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含五苯基吡咯侧基聚丙烯酸酯的制备及其聚集诱导发光增强性能
  • ISSN号:1000-3304
  • 期刊名称:《高分子学报》
  • 时间:0
  • 分类:O626.13[理学—有机化学;理学—化学]
  • 作者机构:[1]北京理工大学化学学院,北京100081, [2]北京理工大学材料学院,北京100081
  • 相关基金:国家自然科学基金(基金号21374010)资助项目
中文摘要:

设计合成了具有聚集诱导发光增强活性(AEE)的含五苯基吡咯的甲基丙烯酸酯单体M-PPP,并通过自由基聚合制备了系列均聚物及不同五苯基吡咯侧基含量的聚甲基丙烯酸酯共聚物.所制备的均聚物P与共聚物CP在THF/H2O体系中均具有AEE特性,在水含量大于20%时荧光开始增加,大于80%时荧光快速增加,95%时相对荧光强度达到最大;单体M-PPP则在水含量低于70%时荧光强度略有降低,随后迅速增加,95%后荧光强度下降.五苯基吡咯侧基含量较高的共聚物表现出更好的AEE特性.进一步的研究发现,共聚物CP在THF/H2O混合溶液中能够对赖氨酸产生荧光点亮型响应.

英文摘要:

Methacrylate monomer M-PPP,which is aggregation-enhanced emission(AEE)active and with a conjugated pentaphenylpyrrole side group,was designed and synthesized through palladium-catalyzed cyclization of arylamine and diaryl acetylene,Suzuki cross-coupling and esterification with EDCI as dehydrant.A series of homopolymers P_1,P_2,P_3 and copolymers CP_(41),CP_(21),CP_(11),CP_(12),CP_(14) were prepared by free radical polymerization of M-PPP and copolymerization of M-PPP with BMA.The molar ratio of M-PPP unit and BMA unit in copolymers CPs was calculated based on the chemical shift and integrations of their CH_2 groups.The content of M-PPP units in the copolymers was lower than those in raw materials,mainly due to the low polymerization activity attributed to the bulky conjugated pentaphenylpyrrole side group.The monomer M-PPP,the polymers P_1,P_2,P_3 and the copolymers CP_(41),CP_(21),CP_(11) were of high thermal stability with their decomposition temperature above 300°C,while the decomposition temperatures of CP_(12),CP_(14) decreased slightly because of the lower content of the conjugated pentaphenylpyrrole side group.Both the monomer M-PPP and the polymers exhibited obvious AEE feature in THF/H_2O mixture.The fluorescence intensity of the polymers increased slowly when the water fraction(f w)was above 20%,and it increased faster when fw is above 80%.The relative fluorescence intensity(I/I0)reached to a maximum at f w of 95%,mainly attributed to the aggregation of the conjugated luminogen pentaphenylpyrrole segment in the side-chain and the entanglement of the flexible polymer main chains in THF/H_2O mixture,which could restrict the motion of pentaphenylpyrrole and intramolecular rotation of the benzene rings,leading to enhanced fluorescence emission.The fluorescence intensity of M-PPP decreased a little when fw was lower than 70%,then increased sharply,and the maximal I/I0 was 3.9 at fw of 95%,which was higher than those of the polymers due to the lower content

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期刊信息
  • 《高分子学报》
  • 中国科技核心期刊
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院化学研究所
  • 主编:张希
  • 地址:北京市海淀区中关村北一街2号
  • 邮编:100190
  • 邮箱:gfzxb@iccas.ac.cn
  • 电话:010-62588927
  • 国际标准刊号:ISSN:1000-3304
  • 国内统一刊号:ISSN:11-1857/O6
  • 邮发代号:2-498
  • 获奖情况:
  • 国家优秀期刊二等奖,中科院优秀期刊二等奖,中国科协优秀期刊
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),英国高分子图书馆,日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),中国北大核心期刊(2000版)
  • 被引量:19174