氢键自组装模板辅助作用合成高规整性梯形聚乙烯基倍半硅氧烷
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摘要
微观结构可控的梯形高分子是高分子科学、超分子化学和材料科学的交叉和前沿。本文首先通过“超分子构筑调控逐步偶联／聚合法”以间苯二胺为模板剂，将具有三官能团的有机硅单体偶联成梯形模板单元，然后在间亚苯胺基的氢键作用下水解缩合，得到高度规整的间苯二胺桥基梯形聚乙烯基硅氧烷(Vi-OLPS)。再在其基础上进一步进行缩合反应，通过在弱碱性条件下(TEA为催化剂)分段水解脱撑的方法脱掉间苯二胺桥基，得到梯形聚乙烯基倍半硅氧烷(Vi-T)。所得到的间苯二胺桥基梯形聚乙烯基硅氧烷和梯形聚乙烯基倍半硅氧烷的结构通过FT-IR，XRD，~(29)Si-NMR和DSC进行了表征，结果表明，所合成聚合物具有规整的梯形结构。该聚合物在非线性光学材料以及液晶显示材料等领域有着广泛的应用前景。采用氢键自组装模板辅助作用来合成高度规整梯形聚倍半硅氧烷的方法为今后新型梯形高分子的合成及其功能化提供了一个新的思路。
在成功的合成了梯形聚倍半硅氧烷后，我们又以2，4-二羟基苯甲酸为原料，先与硫酸二甲酯发生甲基化反应得到2，4-二甲氧基苯甲酸；再以SOCl_2为氯化剂，制得了2，4-二甲氧基苯甲酰氯。反应总产率为74.1％。用薄层色谱法(TLC)跟踪反应进程，通过正交实验确定了氯化反应的最佳反应条件。考察了用不同溶剂重结晶时，对产品纯度及产率的影响。2，4-二甲氧基苯甲酰氯可以作为一个反应性官能团接枝在前面所合成的梯形高分子上而增加梯形结构的活性基团，从而更具合成价值。
Research in microstructure-controllable ladderlike polymer is the advanced and interdisciplinary study for polymer science, supramolecular chemistry and material science. In this thesis, a novel high regularity m-phenylenediamino-Bridged Ladder Polyvinylsiloxane (addr. Vi-OLPS) was synthesized successfully by means of Supramolecular architecture-directed stepwise-coupling polymerization. Then ladderlike Polyvinylsiloxane (Vi-T) was prepared by the way of subsection hydrolysis , TEA as the catalyzer, to remove the m-phenylenediamine which act as a template. The structure of the polymer was characterized by FT-IR, X-ray diffraction ~(29)Si-NMR and DSC. The data show that both Vi-OLPS and Vi-T have ordered ladderlike molecular structure. The Vi-T has a comprehensive applied perspective in misalignment optical material and liquid-crystal display material, which provide a novel method to synthesize polymer and make it funtional.
2,4-Dimethoxybenezoyl chloride was prepared by the reaction of 2,4-dihydroxybenezoyl acid, dimethyl sulfate and thionyl chloride by means of methylation and chlorination. The reaction was tracked by thin-layer chromatography(TLC). And the optimal reaction condition of chlorination determined by orthogonal design methods. The influence of several purification methods on the purity and productivity of the products was discussed. The experiment result showed when the method of recrystallization undergone in pertroleum ether (90～120℃) , the total yield reached 74.1%. And the structure of the product was characterized by FT-IR and ~1H-NMR. The 2,4-Dimethoxybenezoyl chloride could inarch to the Vi-T as a reactivity functional group to enhance the activity of the ladder ploymer.
在成功的合成了梯形聚倍半硅氧烷后，我们又以2，4-二羟基苯甲酸为原料，先与硫酸二甲酯发生甲基化反应得到2，4-二甲氧基苯甲酸；再以SOCl_2为氯化剂，制得了2，4-二甲氧基苯甲酰氯。反应总产率为74.1％。用薄层色谱法(TLC)跟踪反应进程，通过正交实验确定了氯化反应的最佳反应条件。考察了用不同溶剂重结晶时，对产品纯度及产率的影响。2，4-二甲氧基苯甲酰氯可以作为一个反应性官能团接枝在前面所合成的梯形高分子上而增加梯形结构的活性基团，从而更具合成价值。
Research in microstructure-controllable ladderlike polymer is the advanced and interdisciplinary study for polymer science, supramolecular chemistry and material science. In this thesis, a novel high regularity m-phenylenediamino-Bridged Ladder Polyvinylsiloxane (addr. Vi-OLPS) was synthesized successfully by means of Supramolecular architecture-directed stepwise-coupling polymerization. Then ladderlike Polyvinylsiloxane (Vi-T) was prepared by the way of subsection hydrolysis , TEA as the catalyzer, to remove the m-phenylenediamine which act as a template. The structure of the polymer was characterized by FT-IR, X-ray diffraction ~(29)Si-NMR and DSC. The data show that both Vi-OLPS and Vi-T have ordered ladderlike molecular structure. The Vi-T has a comprehensive applied perspective in misalignment optical material and liquid-crystal display material, which provide a novel method to synthesize polymer and make it funtional.
2,4-Dimethoxybenezoyl chloride was prepared by the reaction of 2,4-dihydroxybenezoyl acid, dimethyl sulfate and thionyl chloride by means of methylation and chlorination. The reaction was tracked by thin-layer chromatography(TLC). And the optimal reaction condition of chlorination determined by orthogonal design methods. The influence of several purification methods on the purity and productivity of the products was discussed. The experiment result showed when the method of recrystallization undergone in pertroleum ether (90～120℃) , the total yield reached 74.1%. And the structure of the product was characterized by FT-IR and ~1H-NMR. The 2,4-Dimethoxybenezoyl chloride could inarch to the Vi-T as a reactivity functional group to enhance the activity of the ladder ploymer.
引文
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[14] Kyung-Min Kim, Tomoki Ogoshi, Yoshiki Chujo. Controlled polymer hybrids with ladderlike polyphenylsilsesquioxane as a template via the sol-gel reaction of phenyltrimethoxysilane[J]. J. Polym. Sci. Part A: Polym. Chem.: 2005, 43.
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[18] A. Harada, S. Suzyki, J. Li, M. Kamachi, Complex formation between polyisobutylene and cyclodextrins: inversion of chain-length selectivity between.beta.-cyclodextrin and.gamma.-cyclodextrin[J], Macromolecules, 1993, 26: 5267.
[19] Newkome G. R., Yao Z. Q., Baker G. R., Gupta V. K., Cascade molecular: A new approach to micelles[J]. J. Org. Chem., 1985, 50(11): 2003-2004.
[20] Gibson H. W., Marand H., Polyrotaxanes: Molecular composites derived by physical linkkage of cyclic and linear species[J]. Adv. Mater., 1993, 5(1): 11-21.
[21] Vogtle F．著，张希，林志宏泽，超分子化学[M]，吉林，占林大学出版社，1995．
[22] Brown J. F.Jr., Vogt L. H. Jr., Katchman A., Double chain polymers of phenylsil-Sesquioxane[J]. Am. Chem. Soc., 1960, 82(23): 6194-6195.
[23] Ji S. X., Xu H., Zhou X. S., Dai D. R., Zhang R. B., Preparation of a new ladderlike oligosilsesquioxane with lateral aryl ester group[J]. React. Func. Polym., 2002, 50(1): 23-31.
[24] Liu C. Q., Liu Y., Xie P., Zhang R. B., He C. B., Synthesis and characterization of a novel alcohol-soluble ladderlike polysilsesquioxane containing side-chain with amino terminal groups[J]. React. Funct. Polym., 2000, 46(2): 175-184.
[25] Liu C. Q., Liu Z. H., Xie P., Dai D. R., Zhang R. B., Synthesis and characterization of a novel reactive ladderlike polysilsesquioxane with side-chain ester group (Ester-Ts)[J]. Polym. Intern., 2000, 49(2): 509-517.
[26] 张榕本，许辉，谢萍，王乐天，李泽，曹新宁，曹明，戴道荣，有机硅管状高分子复合物及其制备方法，中国专利，CN 97112268．7，1997，7：17．
[27] Scherf U., Ladder-type materials[J]. J. Mater. Chem., 1999, 9: 1853-1864.
[28] Feher, F. J.; Soulivong, D.; Lewis, G.T. Facile framework cleavage reactions of a completely condensed silsesquioxane framework[J]. J Am Chem Soc, 1997, 119(46): 11323-11324.
[29] Unno, M.; Suto, A.; Matsumoto, H. Pentacyclic Laddersiloxane [J]. J Am Chem Soc, 2002, 124: 1574.
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