting the current. And the PMMA molecular weight distribution index decreased to 1. 461 when the current increased from 0. 1 A to 0. 12 A.
引文
[1] NUNES R W,MARTIN J R,JOHNSON J. F. Influence of molecular weight and molecular weight distribution on mechanical properties of polymers[J]. Polymer Engineering&Science,1982,22(4):205-228.
[2] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. I. methyl methacrylate[J].Die Makromolekulare Chemie,1962,51(1):154-170.
[3] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. II. high methacrylates[J]. MacromolecularChemistry and Physics,1962,51(1):171-176.
[4] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. III. methyl acrylate[J]. Macromolecular Chemistry and Physics,1962,51(2):177-181.
[5] WEI S,QIANG Y. Electro-controlled living cationic polymerization[J], Angewandte Chemie International Edition,2018,57(18):4907-4911.
[6] HIROMASA G. Absolute asymmetric electrochemical polymerization[J],Philosophical Magazine Letters,2016,96(11):409-415.
[7] CRAM S L,SPINKS G M,WALLACE G G,et al. Mechanism of electropolymerisation of methyl methacrylate and glycidyl acrylate on stainless steel[J],Electrochimica Acta,2002,47(12):1935-1948.
[8] FUNT B L,YU K C. Electroinitiated polymerization of methyl methacrylate in a homogeneous medium[J]. Journal of Polymer Science,1962,62(174):359-367.
[9] NAYAK B,BHAKTA R C. Electroinitiated polymerization of methyl methacrylate in two phase media[J]. Journal of Applied Electrochemistry,1983,13(1):105-110.
[10] PISTOIA G,RICCI A,VOSO M A. Electroinitiated polymerization of methylMethacrylate in aqueous sulfuric acid[J]. Journal of Applied Polymer Science,1976,20(9):2441-2450.
[11] AURIZI A, FILIPPESCHI V, PISTOIA G. Anodic polymerization of methyl methacrylate in CH3OH-H2SO4solutions[J]. Journal of Applied Electrochemistry,1977,7(2):139-145.
[12] PISTOIA G,BAGNARELLI O. Electrochemical bulk polymerization of methyl methacrylate in the presence of nitric acid[J]. Journal of Polymer Science,1979,17(4):1001-1013.
[13] PISTOIA G,BAGNARELLI O,MAIOCCO M. Evaluation of factors affecting the radical electropolymerization of methylmethacrylate in the presence of HNO3[J]. Journal of Applied Electrochemistry,1979,9(3):343-349.
[14] ALBECK M,K?NIGSBUCH M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. I.contribution of the electrolysis of methanol to free-radical polymerization[J]. Journal of Polymer Science:Part A,1971,9(5):1375-1386.
[15] ALBECK M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. II. polymerization of ethyl methacrylate in methanol solutions[J]. Journal of Polymer Science:Part A-1,1971,9(7):1789-1798.
[16] ALBECK M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. III. polymerization of acrylates and methacrylates in alcohol solutions[J]. Journal of Polymer Science:Part A-1,1971,9(10):2963-2975.
[17]王海霞,汪存东,高建舟.乳化剂及引发剂对碱溶性丙烯酸酯乳液合成的影响[J].中国胶粘剂,2015,24(8):425-428.
[18]李晨,王娟,田兆勇.甲基丙烯酸甲酯的乳液聚合[J].安徽化工,2008,34(4):36-27.
[19] FUNT B L, RICHARDSON D R. Electrochemical polymerization to a controlled molecular weight distribution[J].JournalofPolymerScience:PartA,1970,8(5):1055-1068.
[20] MáTRQUEZ J, LóPEZ F, MáTRQUEZ O, et al.Electrochemically controlled molecular weight of polystyrene production[J]. Polymer Bulletin,1990,24(4):451-458.
[21]潘祖仁.高分子化学[M]. 5版.北京:化学工业出版社,2011:92-93.
[2] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. I. methyl methacrylate[J].Die Makromolekulare Chemie,1962,51(1):154-170.
[3] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. II. high methacrylates[J]. MacromolecularChemistry and Physics,1962,51(1):171-176.
[4] BURNETT G M,DUNCAN G L. High conversion polymerisation of vinyl systems. III. methyl acrylate[J]. Macromolecular Chemistry and Physics,1962,51(2):177-181.
[5] WEI S,QIANG Y. Electro-controlled living cationic polymerization[J], Angewandte Chemie International Edition,2018,57(18):4907-4911.
[6] HIROMASA G. Absolute asymmetric electrochemical polymerization[J],Philosophical Magazine Letters,2016,96(11):409-415.
[7] CRAM S L,SPINKS G M,WALLACE G G,et al. Mechanism of electropolymerisation of methyl methacrylate and glycidyl acrylate on stainless steel[J],Electrochimica Acta,2002,47(12):1935-1948.
[8] FUNT B L,YU K C. Electroinitiated polymerization of methyl methacrylate in a homogeneous medium[J]. Journal of Polymer Science,1962,62(174):359-367.
[9] NAYAK B,BHAKTA R C. Electroinitiated polymerization of methyl methacrylate in two phase media[J]. Journal of Applied Electrochemistry,1983,13(1):105-110.
[10] PISTOIA G,RICCI A,VOSO M A. Electroinitiated polymerization of methylMethacrylate in aqueous sulfuric acid[J]. Journal of Applied Polymer Science,1976,20(9):2441-2450.
[11] AURIZI A, FILIPPESCHI V, PISTOIA G. Anodic polymerization of methyl methacrylate in CH3OH-H2SO4solutions[J]. Journal of Applied Electrochemistry,1977,7(2):139-145.
[12] PISTOIA G,BAGNARELLI O. Electrochemical bulk polymerization of methyl methacrylate in the presence of nitric acid[J]. Journal of Polymer Science,1979,17(4):1001-1013.
[13] PISTOIA G,BAGNARELLI O,MAIOCCO M. Evaluation of factors affecting the radical electropolymerization of methylmethacrylate in the presence of HNO3[J]. Journal of Applied Electrochemistry,1979,9(3):343-349.
[14] ALBECK M,K?NIGSBUCH M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. I.contribution of the electrolysis of methanol to free-radical polymerization[J]. Journal of Polymer Science:Part A,1971,9(5):1375-1386.
[15] ALBECK M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. II. polymerization of ethyl methacrylate in methanol solutions[J]. Journal of Polymer Science:Part A-1,1971,9(7):1789-1798.
[16] ALBECK M,RELIS J. Electroinitiated polymerization of vinylic monomers in polar systems. III. polymerization of acrylates and methacrylates in alcohol solutions[J]. Journal of Polymer Science:Part A-1,1971,9(10):2963-2975.
[17]王海霞,汪存东,高建舟.乳化剂及引发剂对碱溶性丙烯酸酯乳液合成的影响[J].中国胶粘剂,2015,24(8):425-428.
[18]李晨,王娟,田兆勇.甲基丙烯酸甲酯的乳液聚合[J].安徽化工,2008,34(4):36-27.
[19] FUNT B L, RICHARDSON D R. Electrochemical polymerization to a controlled molecular weight distribution[J].JournalofPolymerScience:PartA,1970,8(5):1055-1068.
[20] MáTRQUEZ J, LóPEZ F, MáTRQUEZ O, et al.Electrochemically controlled molecular weight of polystyrene production[J]. Polymer Bulletin,1990,24(4):451-458.
[21]潘祖仁.高分子化学[M]. 5版.北京:化学工业出版社,2011:92-93.