超分子自组装模板辅助的梯形聚硅氧烷的合成
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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。本论文以氢键和电荷转移相互作用为模板，利用超分子自组装的理论，合成了一系列高规整性的梯形聚硅氧烷。主要的研究内容和结果如下：
1. 利用氢键自组装为模板合成了对苯二醌有机桥基梯形聚硅氧烷。在催化剂二环戊二烯二氯化铂（Cp2PtCl2）存在下，通过硅氢加成反应制备了一种对苯二酚桥基偶联的单体。从该单体出发，以对苯二酚中的酚羟基之间的氢键以及硅羟基之间的氢键自组装为模板，先利用“逐步偶联聚合法”，然后再经氧化，合成一种新型的对苯二醌有机桥基梯形聚硅氧烷。通过FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验对其结构进行了表征，结果表明所得到的有机桥基聚硅氧烷具有较高的规整性。
2. 利用醌-氢醌电荷转移相互作用为模板合成了醌-氢醌交替的有机桥基梯形聚有机硅氧烷。由于对苯二酚中的两个酚羟基的推电子作用，使得它具有电子给体的特性。而对苯二醌中的两个羰基的吸电子作用，使得它具有电子受体的特性，所以醌-氢醌之间很容易形成电荷转移络合物，聚合物的形成主要通过水解和缩合两步反应。借助FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, UV, VPO及溶解性实验对其结构进行
了表征。结果可知，由于电荷转移相互作用较弱，得到聚合物的规整性和分子量的大小都略差于氢键自组装合成的聚合物。
3. 利用硅氢加成反应合成了含氰基的硅烷单体，通过“逐步偶联聚合法”，然后经官能团转化，将氰基还原为胺基，合成了含胺基侧基的梯形聚倍半硅氧烷。同时对硅氢加成反应进行了深入的研究。FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验表明合成的梯形聚倍半硅氧烷具有很好的梯形结构。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，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。
Research in microstructure-controllable ladderlike polymer is a forward inter- and multidisciplinary field of polymer science, supra- molecular chemistry and material science. In this thesis, which is based on theory of supramolecular self-assembling, a series of ladderlike polyorganosiloxane was synthesized successfully with the help of H-bonding and charge transfer self-assembling template. The main contents and results of this thesis are shown below.
1. A novel benzoquinone-bridged ladderlike polyorganosiloxane was synthesized with the help of a H-bonding self-assembling template. Hydroquinone organo-bridged monomer was synthesized by hydrosilyla- tion in the presence of dicyclopentadiene platinum dichloride(Cp2PtCl2) catalyst. The benzoquinone-bridged ladderlike polyorganosiloxane was prepared from the monomer by H-bonding of hydroquinone and silicon hydroxy. The whole synthesis process included “Stepwise Coupling Polymerization” and oxidation. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO and solubility test were combined to verify that the structure of the polymer has high ordered ladderlike structure.
2. A quinone-hydroquinone-bridged ladderlike polyorganosiloxane was synthesized successfully by quinone-hydroquinone charge transfer
interaction self-assembling template. Hydroquinone is an electron donor and quinone is an electron acceptor, so charge transfer complex (CTC) is formed easily. The process involved hydrolysis and polycondensation. The structure of the polymer was characterized by FT-IR, 1H-NMR, 29Si-NMR XRD, DSC, UV, VPO and solubility test. All the characterization data indicated that the polymer possessed a less ordered and lower molecular weight than the polymer synthesized by H-bonding self-assembling template.
3. As starting monomer, cyanosiloxane was synthesized by hydrosilylation. A novel kind of ladderlike polysilsesquioxane having side-chain with amino terminal group was prepared by “Stepwise Coupling Polymeri- zation” and reduction of cyano group. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, DSC, XRD, VPO and solubility test were combined to verify that it has ordered ladderlike structure. The obtained soluble ladderlike polymer has promising application in NLO materials, alignment layer in liquid crystal display. This synthetic method paves another new way for synthesis and functionalization of novel ladderlike polymers.
1. 利用氢键自组装为模板合成了对苯二醌有机桥基梯形聚硅氧烷。在催化剂二环戊二烯二氯化铂（Cp2PtCl2）存在下，通过硅氢加成反应制备了一种对苯二酚桥基偶联的单体。从该单体出发，以对苯二酚中的酚羟基之间的氢键以及硅羟基之间的氢键自组装为模板，先利用“逐步偶联聚合法”，然后再经氧化，合成一种新型的对苯二醌有机桥基梯形聚硅氧烷。通过FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验对其结构进行了表征，结果表明所得到的有机桥基聚硅氧烷具有较高的规整性。
2. 利用醌-氢醌电荷转移相互作用为模板合成了醌-氢醌交替的有机桥基梯形聚有机硅氧烷。由于对苯二酚中的两个酚羟基的推电子作用，使得它具有电子给体的特性。而对苯二醌中的两个羰基的吸电子作用，使得它具有电子受体的特性，所以醌-氢醌之间很容易形成电荷转移络合物，聚合物的形成主要通过水解和缩合两步反应。借助FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, UV, VPO及溶解性实验对其结构进行
了表征。结果可知，由于电荷转移相互作用较弱，得到聚合物的规整性和分子量的大小都略差于氢键自组装合成的聚合物。
3. 利用硅氢加成反应合成了含氰基的硅烷单体，通过“逐步偶联聚合法”，然后经官能团转化，将氰基还原为胺基，合成了含胺基侧基的梯形聚倍半硅氧烷。同时对硅氢加成反应进行了深入的研究。FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验表明合成的梯形聚倍半硅氧烷具有很好的梯形结构。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，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。
Research in microstructure-controllable ladderlike polymer is a forward inter- and multidisciplinary field of polymer science, supra- molecular chemistry and material science. In this thesis, which is based on theory of supramolecular self-assembling, a series of ladderlike polyorganosiloxane was synthesized successfully with the help of H-bonding and charge transfer self-assembling template. The main contents and results of this thesis are shown below.
1. A novel benzoquinone-bridged ladderlike polyorganosiloxane was synthesized with the help of a H-bonding self-assembling template. Hydroquinone organo-bridged monomer was synthesized by hydrosilyla- tion in the presence of dicyclopentadiene platinum dichloride(Cp2PtCl2) catalyst. The benzoquinone-bridged ladderlike polyorganosiloxane was prepared from the monomer by H-bonding of hydroquinone and silicon hydroxy. The whole synthesis process included “Stepwise Coupling Polymerization” and oxidation. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO and solubility test were combined to verify that the structure of the polymer has high ordered ladderlike structure.
2. A quinone-hydroquinone-bridged ladderlike polyorganosiloxane was synthesized successfully by quinone-hydroquinone charge transfer
interaction self-assembling template. Hydroquinone is an electron donor and quinone is an electron acceptor, so charge transfer complex (CTC) is formed easily. The process involved hydrolysis and polycondensation. The structure of the polymer was characterized by FT-IR, 1H-NMR, 29Si-NMR XRD, DSC, UV, VPO and solubility test. All the characterization data indicated that the polymer possessed a less ordered and lower molecular weight than the polymer synthesized by H-bonding self-assembling template.
3. As starting monomer, cyanosiloxane was synthesized by hydrosilylation. A novel kind of ladderlike polysilsesquioxane having side-chain with amino terminal group was prepared by “Stepwise Coupling Polymeri- zation” and reduction of cyano group. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, DSC, XRD, VPO and solubility test were combined to verify that it has ordered ladderlike structure. The obtained soluble ladderlike polymer has promising application in NLO materials, alignment layer in liquid crystal display. This synthetic method paves another new way for synthesis and functionalization of novel ladderlike polymers.
引文
[1] Newkome G. R., Yao Z. Q., Baker G. R., Gupta V. K., Cascade molecular: A new approch to micelles, J. Org. Chem., 1985, 50(11), 2003-2004
[2] Gibson H. W., Marand H., Polyrotaxanes: Molecular composites derived by physical linkkage of cyclic and linear species, Adv. Mater., 1993, 5(1), 11-21
[3] Vogtle F. 著, 张希, 林志宏译, 超分子化学, 吉林, 吉林大学出版社, 1995
[4] 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
[5] 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, React. Func. Polym., 2002, 50(1), 23-31
[6] 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, React. Funct. Polym., 2000, 46(2), 175-184
[7] 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), Polym. Intern., 2000, 49(2), 509-517
[8] 张榕本,许辉,谢萍,王乐天,李泽,曹新宇,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, 1997-07-17
[9] Shea K. J., Loy D. A., Webster O., Arylsilsesquioxane gels and related materials: New hybrids of organic and inorganic networks, J. Am. Chem. Soc., 1992, 114(17), 6700-6710
[10] Brown J. F. Jr., Double chain polymers and nonrandom crosslinking, J. Polym. Sci., Part C, 1963, 1, 83-97
[11] Brown J. F. Jr., Vogt L. H. Jr., Prescott P. I., Preparation and characterization of the lower equilibrated phenylsilsesquioxanes, J. Am. Chem. Soc., 1964, 86(6), 1120- 1125
[12] Tsefstkov F., Kuhn length of polyphenylsilsesquioxanes, Vysocomol. Soed., 1968, 10(2), 547-549
[13] Nishijma Y., Characterization of polyphenylsilsesquioxanes by lasers scatter Progress Polym. Phys., Japan, 1966, 9(2), 457-460
[14] Zhang X. S., Shi L. H., Huang C. R., Study on the structure of equilibrated ladderlike phenylsilsesquioxanes, Chinese J. Polym. Sci., 1987, 5(2), 353-356
[15] Evans E. R., Catalyst for producing fluorosilicone polymers, Eur. Pat. EP 317840, 1989-05-31?
[16] Li G. Z., Ye M. L., Shi L. H., Effecton on polymerization condition on the molecular weight of polyphenylsilsisquioxane, Chinese J. Polym. Sci., 1994, 12(4), 331-336
[17] Han S. F., Li Z. J., Sheng X., Dai D. R., Zhang R. B., Zhu C. F., Wang C., Nonlinear optical polymer films based on sol-gel derived polysilsesquioxane with pendant chromophoric subunits embedded in size-matched pores, J. Sol-Gel Sci. Tech, 18(2), 137-144
[18] Rumanis T., Gonga R., Application research on radial crystalline polysiloxane as stationary phase for capllary columegas chromatography. J. Polym. Sci., Part A Polym. Chem., 2001, 39(8), 1743-1746
[19] Li Z. Q., Qin J. G., Li S. J., Ye C., Second-order nonlinear optical property of polysiloxane containing indole-based multifunctional chromophore, Synth. Metal.,
2003, 135(4), 467-468
[20] Andriano K. A., Tsvetkov V. N., Makarova N. N., Vitovskaya M. G., Rjumtsev E. I., Shtennikova I. N., Preparation and characterixation of the phenylsilsesqui- oxanes, Eur. Polym. J., 1973, 9(1), 27-30
[21] Frye C. L., Klosowski J. M., Concerning the so-called “ladderlike structure” of equilibrated phenylsilsesquioxane, J. Am. Chem. Soc., 1971, 93(18), 4599-4601
[22] 谢萍，张榕本，“逐步偶联聚合反应”在研制有序交联高分子及复合物中的应用, 高分子通报, 1997, 4, 203-212
[23] 刘春青，新型梯形及管状聚有机硅氧烷的合成、表征及功能化，中科院化学所博士研究生论文，2000, 42-51
[24] Li Z., Cao X. Y., Xu H., Xie P., Cao M. Zhang R. B., Synthesis and characteri- zation of reactive ladderlike polyallylsilsesquioxane and polyvinylsilsesquioxane, React. Funct. Polym. 1999, 39(1), 1-7
[25] Xu H., Xie P., Zhang R. B., Synthesis and characterization of oligomeric silsesqui- oxane with pendent carboxylic acid groups, Eur. Polym. J., 2001, 37(12), 2397- 2405
[26] Dou Z., Zhong B. L., The Application of ladderlike polysoloxane on the alogn- ment layer for nematic liquid crystals, J. Northwest Univ., 2002, 23(6), 362-368
[27] 谢萍, 李泽, 张榕本，具有液晶相态特征的功能化梯形聚硅氧烷，高分子通报, 1995 , 6, 65-72
[28] Han S. F., Dai D. R., Li Z., Wu G., Zhang R. B., Synthesis of a novel self- assembling NLO polymeric film, Chinese J. Polym. Sci., 1999, 17(5), 417-422
[29] Bernstein J., Davis R. E., Shimoni L., Chang N. L., Patterns in hydrogen bonding: Function and graph set analysis in crystals, Angew. Chem. Int. Ed. Engl., 1995, 34(15), 1555-1573
[30] Sun J., Tang H. D., Jiang J. Q., Xie P., Zhang R. B., Fu P. F., Wu Q., H-bonding assisted template synthesis of a novel ladder-like organo-bridged polymethyl- siloxane, Polymer, 2003, 44(10), 2867-2874
[31] Shea K. J., Sasaki D. Y., On the control of microenvironment shape of function- alized network polymers prepared by template polymerization, J. Am. Chem. Soc., 1989, 111(9), 3442-1444
[32] Fuhrhop J., Bioorganische Chemie, Second Edition, Thieme, Stuttgart, 1982, 55-62
[33] Shea K. J., Choi K. M., Preparation of nano-sized chromium clasters and intimate mixtures of chromium/CdS phases in a porous hybrid xerogel by an internal doping method, J. Am. Chem. Soc., 1994, 116(20), 9052-9062
[34] Trancois B., Self-assembly synthesized microhole film of lithium sulfonate, Adv. Mater., 1995, 7(5), 1041-1048
[35] Seto C. T., Whitesides G. M., Self-assembly of a hydrogen-bonded 2+3 supromole- cular complex, J. Am. Chem. Soc., 1991, 113(2), 713-715
[36] 刘英进, 山本峻三, 末石芳巳, 电荷转移复合物在反应中作用的研究进展, 化学研究与应用, 2000, 12(5), 491-496
[37] 张卫华, 柳士忠, 陈晋阳, 电荷转移配合物的室温固相合成与性质研究, 化学研究与应用, 1999, 11(6), 622-625
[38] 卢建忠，韦寿莲，江云宝，许金钩，分子内扭转电荷转移醇类分子识别功能，科学通报，1997, 42(21), 2300-2303
[39] 宋化灿，有机电荷转移络合物的研究方法及其发展趋势，郑州轻工业学院学报，1995, 10(1), 1-9
[40] 英柏宁，宋化灿，苏镜娱，电荷转移络合物在有机化学中的作用，化学通报，1996, 7, 20-23
[41] Lehn M. J., Rigault A., Helicates: Tetra- and pentanuclear double helix complexes of Cu1 and poly(bipyridine) strands, Angew. Chem. Int. Ed. Engl., 1988, 27(8), 1095-1099
[42] Ashton P. R., Claessens C. G., White W., Williams D. J., Molecular Mosaics Formed by a square cyclophane and its inclusion complex with ferrocene, Angew. Chem. Int. Ed. Engl., 1995, 34(17), 1862-1865
[43] Ogino H., Relatively high-yield synthesis of rotaxanes: Synthesis of cyclodextrins threaded byα,ω-diaminoalkanes coordinated to cobalt(Ш) compounds, J. Am. Chem. Soc., 1981, 103(5), 1303-1304
[44] 汪昆华, 聚合物近代仪器分析, 北京, 清华大学出版社, 1991, 52-60
[45] Feher F. J., Newan D. A., Enhanced silylation reactiving of a model for silica surfaces, J. Am. Chem. Soc., 1990, 112(5), 1931-1936
[46] Bother-By A. A., Stephens R. L., Structure determination of a tetrasaccharide: tromsient nuclear overhauser effects in the rotating frame, J. Am. Chem. Soc.,
1984, 106(3), 811-813
[47] Brinker C. J., Structure determination of tubular polymers prepared by template polymerization, Chem. Mater., 1996, 8(9), 1682-1686
[48] 薛奇，高分子结构研究中的光谱方法，北京，高等教育出版社，1995
[49] 龙英才,姜慧文,曾虹, 用TG/DTG/DTA研究硅沸石与有机分子的主体/客体相互作用, 化学学报，1996, 54(6), 545-553
[50] Shea K. J., Choi K. M., Thermophenomena of nano-side chromium/CdS phases in a mricrofinestra structure, Chem. Mater., 1993, 5(4), 1067-1070
[51] Bremard C., Bougeard D., Study on molecular microstructure by the method of calculation, Adv. Mater., 1995, 7(1), 10-16
[52] Xie Z. S., He Z. Q., Dai D. R., Zhang R. B., Study on the synthesis and characteri- zation of the soluble high molecular weight and ladderlike polymethylsilses quioxane, Chinese J. Polym. Sci., 1989, 7(2), 183-188
[53] Xie Z. S., Dai D. R., Zhang R. B., Synthesis and characterization of the soluble high molecular weight and ladderlike polymethylsilsesquioxane and copolymethyl phenylsilsesquoxane by preamminolysis method, Chinese J. Polym. Sci., 1991, 9(3), 266-272
[54] Xie Z. S., Jin S. Z., Wan Y. Z., Zhang R. B., Synthesis and characterization of the soluble high molecular weight and ladderlike polymethylsilsesquioxane and its copolymers, Chinese J. Polym. Sci., 1992, 10(4), 362-365
[55] Zhang R. B., Xie Z. S., Wan Y. Z., Jin S. Z., Hou J. A., Synthesis and mesomor- phic properties of fishbond-like liquid crystalline polysilsesquioxane: Fishbond- like β-diketone based liquid crystalline polysilsesquioxane and their copper complexes, Chinese J. Polym. Sci., 1993, 11(3), 210-219
[56] Xie P., Guo S. J., Dai D. R., Jin S. Z., Liu D. S., Li Z., Zhang R. B., Synthesis and mesomorphic properties of galley-like liquid crystalline polymethylsiloxane and their metal complexes, Ploym. Adv. Tech., 1996, 7(1), 98
[57] Zhang R. B., Xie Z. S., Wan Y. Z., Side chain liquid crystalline polysiloxanes
containing crown ether and benzyl ethermoieties, Chinese J. Polym. Sci., 1993, 11 (3), 210-217
[58] Xu H., Zheng M., Bai F. L., Dai D. R., Xie P., Zhang R. B., Structure invesrigation of a new polycrganosiloxane containing nanotubular cavities using organic fluorescent probes, Chinese J. Polym. Sci., 1999, 17(4), 383-389
[59] 张榕本，曹新宇，谢萍，李泽，许辉，王乐天，曹明，戴道荣，有机硅管状高分子及其制备方法和用途, 中国专利，CN 97112236.9, 1999-01-27
[60] Apefl M. A., Finkelmann H., Janini G. M., Laub R. J., Luhmann H., Price A., Roberts W. L., Shaw T. J., Smith A., Synthesis and properties of high temperature mesomorphic polysiloxane solvent: Biphenyl- and terphenyl-based nematic systems, Anal. Chem., 1985, 57(3), 651-658
[61] Li Y., Kawakami Y., Efficient synthesis of poly(silyl ether)s by Pd/C catalyzed cross-dehydrocoupling polymerization of bishydrosilanes with diols, Macromol- ecules, 1999, 32(20), 6871-6873
[62] Theodora W. G., Prter G. M., Protective groups in organic synthesis, Second edition, INC, New York, 1991, 143-145
[63] Elizabeth A., Willams, Joseph D., Ronald W. L., Silicon-29 NMR Solvent effect on chemical shifts of silanols and silylamines, J. Organomet. Chem., 1976, 108(1), 153-158
[64] Kensuke N., Tomokazu U., Yoshiki C., Synthesis and properties of alternating acceptor-donor π-conjugated copolymers of cyclodiborazane with dithiafulvene, Macromolecules, 2000, 33(20), 7467-7470
[65] Anelli P. L., Speneer N., Stoddart J. F., A molecular shuttle, J. Am. Chem. Soc., 1991, 113(13), 5131-5133
[66] Prout C. K., Wright J. D., Observation on the crystal structure of electron donor-accepor complexes, Angew. Chem. Int. Ed. Dngl., 1968, 7(9), 659
[67] Speier J. L., Webster J. A., Barne G. H., The addition of silicon hydrides to olefinic double bonds PartⅡ: The use of group metal catalysts, J. Am. Chem. Soc., 1957,
79(4), 574-579
[68] Yang W. T., Ritscher J. S., Method for manufacturing vinylalkoxysilanes. US: 5 041 5952, 1991-10-19
[69] Hu C. Y., Han X. M., Jiang Y. Y., Hydrosilylation of acetytlene catalyzed by a sulfur-containing polysiloxane platinum complex, J. Mol. Catal., 1986, 35(1), 32-34
[70] Speier J. L., Homogeneous catalysis of hydrosilation by transition metals, Adv. Org. Met. Chem., 1979, 17(1), 407-447
[71] Skvortsov N. K., Spevak V. N., Pashnova L. V., Synthesis of hydrosilylation platinum catalyst containing phosphine sulfide ligand, Russ. J. Gen. Chem., 1997, 67(3), 487-490
[72] Jex V. B., Mcmahon J. E., Process for producing cyanoalkysilanes, FR: 1 169 052, 1955
[73] Bank, Howard M., Supported catalysts for addition of silicon hydrides to unstaturated olefinic nitriles, US: 5 126 469, 1952
[74] Bluestein B A. Research in β-Cyanoalkysilanes, US: 2 971 970, 1961
[75] Harada A., Li J., Kamachi M., Preparaton and characterization of a polyrotaxane consisting of monodisperse poly(ethylene glycol) andα-cyclodextrins, J. Am. Chem. Soc., 1994, 116(12), 3192-3196
[76] Liu C. Q., Liu Z. H., Liu Y., Xie P., Zhang R. B., Synthesis and characterization of a novel terephthalate-bridged ladderlike polymethylsiloxnae, Polym. Int., 2000, 49(7), 1658-1664
[2] Gibson H. W., Marand H., Polyrotaxanes: Molecular composites derived by physical linkkage of cyclic and linear species, Adv. Mater., 1993, 5(1), 11-21
[3] Vogtle F. 著, 张希, 林志宏译, 超分子化学, 吉林, 吉林大学出版社, 1995
[4] 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
[5] 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, React. Func. Polym., 2002, 50(1), 23-31
[6] 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, React. Funct. Polym., 2000, 46(2), 175-184
[7] 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), Polym. Intern., 2000, 49(2), 509-517
[8] 张榕本,许辉,谢萍,王乐天,李泽,曹新宇,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, 1997-07-17
[9] Shea K. J., Loy D. A., Webster O., Arylsilsesquioxane gels and related materials: New hybrids of organic and inorganic networks, J. Am. Chem. Soc., 1992, 114(17), 6700-6710
[10] Brown J. F. Jr., Double chain polymers and nonrandom crosslinking, J. Polym. Sci., Part C, 1963, 1, 83-97
[11] Brown J. F. Jr., Vogt L. H. Jr., Prescott P. I., Preparation and characterization of the lower equilibrated phenylsilsesquioxanes, J. Am. Chem. Soc., 1964, 86(6), 1120- 1125
[12] Tsefstkov F., Kuhn length of polyphenylsilsesquioxanes, Vysocomol. Soed., 1968, 10(2), 547-549
[13] Nishijma Y., Characterization of polyphenylsilsesquioxanes by lasers scatter Progress Polym. Phys., Japan, 1966, 9(2), 457-460
[14] Zhang X. S., Shi L. H., Huang C. R., Study on the structure of equilibrated ladderlike phenylsilsesquioxanes, Chinese J. Polym. Sci., 1987, 5(2), 353-356
[15] Evans E. R., Catalyst for producing fluorosilicone polymers, Eur. Pat. EP 317840, 1989-05-31?
[16] Li G. Z., Ye M. L., Shi L. H., Effecton on polymerization condition on the molecular weight of polyphenylsilsisquioxane, Chinese J. Polym. Sci., 1994, 12(4), 331-336
[17] Han S. F., Li Z. J., Sheng X., Dai D. R., Zhang R. B., Zhu C. F., Wang C., Nonlinear optical polymer films based on sol-gel derived polysilsesquioxane with pendant chromophoric subunits embedded in size-matched pores, J. Sol-Gel Sci. Tech, 18(2), 137-144
[18] Rumanis T., Gonga R., Application research on radial crystalline polysiloxane as stationary phase for capllary columegas chromatography. J. Polym. Sci., Part A Polym. Chem., 2001, 39(8), 1743-1746
[19] Li Z. Q., Qin J. G., Li S. J., Ye C., Second-order nonlinear optical property of polysiloxane containing indole-based multifunctional chromophore, Synth. Metal.,
2003, 135(4), 467-468
[20] Andriano K. A., Tsvetkov V. N., Makarova N. N., Vitovskaya M. G., Rjumtsev E. I., Shtennikova I. N., Preparation and characterixation of the phenylsilsesqui- oxanes, Eur. Polym. J., 1973, 9(1), 27-30
[21] Frye C. L., Klosowski J. M., Concerning the so-called “ladderlike structure” of equilibrated phenylsilsesquioxane, J. Am. Chem. Soc., 1971, 93(18), 4599-4601
[22] 谢萍，张榕本，“逐步偶联聚合反应”在研制有序交联高分子及复合物中的应用, 高分子通报, 1997, 4, 203-212
[23] 刘春青，新型梯形及管状聚有机硅氧烷的合成、表征及功能化，中科院化学所博士研究生论文，2000, 42-51
[24] Li Z., Cao X. Y., Xu H., Xie P., Cao M. Zhang R. B., Synthesis and characteri- zation of reactive ladderlike polyallylsilsesquioxane and polyvinylsilsesquioxane, React. Funct. Polym. 1999, 39(1), 1-7
[25] Xu H., Xie P., Zhang R. B., Synthesis and characterization of oligomeric silsesqui- oxane with pendent carboxylic acid groups, Eur. Polym. J., 2001, 37(12), 2397- 2405
[26] Dou Z., Zhong B. L., The Application of ladderlike polysoloxane on the alogn- ment layer for nematic liquid crystals, J. Northwest Univ., 2002, 23(6), 362-368
[27] 谢萍, 李泽, 张榕本，具有液晶相态特征的功能化梯形聚硅氧烷，高分子通报, 1995 , 6, 65-72
[28] Han S. F., Dai D. R., Li Z., Wu G., Zhang R. B., Synthesis of a novel self- assembling NLO polymeric film, Chinese J. Polym. Sci., 1999, 17(5), 417-422
[29] Bernstein J., Davis R. E., Shimoni L., Chang N. L., Patterns in hydrogen bonding: Function and graph set analysis in crystals, Angew. Chem. Int. Ed. Engl., 1995, 34(15), 1555-1573
[30] Sun J., Tang H. D., Jiang J. Q., Xie P., Zhang R. B., Fu P. F., Wu Q., H-bonding assisted template synthesis of a novel ladder-like organo-bridged polymethyl- siloxane, Polymer, 2003, 44(10), 2867-2874
[31] Shea K. J., Sasaki D. Y., On the control of microenvironment shape of function- alized network polymers prepared by template polymerization, J. Am. Chem. Soc., 1989, 111(9), 3442-1444
[32] Fuhrhop J., Bioorganische Chemie, Second Edition, Thieme, Stuttgart, 1982, 55-62
[33] Shea K. J., Choi K. M., Preparation of nano-sized chromium clasters and intimate mixtures of chromium/CdS phases in a porous hybrid xerogel by an internal doping method, J. Am. Chem. Soc., 1994, 116(20), 9052-9062
[34] Trancois B., Self-assembly synthesized microhole film of lithium sulfonate, Adv. Mater., 1995, 7(5), 1041-1048
[35] Seto C. T., Whitesides G. M., Self-assembly of a hydrogen-bonded 2+3 supromole- cular complex, J. Am. Chem. Soc., 1991, 113(2), 713-715
[36] 刘英进, 山本峻三, 末石芳巳, 电荷转移复合物在反应中作用的研究进展, 化学研究与应用, 2000, 12(5), 491-496
[37] 张卫华, 柳士忠, 陈晋阳, 电荷转移配合物的室温固相合成与性质研究, 化学研究与应用, 1999, 11(6), 622-625
[38] 卢建忠，韦寿莲，江云宝，许金钩，分子内扭转电荷转移醇类分子识别功能，科学通报，1997, 42(21), 2300-2303
[39] 宋化灿，有机电荷转移络合物的研究方法及其发展趋势，郑州轻工业学院学报，1995, 10(1), 1-9
[40] 英柏宁，宋化灿，苏镜娱，电荷转移络合物在有机化学中的作用，化学通报，1996, 7, 20-23
[41] Lehn M. J., Rigault A., Helicates: Tetra- and pentanuclear double helix complexes of Cu1 and poly(bipyridine) strands, Angew. Chem. Int. Ed. Engl., 1988, 27(8), 1095-1099
[42] Ashton P. R., Claessens C. G., White W., Williams D. J., Molecular Mosaics Formed by a square cyclophane and its inclusion complex with ferrocene, Angew. Chem. Int. Ed. Engl., 1995, 34(17), 1862-1865
[43] Ogino H., Relatively high-yield synthesis of rotaxanes: Synthesis of cyclodextrins threaded byα,ω-diaminoalkanes coordinated to cobalt(Ш) compounds, J. Am. Chem. Soc., 1981, 103(5), 1303-1304
[44] 汪昆华, 聚合物近代仪器分析, 北京, 清华大学出版社, 1991, 52-60
[45] Feher F. J., Newan D. A., Enhanced silylation reactiving of a model for silica surfaces, J. Am. Chem. Soc., 1990, 112(5), 1931-1936
[46] Bother-By A. A., Stephens R. L., Structure determination of a tetrasaccharide: tromsient nuclear overhauser effects in the rotating frame, J. Am. Chem. Soc.,
1984, 106(3), 811-813
[47] Brinker C. J., Structure determination of tubular polymers prepared by template polymerization, Chem. Mater., 1996, 8(9), 1682-1686
[48] 薛奇，高分子结构研究中的光谱方法，北京，高等教育出版社，1995
[49] 龙英才,姜慧文,曾虹, 用TG/DTG/DTA研究硅沸石与有机分子的主体/客体相互作用, 化学学报，1996, 54(6), 545-553
[50] Shea K. J., Choi K. M., Thermophenomena of nano-side chromium/CdS phases in a mricrofinestra structure, Chem. Mater., 1993, 5(4), 1067-1070
[51] Bremard C., Bougeard D., Study on molecular microstructure by the method of calculation, Adv. Mater., 1995, 7(1), 10-16
[52] Xie Z. S., He Z. Q., Dai D. R., Zhang R. B., Study on the synthesis and characteri- zation of the soluble high molecular weight and ladderlike polymethylsilses quioxane, Chinese J. Polym. Sci., 1989, 7(2), 183-188
[53] Xie Z. S., Dai D. R., Zhang R. B., Synthesis and characterization of the soluble high molecular weight and ladderlike polymethylsilsesquioxane and copolymethyl phenylsilsesquoxane by preamminolysis method, Chinese J. Polym. Sci., 1991, 9(3), 266-272
[54] Xie Z. S., Jin S. Z., Wan Y. Z., Zhang R. B., Synthesis and characterization of the soluble high molecular weight and ladderlike polymethylsilsesquioxane and its copolymers, Chinese J. Polym. Sci., 1992, 10(4), 362-365
[55] Zhang R. B., Xie Z. S., Wan Y. Z., Jin S. Z., Hou J. A., Synthesis and mesomor- phic properties of fishbond-like liquid crystalline polysilsesquioxane: Fishbond- like β-diketone based liquid crystalline polysilsesquioxane and their copper complexes, Chinese J. Polym. Sci., 1993, 11(3), 210-219
[56] Xie P., Guo S. J., Dai D. R., Jin S. Z., Liu D. S., Li Z., Zhang R. B., Synthesis and mesomorphic properties of galley-like liquid crystalline polymethylsiloxane and their metal complexes, Ploym. Adv. Tech., 1996, 7(1), 98
[57] Zhang R. B., Xie Z. S., Wan Y. Z., Side chain liquid crystalline polysiloxanes
containing crown ether and benzyl ethermoieties, Chinese J. Polym. Sci., 1993, 11 (3), 210-217
[58] Xu H., Zheng M., Bai F. L., Dai D. R., Xie P., Zhang R. B., Structure invesrigation of a new polycrganosiloxane containing nanotubular cavities using organic fluorescent probes, Chinese J. Polym. Sci., 1999, 17(4), 383-389
[59] 张榕本，曹新宇，谢萍，李泽，许辉，王乐天，曹明，戴道荣，有机硅管状高分子及其制备方法和用途, 中国专利，CN 97112236.9, 1999-01-27
[60] Apefl M. A., Finkelmann H., Janini G. M., Laub R. J., Luhmann H., Price A., Roberts W. L., Shaw T. J., Smith A., Synthesis and properties of high temperature mesomorphic polysiloxane solvent: Biphenyl- and terphenyl-based nematic systems, Anal. Chem., 1985, 57(3), 651-658
[61] Li Y., Kawakami Y., Efficient synthesis of poly(silyl ether)s by Pd/C catalyzed cross-dehydrocoupling polymerization of bishydrosilanes with diols, Macromol- ecules, 1999, 32(20), 6871-6873
[62] Theodora W. G., Prter G. M., Protective groups in organic synthesis, Second edition, INC, New York, 1991, 143-145
[63] Elizabeth A., Willams, Joseph D., Ronald W. L., Silicon-29 NMR Solvent effect on chemical shifts of silanols and silylamines, J. Organomet. Chem., 1976, 108(1), 153-158
[64] Kensuke N., Tomokazu U., Yoshiki C., Synthesis and properties of alternating acceptor-donor π-conjugated copolymers of cyclodiborazane with dithiafulvene, Macromolecules, 2000, 33(20), 7467-7470
[65] Anelli P. L., Speneer N., Stoddart J. F., A molecular shuttle, J. Am. Chem. Soc., 1991, 113(13), 5131-5133
[66] Prout C. K., Wright J. D., Observation on the crystal structure of electron donor-accepor complexes, Angew. Chem. Int. Ed. Dngl., 1968, 7(9), 659
[67] Speier J. L., Webster J. A., Barne G. H., The addition of silicon hydrides to olefinic double bonds PartⅡ: The use of group metal catalysts, J. Am. Chem. Soc., 1957,
79(4), 574-579
[68] Yang W. T., Ritscher J. S., Method for manufacturing vinylalkoxysilanes. US: 5 041 5952, 1991-10-19
[69] Hu C. Y., Han X. M., Jiang Y. Y., Hydrosilylation of acetytlene catalyzed by a sulfur-containing polysiloxane platinum complex, J. Mol. Catal., 1986, 35(1), 32-34
[70] Speier J. L., Homogeneous catalysis of hydrosilation by transition metals, Adv. Org. Met. Chem., 1979, 17(1), 407-447
[71] Skvortsov N. K., Spevak V. N., Pashnova L. V., Synthesis of hydrosilylation platinum catalyst containing phosphine sulfide ligand, Russ. J. Gen. Chem., 1997, 67(3), 487-490
[72] Jex V. B., Mcmahon J. E., Process for producing cyanoalkysilanes, FR: 1 169 052, 1955
[73] Bank, Howard M., Supported catalysts for addition of silicon hydrides to unstaturated olefinic nitriles, US: 5 126 469, 1952
[74] Bluestein B A. Research in β-Cyanoalkysilanes, US: 2 971 970, 1961
[75] Harada A., Li J., Kamachi M., Preparaton and characterization of a polyrotaxane consisting of monodisperse poly(ethylene glycol) andα-cyclodextrins, J. Am. Chem. Soc., 1994, 116(12), 3192-3196
[76] Liu C. Q., Liu Z. H., Liu Y., Xie P., Zhang R. B., Synthesis and characterization of a novel terephthalate-bridged ladderlike polymethylsiloxnae, Polym. Int., 2000, 49(7), 1658-1664