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摘要
通过电子转移活化再生催化剂原子转移自由基聚合法(ARGET ATRP)依次聚合单体甲基丙烯酸甲酯(MMA)和甲基丙烯酸-2,2,6,6-四甲基-4-哌啶基酯(TMPM),制得嵌段共聚物PMMA-PTMPM,再用3-氯过氧苯甲酸(mCPBA)将TMPM中的哌啶基氧化为2,2,6,6-四甲基哌啶氮氧自由基(TEMPO),得到负载链段为聚甲基丙烯酸甲酯的氮氧自由基嵌段共聚物PMMA-PTMA。通过红外光谱、核磁共振波谱、紫外可见分光光度计和凝胶渗透色谱等手段对共聚物进行表征。研究了嵌段共聚物在分子氧氧化体系下对伯醇的选择性催化氧化性能,并与均聚物PTMA和负载链段为聚乙二醇的氮氧自由基嵌段共聚物PEG-PTMA进行比较。结果表明,嵌段共聚物在分子氧氧化体系中催化性能良好,整体性能优于PTMA和PEG-PTMA,并且嵌段共聚物回收方便,可以实现重复使用。
Abstract
The methyl methacrylate (MMA) and 2,2,6,6-tetramethylpiperidyl methacrylate (TMPM) monomers are sequentially polymerized to prepare block copolymer PMMA-PTMPM via the activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) method.The piperidinyl in TMPM is oxidized to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) by 3-chloroperoxybenzoic acid (mCPBA),and a nitroxide radical block copolymer PMMA-PTMA with PMMA as support segment is obtained.The copolymer is characterized by infrared spectroscopy,nuclear magnetic resonance spectroscopy,ultraviolet-visible spectrophotometer and gel permeation chromatography.The properties of block copolymer in the selective catalytic oxidation of benzyl alcohol in the molecular oxygen oxidation system are studied,and compared with those of the homopolymeric PTMA and the nitroxide radical block copolymer PEG-PTMA with polyethylene glycol as support segment.The results show that the block copolymer exhibits excellent catalytic properties in the molecular oxygen oxidation system and has a better overall performance than PTMA and PEG-PTMA.Furthermore,the block copolymer can be easily recycled for reusing.
关键词
嵌段共聚物
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催化氧化
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分子氧
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氮氧自由基
Key words
block copolymer
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catalytic oxidation
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molecular oxygen
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nitroxide radical
Author summay
崔笑菲(1993-),女,硕士研究生,主要从事功能高分子材料制备,506748147@qq.com
PMMA-PTMA的合成及其催化分子氧氧化苯甲醇[J].
, 2018, 38(1): 80-83 DOI:10.16606/j.cnki.issn0253-4320.2018.01.018