Synthesis of Core Cross-Linked Star Polymers Consisting of Well-Defined Aromatic Polyamide Arms
Synthesis of Core Cross-Linked Star Polymers Consisting of Well-Defined Aromatic Polyamide Arms
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DOI：
10.1021/ma902412t
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发表时间：
2010-04-13
期刊：
影响因子：
5.5
通讯作者：
Yokozawa, Tsutomu
中科院分区：
文献类型：
--
作者：
Ohishi, Tomoyuki;Masukawa, Tomohiro;Yokozawa, Tsutomu
采用核交联法合成了由聚(N-辛基-间-苯甲酰胺)和聚(N-H-间-苯甲酰胺)组成的均聚物臂、嵌段臂和米克托臂星形聚合物。以4-乙烯基苯甲酸苯酯为引发剂，通过3-(烷基氨基)苯甲酸酯1的链增长缩聚合成了具有苯乙烯基末端的大分子单体(MM)，并在2,2'-偶氮双(异丁腈)存在下与N,N'-亚甲基双(丙烯酰胺)作为二乙烯基单体在60℃下共聚，得到相应的星形单体。聚合物。在含有聚(N-H-间-苯甲酰胺)臂的星形聚合物的合成中，用三氟乙酸去除所得星形聚合物的酰胺氮上的4-(辛氧基)苄基。通过多角度激光散射测定的每个分子的臂数在36-100的范围内变化，具体取决于1的N-烷基和MM的分子量。星形聚合物在二甲基亚砜中的 H-1 NMR 谱表明，嵌段臂和米克托臂星形聚合物的聚（N-辛基-间苯甲酰胺）链段和臂分别在室温下紧密堆积，并在较高温度下变得延伸。
Homopolymer-arm, block-arm, and miktoarm star polymers consisting of poly(N-octyl-m-benzamide) and poly(N-H-m-benzamide) were synthesized by means of a core cross-linking method. Macromonomers (MM) with the styryl terminal moiety were synthesized by chain-growth condensation polymerization of 3-(alkylamino)benzoic acid esters 1 in the presence of phenyl 4-vinylbenzoate as an initiator, and copolymerization with N,N'-methylenebis(acrylamide) as a divinyl monomer in the presence of 2,2'-azobis(isobutyronitrile) at 60 degrees C yielded the corresponding star polymers. In the synthesis of star polymers containing poly(N-H-m-benzamide) arms, the 4-(octyloxy)benzyl group on the amide nitrogen of the obtained star polymers was removed with trifluoroacetic acid. The number of arms per molecule, determined by multiangle laser light scattering, varied in the range of 36-100 depending on the N-alkyl group of 1 and the molecular weight of MM. The H-1 NMR spectra of the star polymers in dimethyl sulfoxide revealed that the poly(N-octyl-m-benzamide) segments and arms of the block-arm and miktoarm star polymers, respectively, were compactly packed at room temperature and became extended at higher temperatures.