The controlled polymerization of methacrylic monomers by nitroxide-mediated polymerization (NMP) still represents a challenge in polymer science. This issue can be circumvented by the addition of a small amount of a comonomer known to exhibit a controlled character in NMP, the most representative example being styrene. The purpose of this work is to explore the use of 4-vinyl pyridine (4VP) as controlling comonomer, while conferring at the same time some functionality to the polymer chains. The NMP of methyl methacrylate (MMA), poly(ethylene glycol) methyl ether methacrylate (PEOMA₉₅₀, M_n = 950 g mol⁻¹) and methacrylic acid (MAA) using a small amount of 4VP under mild experimental conditions (<90 °C, atmospheric pressure), was investigated in this work. The copolymerization of MMA or PEOMA₉₅₀ with 10 mol% 4VP, mediated by the use of the BlocBuilder^® alkoxyamine and a small amount of free nitroxide SG1, exhibited all the features of a controlled system in agreement with the favored incorporation of 4VP at the chain ends, leading to an efficient deactivation of the propagating radicals by the nitroxide SG1. In contrast, the polymerization of MAA was uncontrolled in the same conditions likely due to acid/base interaction between MAA and 4VP, affecting the reactivity of the functional comonomer. Consistently, the copolymerization of MAA with MMA also led to a progressive loss of control as the MAA content in the feed was increased. Among all the polymers synthesized, the P(MMA₇₂-co-4VP₁₀)-SG1 macroalkoyamine was then successfully used to reinitiate the copolymerization of n-butyl methacrylate (BMA) and 4VP both in solution and via dispersion polymerization in a mixture of ethanol and water. Finally, raspberry-like polymer/silica composite particles were prepared through nitroxide-mediated dispersion polymerization performed in the presence of silica nanoparticles, taking benefit of the strong acid-base interaction between 4VP and silica.

通过硝基氧介导的聚合反应（NMP）控制甲基丙烯酸单体的聚合仍然是聚合物科学中的一个挑战。可通过添加少量已知在NMP中表现出受控特性的共聚单体来解决此问题，最典型的例子是苯乙烯。这项工作的目的是探索使用4-乙烯基吡啶（4VP）作为控制共聚单体，同时赋予聚合物链一些功能。甲基丙烯酸甲酯（MMA），聚乙二醇（甲基乙二醇）甲基丙烯酸甲酯（NPE）的NMP（PEOMA ₉₅₀，M _n  = 950 g mol ^-1）和甲基丙烯酸（MAA）在温和的实验条件（<90°C，大气压）下使用少量4VP进行了研究。MMA或PEOMA的共聚₉₅₀与10摩尔％4VP，通过使用BlocBuilder介导^®烷氧基胺和少量游离氮氧化物SG1表现出受控系统的所有特征，与在链端有利于4VP的引入相吻合，从而导致氮氧化物SG1有效地使传播自由基失活。相反，在相同条件下，MAA的聚合不受控制，这可能是由于MAA和4VP之间的酸/碱相互作用，从而影响了功能性共聚单体的反应性。一致地，随着进料中MAA含量的增加，MAA与MMA的共聚也导致控制的逐渐丧失。在合成的所有聚合物中，P（MMA ₇₂ - co -4VP ₁₀）-SG1大烷基胺成功地用于引发n的共聚合。甲基丙烯酸丁酯（BMA）和4VP在溶液中和通过在乙醇和水的混合物中分散聚合而形成。最后，利用4VP和二氧化硅之间强的酸碱相互作用，通过在二氧化硅纳米颗粒存在下进行的由氮氧化物介导的分散聚合制备树莓状聚合物/二氧化硅复合颗粒。