适配双链与非适配单链包结γ-CD聚准轮烷嵌段共聚物合成与表征
发布时间：2019-03-31 14:36
【摘要】：首先在精准控制摩尔投料比条件下,通过缓慢加料方式制备出以2-溴异丁酰基为端基的双三缩四乙二醇偶氮苯二甲酸酯(Br-EG_4-AZO-EG_4-Br,1)作为引发剂,然后在[γ-CD]/[1]=4的条件下,将1与γ-环糊精(γ-CD)在水溶液中进行自组装制备得到双链包结聚准轮烷(i PPR),进而用该聚准轮烷原位引发N-异丙基丙烯酰胺(NIPAAm)进行原子转移自由基聚合(ATRP)得到聚准轮烷嵌段共聚物(PPRs).分析结果表明,该类共聚物以γ-CD与偶氮苯和折叠三缩四乙二醇链自组装形成的适配双链包结结构的形式存在,而在与由1引发NIPAAm进行ATRP聚合所制备的PNIPAAm-EG_4-AZO-EG_4-PNIPAAm进行自组装包结时,γ-CD则均匀分布在整条共聚物链上生成非适配单链包结聚准轮烷嵌段共聚物(a PPRs).与引发剂1和a PPRs相比,PPRs中代表反式偶氮苯基团的紫外吸收峰发生明显红移,但紫外光照射产生的顺式异构化几乎不导致γ-CD滑脱下链,说明γ-CD与偶氮苯和折叠三缩四乙二醇包结形成的适配双链包结结构不仅稳定性高,而且还能可逆地转化为γ-CD与双三缩四乙二醇链包结形式的适配双链包结结构.
[Abstract]:At first, bis-triethyleneglycol azophthalate (Br-EG_4-AZO-EG_4-Br,1) with 2-bromoisobutyryl group as terminal group was prepared by slow feeding method under the condition of accurate and controlled molar ratio, which was used as initiator. Then, under the condition of [纬-CD] / [1] = 4, the self-assembly of 1 and 纬-cyclodextrin (纬-CD) was carried out in aqueous solution to prepare double-stranded inclusion poly (quasi-rotane) (i PPR),. Then the poly (quasi-rotane) block copolymer (PPRs). Was synthesized by atom transfer radical polymerization (ATRP) with N-isopropylacrylamide (NIPAAm) initiated by the in-situ initiation of the poly (quasi-rotane). The results show that the copolymer exists in the form of self-assembly of 纬-CD with azobenzene and folded triethyleneglycol chains. On the other hand, when self-assembled with PNIPAAm-EG_4-AZO-EG_4-PNIPAAm prepared by ATRP polymerization of 1-initiated NIPAAm, 纬-CD homogeneously distributed over the whole chain of copolymers to form unsuitable single-stranded inclusion copolymers of quasi-rotane block copolymers (a PPRs). Compared with initiators 1 and a PPRs, the UV absorption peaks representing trans-azobenzene groups in PPRs showed a significant red shift, but the cis-isomerization produced by UV irradiation did not lead to the slippage of 纬-CD. The results show that the suitable double-stranded inclusion structure formed by 纬-CD with azobenzene and folded triethyleneglycol not only has high stability, but also can be inversely transformed into a suitable double-stranded structure in the form of 纬-CD and double triethyleneglycol entrapment.
【作者单位】： 北京理工大学材料学院;
【分类号】：O631
[Abstract]:At first, bis-triethyleneglycol azophthalate (Br-EG_4-AZO-EG_4-Br,1) with 2-bromoisobutyryl group as terminal group was prepared by slow feeding method under the condition of accurate and controlled molar ratio, which was used as initiator. Then, under the condition of [纬-CD] / [1] = 4, the self-assembly of 1 and 纬-cyclodextrin (纬-CD) was carried out in aqueous solution to prepare double-stranded inclusion poly (quasi-rotane) (i PPR),. Then the poly (quasi-rotane) block copolymer (PPRs). Was synthesized by atom transfer radical polymerization (ATRP) with N-isopropylacrylamide (NIPAAm) initiated by the in-situ initiation of the poly (quasi-rotane). The results show that the copolymer exists in the form of self-assembly of 纬-CD with azobenzene and folded triethyleneglycol chains. On the other hand, when self-assembled with PNIPAAm-EG_4-AZO-EG_4-PNIPAAm prepared by ATRP polymerization of 1-initiated NIPAAm, 纬-CD homogeneously distributed over the whole chain of copolymers to form unsuitable single-stranded inclusion copolymers of quasi-rotane block copolymers (a PPRs). Compared with initiators 1 and a PPRs, the UV absorption peaks representing trans-azobenzene groups in PPRs showed a significant red shift, but the cis-isomerization produced by UV irradiation did not lead to the slippage of 纬-CD. The results show that the suitable double-stranded inclusion structure formed by 纬-CD with azobenzene and folded triethyleneglycol not only has high stability, but also can be inversely transformed into a suitable double-stranded structure in the form of 纬-CD and double triethyleneglycol entrapment.
【作者单位】： 北京理工大学材料学院;
【分类号】：O631
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