Poly(alkyl methacrylate)s (alkyl = methyl, ethyl, n-butyl and n-hexyl) synthesized by Atom Transfer Radical Polymerization (ATRP) using 2,2,2 tribromoethanol as initiator present a first mass loss below 200 °C in thermogravimetric experiments. In order to investigate the possible mechanism of this degradation step, the polymers were subjected to thermal treatment at 150 °C under argon atmosphere. The volatiles were analyzed by gas chromatography coupled to mass spectrometry, while the thermally treated polymers were analyzed by thermogravimetry, ¹H and ¹³C nuclear magnetic resonance and size exclusion chromatography. The main mechanism of the first step of degradation is HBr elimination from initiator fragments attached to the chain ends, resulting in vinylidene, lactone and aldehyde terminal groups of the polymer chains. Moreover, volatiles produced by the chain-end elimination were mainly alkyl bromides, alkyl alcohols, alkyl methacrylates and products successive to HBr elimination and polymer chain scission. The amount of monomer release at 150 °C varied with the alkyl group in the range of 3–17 wt %; however, polymer chain configuration, molar mass and dispersity did not significantly change. Polymer chains free of the ATRP initiator were thermally stable at least up to 250 °C.

使用2,2,2三溴乙醇作为引发剂通过原子转移自由基聚合（ATRP）合成的聚（甲基丙烯酸烷基酯）（烷基=甲基，乙基，正丁基和正己基）在热重分析中出现低于200°C的首次质量损失实验。为了研究该降解步骤的可能机理，将聚合物在氩气氛下于150℃进行热处理。通过气相色谱-质谱联用分析挥发物，同时通过热重分析（¹ H和^13）分析热处理过的聚合物C核磁共振和尺寸排阻色谱法。降解第一步的主要机理是从连接在链端的引发剂片段中除去HBr，从而形成聚合物链的亚乙烯基，内酯和醛端基。而且，通过链端消除产生的挥发物主要是烷基溴化物，烷基醇，甲基丙烯酸烷基酯和继HBr消除和聚合物断链之后的产物。在150°C下，单体的释放量随烷基的3-17 wt％范围而变化。但是，聚合物链的构型，摩尔质量和分散度没有明显变化。不含ATRP引发剂的聚合物链在至少250°C的温度下具有热稳定性。