无水FeCl3存在下丙烯酸甲酯的单电子转移活性自由基聚合动力学

doi:10.11944/j.issn.1000-0518.2017.01.160095

摘要/Abstract

摘要：

单电子转移活性自由基聚合(SET-LRP)是一种可以对聚合物进行有效分子设计,合成不同拓扑结构并且能够有效调节其相对分子质量和相对分子质量分布的新型聚合方法,具有潜在的应用前景。以2-溴丙酸甲酯作为引发剂,Cu(0)/三(N,N-二甲基氨基乙基)胺(Me₆-TREN)为复合催化体系,通过在二甲基亚砜中添加不同摩尔浓度的无水FeCl₃来研究其对丙烯酸甲酯的SET-LRP聚合动力学的影响。结果表明,随着三价铁离子量的增加,其链增长速率常数下降并且出现诱导期延长现象,说明三价铁离子参与了SET-LRP的聚合动力学过程,它和在同样实验条件下二价铜所起的作用截然不同,这可能是由于三价铁离子的氧化导致反应体系中一价铜的浓度降低引起的。此项工作从另外一个角度解释了零价铜催化下SET-LRP聚合诱导期产生的原因。

关键词: 无水氯化铁, 单电子转移活性自由基聚合, 聚合动力学, 聚丙烯酸甲酯

Abstract:

Single-electron transfer living radical polymerization(SET-LRP) as an effective method is adopted to synthesize polymers with defined relative molecular mass, composition and specified molecular structure, which is powerful to adjust the molecular mass distribution of the obtained polymers in a wide range. To study the effects of the externally added anhydrous ferric chloride on the general SET-LRP polymerization kinetics of methyl acrylate, we carry out the research by using methyl 2-bromopropionate as the initiator and Cu(0)/tris(2-(dimethylamino)ethy)amine(Me₆-TREN) as the composite catalytic system in dimethyl sulfoxide with different ratios of anhydrous ferric chloride. The experimental results indicate that the externally added anhydrous ferric chloride has an important influence on the polymerization kinetics of methyl acrylate. With increasing the concentration of iron ions in the solvent, the polymerization rates decrease and the induction period appears to be prolonged indicating that iron ions are involved in SET-LRP polymerization kinetics. This may be due to the decreased concentration of Cu(Ⅰ) relative to that of the reaction without the addition of any anhydrous ferric chloride. The current work will stimulate us to further clarify the origin of induction period in the copper(0) catalyzed SET-LRP of typical monomers.

Key words: anhydrous ferric chloride, single-electron transfer living radical polymerization, polymerization kinetics, poly(methyl acrylate)

程金华, 姜鸿基. 无水FeCl₃存在下丙烯酸甲酯的单电子转移活性自由基聚合动力学[J]. 应用化学, 2017, 34(1): 40-45.

CHEN Jinhua, JIANG Hongji. Kinetics of Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in the Presence of Anhydrous Ferric Chloride[J]. Chinese Journal of Applied Chemistry, 2017, 34(1): 40-45.

参考文献

[1]	Percec V,Guliashvili T,Ladislaw J S,et al. Ultrafast Synthesis of Ultrahigh Molar Mass Polymers by Metal-Catalyzed Living Radical Polymerization of Acrylates, Methacrylates, and Vinyl Chloride Mediated by SET at 25 ℃[J]. J Am Chem Soc,2006,128(43):14156-14165.
[2]	Guliashvili T,Percec V.Synthesis of Perfectly Bifunctional Polyacrylates by Single-Electron-Transfer Living Radical Polymerization[J]. J Polym Sci Part A:Polym Chem,2007,45(9):1607-1618.
[3]	Rosen B M,Percec V.Implications of Monomer and Initiator Structure on the Dissociative Electron-transfer Step of SET-LRP[J]. J Polym Sci Part A:Polym Chem,2008,46(16):5663-5697.
[4]	Monteiro M J,Guliashvili T,Percec V.Kinetic Simulation of Single Electron Transfer-living Radical Polymerization of Methyl Acrylate at 25 ℃[J]. J Polym Sci Part A:Polym Chem,2007,45(10):1835-1847.
[5]	Rosen B M,Percec V.A Density Functional Theory Computational Study of the Role of Ligand on the Stability of Cui and Cuii Species Associated with ATRP and SET-LRP[J]. J Polym Sci Part A:Polym Chem,2007,45(21):4950-4964.
[6]	Ligadas G,Percec V.A Comparative Analysis of SET-LRP of MA in Solvents Mediating Different Degrees of Disproportionation of Cu(Ⅰ)Br[J]. J Polym Sci Part A:Polym Chem,2008,46(20):6880-6895.
[7]	Ligadas G,Percec V.Ultrafast SET-LRP of Methyl Acrylate at 25 ℃ in Alcohols[J]. J Polym Sci Part A:Polym Chem,2008,46(8):2745-2754.
[8]	Ligadas G,Rosen B M,Percec V,et al. Effect of Cu(0) Particle Size on the Kinetics of SET-LRP in DMSO and Cu-mediated Radical Polymerization in MeCN at 25 ℃[J]. Macromolecules,2008,41(22):8365-8371.
[9]	Rosen B M,Nguyen N H,Percec V,et al. Cooperative and Synergistic Solvent Effects in SET-LRP of MA[J]. J Polym Sci Part A:Polym Chem,2009,47(21):5591-5605.
[10]	Nguyen N H,Rosen B M,Percec V,et al. New Efficient Reaction Media for SET-LRP Produced from Binary Mixtures of Organic Solvents and H2O[J]. J Polym Sci Part A:Polym Chem,2009,47(21):5577-5590.
[11]	Ladislaw J S.Precision Synthesis of Covalent and Supramolecular Polymers[D]. Philadelphia:University of Pennsylvania,2008.
[12]	Matyjaszewski K,Pintauer T,Gaynor S.Removal of Copper-based Catalyst in Atom Transfer Radical Polymerization Using Ion Exchange Resins[J]. Macromolecules,2000,33(4):1476-1478.
[13]	Rosen B M,Percec V.Single-electron Transfer and Single-electron Transfer Degenerative Chain Transfer Living Radical Polymerization[J]. Chem Rev,2009,109(11):5069-5119.
[14]	Gibson V C,O'Reilly R K,Williams D,et al. Polymerization of Methyl Methacrylate Using Four-coordinate (α-Diimine) Iron Catalysts:Atom Transfer Radical Polymerization vs Catalytic Chain Transfer[J]. Macromolecules,2003,36(8):2591-2593.
[15]	Shao Q,Sun H M,Pang X G,et al. A Neutral Ni(Ⅱ) Acetylide-mediated Radical Polymerization of Methyl Methacrylate Using the Atom Ttransfer Radical Polymerization Method[J]. Eur Polym,2004,40(1):97-102.
[16]	Ren W Y,Jiang L,Dan Y,et al. The Application of Copper(Ⅱ) of Deactivator on the Single-electron Transfer Living Radical Polymerization of e-Butyl Acrylate[J]. J Polym Sci Part A:Polym Chem,2010,48(13):2793-2797.
[17]	Nguyen N H,Percec V.Dramatic Acceleration of SET-LRP of Methyl Acrylate During Catalysis with Activated Cu(0) Wire[J]. J Polym Sci Part A:Polym Chem,2010,48(22):5109-5119.
[18]	Nguyen N H,Percec V.Acid Dissolution of Copper Oxides as a Method for the Activation of Cu(0) Wire Catalyst for SET-LRP[J]. J Polym Sci Part A:Polym Chem,2011,49(19):4241-4252.

无水FeCl₃存在下丙烯酸甲酯的单电子转移活性自由基聚合动力学

Kinetics of Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in the Presence of Anhydrous Ferric Chloride

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 11

编辑推荐

Metrics

本文评价

[1]	丁伟, 刘康, 栾和鑫, 于涛, 曲广淼. 水溶液中单电子转移活性自由基聚合法制备新型阳离子共聚丙烯酰胺/丙烯酸酯[J]. 应用化学, 2013, 30(06): 648-654.
[2]	毕可臻, 张跃军. 丙烯酰胺与二甲基二烯丙基氯化铵共聚动力学[J]. 应用化学, 2011, 28(12): 1354-1359.
[3]	丁伟, 孙颖, 吕崇福, 景慧, 于涛, 曲广淼. 离子液体中单电子转移活性自由基聚合法制备星形聚丙烯酰胺[J]. 应用化学, 2011, 28(10): 1148-1154.
[4]	丁伟, 吕崇福, 孙颖, 景慧, 魏继军, 栾和鑫, 于涛, 曲广淼. 苯乙烯的单电子转移活性自由基聚合[J]. 应用化学, 2011, 28(09): 999-1005.
[5]	丁伟, 孙颖, 吕崇福, 魏继军, 于涛. 单电子转移活性自由基聚合的现状及展望[J]. 应用化学, 2011, 28(03): 245-253.
[6]	张洪涛, 黄锦霞, 江兵兵, 李小琴. 制备单分散交联聚苯乙烯微球共聚合动力学和粒径的研究[J]. 应用化学, 2001, 18(9): 726-730.
[7]	蔡小平, 龚志, 王佛松, 朱行洁, 李秀华. Nd(i－PrO)₂Cl－AlEt₃均相二元催化剂异戊二烯聚合动力学──Ⅲ．AlEt₃的链转移作用[J]. 应用化学, 1996, 0(6): 81-83.
[8]	孙涛, 杨继华, 逄束芬, 欧阳均. 丁二烯在NdCl₃·2Phen-HAl(i-Bu)₂催化体系下的聚合动力学[J]. 应用化学, 1990, 0(1): 80-82.
[9]	毕喜平, 李滨耀, 张东华. 聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究 Ⅱ.强迫互容效应及形态结构[J]. 应用化学, 1988, 0(6): 39-43.
[10]	毕喜平, 李滨耀, 张东华. 聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究 Ⅴ.互穿缠结对相区结构的稳定作用[J]. 应用化学, 1988, 0(5): 53-57.
[11]	周广滨, 许国津, 李晶洁. 丁二烯/甲苯/叔丁氧基钾-正丁基锂体系聚合反应的研究 Ⅱ.反应动力学[J]. 应用化学, 1988, 0(1): 21-26.