The grafting of (functionalized) polystyrene from bulk or surface-functionalized polyolefins via nitroxide mediated polymerization is described. High density polyethylene and a poly(ethylene-co-α-olefin) copolymer (EOC) modified with different functional 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) derivatives were used as macroinitiators for the “grafting from” polymerization of various styrene-based monomers to yield polyolefin-g-polystyrene graft copolymers. The successful grafting of styrene and styrene derivatives was demonstrated by complementary analyses such as infrared (ATR-FTIR) and NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, and differential scanning calorimetry. Typically, IR spectroscopy of the grafted copolymers showed the bands attributable to the aromatic moieties and the obtained thermograms evidenced a lower degradation temperature for the grafted copolymers compared to that of polyolefin starting materials. In addition, solid state ¹⁹F-NMR was chosen to confirm the growth of polystyrene (PS) chains when EOC functionalized with a fluoroalkyl TEMPO was used for NMP. The extent of grafting of PS chains onto the polyolefin backbone was found to depend on the nature of the macroinitiator, especially on the structure and cleavage temperature of alkoxyamine derivatives created by TEMPO functionalization, on its content and on the adopted experimental conditions.

中文翻译：

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苯乙烯和取代的苯乙烯接枝的功能性聚烯烃，通过一氧化氮介导的聚合反应†

描述了通过氮氧化物介导的聚合从本体或表面官能化的聚烯烃接枝（官能化的）聚苯乙烯。高密度聚乙烯和经不同官能的2,2,6,6-四甲基哌啶-1-氧基自由基（TEMPO）衍生物改性的聚（乙烯-共-α-烯烃）共聚物（EOC）被用作大分子引发剂，用于“接枝自”各种苯乙烯类单体的聚合反应，得到聚烯烃克-聚苯乙烯接枝共聚物。通过互补分析（例如红外（ATR-FTIR）和NMR光谱，尺寸排阻色谱，热重分析和差示扫描量热法）证明了苯乙烯和苯乙烯衍生物的成功接枝。通常，接枝共聚物的IR光谱显示出归因于芳族部分的谱带，并且所获得的热谱图证明与聚烯烃起始材料相比，接枝共聚物的降解温度更低。此外，固态¹⁹选择F-NMR以确认当用氟烷基TEMPO官能化的EOC用于NMP时，聚苯乙烯（PS）链的生长。发现PS链接枝到聚烯烃主链上的程度取决于大分子引发剂的性质，尤其取决于TEMPO官能化产生的烷氧基胺衍生物的结构和裂解温度，其含量和所采用的实验条件。