高分子聚集和解聚的研究-高分子物理与化学专业论文.docxVIP

摘费 中国科学技术火学博‘J?学位论文 量(％卿)，均表现出了滞后效应。加热过程中当温度低于PNIPAM的LCST(～32。C) 时，在分子问聚集前PNIPAM分子链首先进行分子内的塌缩。冷却过程中，当温 度降到LCST时，弘。聊保持不变，Rg5}NRhM时增大。然而，它们的比值Rg IR^减小。这表明，聚集体的溶胀过程并非均匀的，聚集体的表面比内部先溶胀， 而不会解聚。FTIR光谱表明，随温度升高，C--O D—O．D的吸收峰强度降低， C=O H-N的吸收峰在高于LCST的温度出现，并且逐渐增强。这说明在加热过 程中脱水和额外氢键在塌缩态出现。链的收缩是熵驱动的。由于额外的氢键如同 “交联点”，使聚集体就像“凝胶”一样，导致了滞后效应的产生。必须在温度远 低于LCST(～2 oC)，我们才‘能观察到解聚过程。 我们在温敏性的高分子刷的塌缩一溶胀实验中也观察到这种因为氢健形成而 产生的滞后效应。 用表面引发的方法，将异丙基丙烯酰胺与丙烯酸钠无规共聚的高分子刷接枝 到二氧化硅改性的石英晶体表面。进而用微石英天平来观察温敏的高分子刷在水 中的塌缩和溶胀过程。频率和耗散因子在20．38。C之间随温度的变化显示：高分 子刷经历了连续的塌缩过程。我们的结果表明：高分子刷塌缩到了它制备过程中 的状态，也就是说高分子刷具有“记忆”功能，能够记忆之前的塌缩状态。在冷 却过程中我们观察到滞后现象。FTIR证实了高分子链塌缩过程中形成的额外氢键 导致了滞后效应。  Abstract The aggregation and association behaviors in polymer solution or dispersion have attracted much attention．This is partially due to their practical importance in colloid science(stability)，metallurgy(phase seperation)，biology(growth of tumors)，and also partially due to the shortage of our knowledge about these fascination phenomena Basically,there exist two kinds of distinct regime；namely，diffusion limited cluster aggregation(DLCA)and reaction limited cluster aggregation(RLCA)in the aggregation process in dispersion Using thermally—induced controllable association of narrowly distributed spherical poly(vinyl caprolactam—CO—sodium acrylate)(PVCL—CO—PSA)microgels in the presence of c5++as a model system．we studied the reversible aggregation near the lower critical dispersion temperature(LCDT～3 5 oC)．We found that when such an aggregation is a diffusion limited process，it is usually governed by a second—order aggregation and a first—order fragmentation kinetics．The aggregation and fragmentation rates strongly depend on the dispersion temperature．The final ratio of the two rates approaches one， indicating that there exists a dynamic equilibrium between the two opposite processes． The intermediate regime between DLCA and RLCA was also examined in the system．We found the increase of temperature，as well as