Stable Free Radical Polymerization in Emulsion: Modeling the Thermodynamics of Monomer Transfer between Droplets and Particles

Jordan Pohn; Catherine Buragina; Michael K. Georges; Barkev Keoshkerian; Michael F. Cunningham

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Stable Free Radical Polymerization in Emulsion: Modeling the Thermodynamics of Monomer Transfer between Droplets and Particles

机译：乳液中稳定的自由基聚合：液滴与颗粒之间单体转移的热力学模型

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A mathematical model is developed from polymer solution thermodynamics and stable free radical polymerization kinetics to predict the monomer swelling behavior of large droplets and small particles that coexist during the seeded polymerization of styrene in emulsion. This model is used to predict the sensitivity of polymerized latex stability (based on the persistence of large particles) to changes in seed particle size and final latex target molecular weight. Simulation results show that the use of small seed particles (diameter50 nm) in recipe formulation will lead to polymerization occurring preferentially in the large droplets, and offers theoretical evidence that TEMPO-mediated ab initio emulsion polymerizations will not be feasible. Our predictions are consistent with experimental evidence suggesting that the presence of large particles leads to the formation of undesirable coagulum in the final product.

机译：从聚合物溶液的热力学和稳定的自由基聚合动力学建立了数学模型，以预测乳液在苯乙烯的种子聚合过程中同时存在的大液滴和小颗粒的单体溶胀行为。该模型用于预测聚合乳胶稳定性（基于大颗粒的持久性）对种子粒径和最终乳胶目标分子量变化的敏感性。模拟结果表明，在配方配方中使用较小的种子颗粒（直径50 nm）将导致大液滴中优先发生聚合反应，并提供了TEMPO介导的从头开始乳液聚合的可行性的理论证据。我们的预测与实验证据一致，表明存在大颗粒会导致最终产品中形成不希望的凝结物。

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《Macromolecular theory and simulations》 |2008年第2期|共13页
作者
Jordan Pohn; Catherine Buragina; Michael K. Georges; Barkev Keoshkerian; Michael F. Cunningham;
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正文语种 eng
中图分类高分子化学（高聚物）;
关键词
molecular weight; polymerized latex; styrene;

机译：分子量;聚合胶乳;苯乙烯;

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专利

1. Stable free radical polymerization in emulsion: Modeling the thermodynamics of monomer transfer between droplets and particles [J] . Pohn J, Buragina C, Georges MK, Macromolecular theory and simulations . 2008,第2a3期

机译：乳液中稳定的自由基聚合：模拟液滴和颗粒之间的单体转移热力学
2. Preparation of size-controlled polymer particles by polymerization of O/W emulsion monomer droplets obtained through phase inversion temperature emulsification using amphiphilic comb-like block polymers [J] . Sasaki Yusuke, Konishi Naho, Kasuya Masakatsu, Colloids and Surfaces, A. Physicochemical and Engineering Aspects . 2015,第Null期

机译：通过使用两亲性梳状嵌段聚合物通过相转化温度乳化获得的O / W乳液单体液滴的聚合来制备尺寸受控的聚合物颗粒
3. Non-equilibrium particle morphology development in seeded emulsion polymerization. 1: penetration of monomer and radicals as a function of monomer feed rate during second stage polymerization [J] . Jeffrey Stubbs, Ola Karlsson, Jan-Eric Jonsson, Colloids and Surfaces, A. Physicochemical and Engineering Aspects . 1999,第1a3期

机译：种子乳液聚合中非平衡颗粒形态的发展。 1：第二阶段聚合过程中单体和自由基的渗透率与单体进料速率的关系
4. Features of Emulsion Polymerization – How Does the Monomer Move from the Droplets into the Latex Particles? [C] . Chunxiang Wei, Klaus Tauer International Workshop on Polymer Reaction Engineering . 2016

机译：乳液聚合的特征 - 单体如何从液滴移动到胶乳颗粒中？
5. "Living"/controlled radical polymerization: From emulsion atom transfer radical polymerization to the synthesis of new nitroxides for stable free radical polymerization. [D] . Chan-Seng, Delphine. 2007

机译：“活性” /受控自由基聚合：从乳液原子转移自由基聚合到合成新的氮氧化物以稳定自由基聚合。
6. A Methodology Towards Mechanical Properties Optimization of Three-Component Polymers by the Gradual Variation of Feed Composition in Semi-Continuous Emulsion-Free Radical Polymerization [O] . Francisco J. Rivera-Gálvez, Luis J. González-Ortiz, Miguel A. López-Manchado, 2019

机译：通过半连续无乳液自由基聚合进料组成的逐步变化实现三组分聚合物力学性能优化的方法学
7. Synthesis of A3B3-type polystyrene–poly(methyl methacrylate) miktoarm star polymers via combination of stable free radical and atom transfer radical polymerization routes [O] . Hakan Durmaz, Sermin Aras, Gurkan Hizal, 2005

机译：通过稳定的自由基和原子转移自由基聚合途径合并A3B3型聚苯乙烯 - 聚（甲基丙烯酸甲酯）miktoarm星聚合物
8. Stereospecificity in the Free Radical Polymerization of Vinyl Acetate (Part Ⅰ). Synthesis of Model Branched Polymers (Part Ⅱ). Thermally Stable Polymers Containing the Triazine Ring (Part Ⅲ). Models of Stereoregular Polymers (Part Ⅳ) [R] . Barbara Boteler, T. G. Fox, Franz Wenger 1959

机译：乙酸乙烯酯自由基聚合的立体特异性（Ⅰ）。模型支化聚合物的合成（Ⅱ）。含三嗪环的热稳定聚合物（第Ⅲ部分）。立体聚合物模型（第四部分）

Stable Free Radical Polymerization in Emulsion: Modeling the Thermodynamics of Monomer Transfer between Droplets and Particles

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