高等学校化学学报

高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (3): 418.

• 论文 • 上一篇    下一篇

聚芳醚酮在溶液中的分子构象与分子极化

柯杨船, 封继康, 任爱民, 郑玉斌, 吴忠文   

  1. 吉林大学化学系, 长春, 130023
  • 收稿日期:1996-05-13 出版日期:1997-03-24 发布日期:1997-03-24
  • 通讯作者: 封继康.
  • 作者简介:柯杨船, 男, 30岁, 博士, 讲师.
  • 基金资助:

    国家“863”项目;国家自然科学基金

Conformation and Polarization for Monodisperse Oligomers and Polymers of Poly(aryl ether ketone)s in Solution

KE Yang-Chuan, FENG Ji-Kang, REN Ai-Min, ZHENG Yu-Bin, WU Zhong-Wen   

  1. Department of Chemistry, Jilin University, Changchun, 130023
  • Received:1996-05-13 Online:1997-03-24 Published:1997-03-24

PDF (PC)

摘要： 经从头计算,得到4,4'-二氟苯酮二面角为44°,MES3二面角为51°;用UV光谱法研究了单分散齐聚物在H2SO4中的分子构象与极化,结果表明:H2SO4使碳基质子化是产生极化的主要因素之一,由此产生的新吸收峰在λ=400nm左右;极化作用产生的平面构象经重叠后在λ=500nm左右产生另一新的吸收峰.由质子化模型并考虑组态相互作用的计算结果与文献一致.证明了聚芳醚酮高聚物在H2SO4中,于400nm左右处产生的峰(UV)为羰基极化的结果,指明在H2SO4中测其分子量时应按羰基含量校正.

关键词: 构象, 质子化, 极化, 组态相互作用计算

Abstract: By means of ab initio method the dihedral angle of 44° for 4, 4' -difluorobenzophenone and of 51° for MES3 are obtained.UVspectra frorn monodisperse oligomers and their molecular polarization in H2SO4 show that the protonation of H2SO4 acting on carbonyl group is one of the major factors of the polarization.The protonation produces a new absorption peak at λ=4OOnm or so (UV); Meanwhile, the overlapping of planar conformation from polarization produces another new absorption peak at λ=500 nm.Based on the protonation model, the configuration interaction(CI) calculation on it is made, the results of which are ln good agreement with those from experiment.All these prove that the absorption peak at λ=4OOnm for poly (aryl ether ketone)s is resulted from carbonyl polarization.Thus, the polymer molecular weight measured in H2SO4 should be corrected according to ketone content in the main chain.

Key words: Conformation, Protonation, Polarization, Configuration interaction calculation

TrendMD: