芴类偶氮聚炔高分子材料的合成及性能研究
|
摘要
目前，偶氮苯聚合物在光信息存储材料、非线性光学材料、液晶材料、生物活性光控制及纳米材料等领域都有重要的应用价值。偶氮型聚合物正成为功能高分子材料的一前沿课题,展现出广泛的应用前景,特别是在光致变色方面的应用。鉴于偶氮苯聚合物的重要研究应用,本文合成了四种新型的端炔基含芴偶氮苯衍生物小分子和三个含芴偶氮苯聚炔高分子,对其结构进行了表征,并对它们光学性能及热性能进行了研究。论文的主要工作如下：
1.简要综述了聚炔及其衍生物、偶氮苯聚合物、芴类衍生物的研究进展。
2.设计并合成了四个新的目标单体分子。并且利用FTIR和1H NMR对化合物的结构进行了确定和表征。
3.选择3个单体以均聚方式在[Rh(nbd)Cl]2-Et3N催化下成功地合成了含芴偶氮苯聚炔共轭高分子,通过红外、核磁对聚合物结构进行了表征。
4.对单体和聚合物的紫外吸收光谱进行了研究,发现聚合物的最大吸收峰与单体相比发生了红移,这可能是聚合物主链共轭结构的贡献。
5.利用TGA和DSC对单体和聚合物进行了热性能的研究,发现聚合物较单体具有较高的热稳定性。
At present, the azobenzene polymer are very useful in optical information storage materials, nonlinear optical materials, liquid crystalline materials, bioactive light control and nanomaterials, etc. Azobenzene polymer are becoming a new frontier in functional polymer materials, and show a broad application prospect, especially in the photochromic applications. In view of the significant application of the azobenzene polymer, four new fluorene-type azobenzene with a terminal propargyl functional group small molecule compounds, and three fluorene-type azobenzene polyacetylenes were synthesized and characterized by FT-IR and1H-NMR. Their thermal properties and optical properties were also investigated. The main contents of this thesis include the following points:
1. The development of polyacetylenes and their derivatives, azobenzene polymers, and fluorene and its derivatives were reviewed briefly.
2. Four new fluorene derivatives were designed and synthesized, and their structures were characterized by FT-IR and1H-NMR.
3. Three fluorene-type homopolymer with azobenzene polypropargyl functional group were designed and synthesized using [Rh(nbd)Cl]2-Et3N as catalyst, and their structures were characterized by FT-IR and1H-NMR.
4. The UV-vis absorption spectra of the monomers and polymers were studied, and the results showed that the maximum absorption peak of the polymer occurred red shift compared with their monomers, and it probably because the influence of the highly conjugated structure of the polymer.
5. The TGA and DSC of the monomer and polymer were investigated. The results showed that the polymer had good thermal stability.
1.简要综述了聚炔及其衍生物、偶氮苯聚合物、芴类衍生物的研究进展。
2.设计并合成了四个新的目标单体分子。并且利用FTIR和1H NMR对化合物的结构进行了确定和表征。
3.选择3个单体以均聚方式在[Rh(nbd)Cl]2-Et3N催化下成功地合成了含芴偶氮苯聚炔共轭高分子,通过红外、核磁对聚合物结构进行了表征。
4.对单体和聚合物的紫外吸收光谱进行了研究,发现聚合物的最大吸收峰与单体相比发生了红移,这可能是聚合物主链共轭结构的贡献。
5.利用TGA和DSC对单体和聚合物进行了热性能的研究,发现聚合物较单体具有较高的热稳定性。
At present, the azobenzene polymer are very useful in optical information storage materials, nonlinear optical materials, liquid crystalline materials, bioactive light control and nanomaterials, etc. Azobenzene polymer are becoming a new frontier in functional polymer materials, and show a broad application prospect, especially in the photochromic applications. In view of the significant application of the azobenzene polymer, four new fluorene-type azobenzene with a terminal propargyl functional group small molecule compounds, and three fluorene-type azobenzene polyacetylenes were synthesized and characterized by FT-IR and1H-NMR. Their thermal properties and optical properties were also investigated. The main contents of this thesis include the following points:
1. The development of polyacetylenes and their derivatives, azobenzene polymers, and fluorene and its derivatives were reviewed briefly.
2. Four new fluorene derivatives were designed and synthesized, and their structures were characterized by FT-IR and1H-NMR.
3. Three fluorene-type homopolymer with azobenzene polypropargyl functional group were designed and synthesized using [Rh(nbd)Cl]2-Et3N as catalyst, and their structures were characterized by FT-IR and1H-NMR.
4. The UV-vis absorption spectra of the monomers and polymers were studied, and the results showed that the maximum absorption peak of the polymer occurred red shift compared with their monomers, and it probably because the influence of the highly conjugated structure of the polymer.
5. The TGA and DSC of the monomer and polymer were investigated. The results showed that the polymer had good thermal stability.
引文
[1]Chen J W, Xu B, O X Y, et al. Aggregation-Induced Emission of cis,cis-1,2,3,4-Tetraphenylbutadiene from Restricted Intramolecular Rotation[J]. J. Phys. Chem. A,2004, 108 (37):7522-7526
[2]Ye G, Xu G Q, Yu Z Q, et al.Frustrated Molecular Packing in Highly Ordered Smectic Phase of Side-Chain Liquid Crystalline Polymer with Rigid Polyacetylene Backbone[J].J. Am. Chem. Soc.2005,127:7668-7669
[3]Lai L M, Jacky W Y, Qin A J, et al.Synthesis, Helicity, and Chromism of Optically Active Poly(phenylacetylene)s Carrying Different Amino Acid Moieties and Pendant Terminal Groups[J].J. Phys. Chem. B,2006,110:11128-11138
[4]Dmitri V T, Charles T B, Cherie R K, et al.Alignment, Electronic Properties, Doping, and On-Chip Growth of Colloidal PbSe Nanowires[J].J. Phys. Chem. C 2007,111:13244-13249
[5]Jacky W Y, Qin A J, Dong Y P, et al. Functional Disubstituted Polyacetylenes:Synthesis, Liquid Crystallinity, Light Emission, and Fluorescent Photopatterning of Biphenyl-Containing Poly(1-phenyl-octyne)s with Different Functional Bridges[J]. J. Phys. Chem. B,2006,110 (43): 21613-21622
[6]Naarmann N, Theophilou N. New Properties for the Production of Metal-Like, Stable Polyacetylene[J]. Synth.Met.1987,22:1-8.
[7]Toshio M,Tang B Z, Akira T, et al. Mechanical Properties of Substituted Polyacetylenes [J]. Macromolecules,1986,19:1459-1464
[8]Kong X X, Jacky W, Tang B Z. et al. Synthesis, Mesomorphism, Isomerization, and Aromatization of Stereoregular Poly{[4-({[6-({[4(?)-(heptyl)oxy-4-biphenylyl] carbonyl} oxy)-hexyl]oxy}carbonyl)phenyl]acetylene}[J].Macromolecules,1999,32:1722-1730
[9]Chen J W, Peng H, Charles C. et al.W.Hyperbranched Poly(phenylenesilolene)s:Synthesis, Thermal Stability,Electronic Conjugation, Optical Power Limiting, and Cooling-Enhanced Light Emission[J]. Macromolecules,2003,36:4319-4327
[10]Tang B Z, Kong X, Wan X. et al. Synthesis and Properties of Stereoregular Polyacetylenes Containing Cyano Groups, Poly[[4-[[n-[(4'-Cyano-4-biphenylyl)
-oxy]alkyl]oxy]carbonyl]phenyl]acetylenes[J]. Macromolecules,1997,30: 5620-5628
[11]Tang B Z, Leung S M, Peng H. Direct Fullerenation of Polycarbonate via Simple Polymer Reactions[J].Macromolecules,1997,30:2848-2852
[12]Lam W Y, Kong X, Tang B Z, et al.Synthesis and Mesomorphic Properties of A Side Chain Liquid Crystalline Poly acetylene Containing Phenyl Benzoate Mesogens[J]. Polymer.Mater.Sci.Eng.1999,80(15):9-16
[13]Sergei S S, Brent S. S, et al. Krzysztof M, Cylindrical molecular brushes:Synthesis, characterization, and properties[J]. Progress in Polymer Science,2008,33:759-785
[14]Katrien V. B, Filip E, Du P, et al.Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques[J]. Prog. Polym. Sci,2006,31:671-722
[15]Yu SY, Atilla T M. Mechanistic transformations involving living and controlled/living polymerization methods[J].Prog. Polym. Sci.2006,31:1133-1170
[16]Liu J H, Yan J J, Chen E Q, et al. Chain helicity of a poly(phenylacetylene) with chiral centers between backbone and mesogenic groups on side chains [J]. Polymer,2008,49: 3366-3370
[17]Sergei S S, Brent S S, Krzysztof M, et al. Cylindrical molecular brushes:Synthesis, characterization, and properties[J].Progress in Polymer Science,2008,33:759-785
[18]Cho M J, Choia D H, Philip A, et al. Recent progress in second-order nonlinear optical polymers and dendrimers[J]. Progress in Polymer Science,2008,33:1013-1058
[19]Jeffery T, Ferber B. One-pot palladium-catalyzed highly chemo-,regio-, and stereoselective synthesis of trans-stilbene derivatives.A concise and convenient synthesis of resveratrol[J]. Tetrahedron Lett,2002,44:193-197.
[20]Raimundo J M, Blanchard P, Gallego P N, et al. Design and synthesis of push-pull chromophores for second-order nonlinear optics derived from rigidified thiophene-based-conjugating spacers[J]. J Org Chem,2002,67:205-208.
[21]Rau H. Photochromism:Molecules and system (eds. Durr H, Laurent H B)[J]. Amterdam: Elsevier Press,1990,8:165-192
[22]王建营,冯长根,胡文祥.光致变色聚合物研究进展[J].化学进展,2006,18：288-307
[23]Rao V P, Jen A Y, Chandrasekhar J, et al. The important role of heteroaromatics in the design of efficient second-order nonlinear optical molecules:theoretical investigation on push-pull heteroaromatic stilbenes[J]. J Am Chem Soc,1996,118:12443-12448.
[24]Agolini F, Gay F P. Synthesis and Properties of Azoaromatic Polymers[J]. Macromolecules, 1970,3 (3):349-351.
[25]HempelR, Vida H, Morgenstem J, et al. Effects of cereal harvest on abundance and spatial distribution of the rodent Akodon azarae in central Argentina[J]. Prak. Chem.1976,318 (6): 983-992
[26]Haitjema H J, Morgen G L, Tan Y, et al. Photoresponsive Behavior of Azobenzene-Based (Meth)acrylic (Co)polymers in Thin Films[J]. Macromolecules,1994,27:6201-6206
[27]Meng X, Natanson A, Rochon P, et al Azo Polymers for Reversible Optical Storage.10. Cooperative Motion of Polar Side. Groups in Amorphous Polymers[J]. Macromolecules,1996, 29(3):946-952
[28]Ho M S, Natansohn A, Rochon P, et al Azo Polymers for Reversible Optical Storage.7. The Effect of the Size of the Photochromic Groups[J]. Macromolecules,1995,28 (18):6124-6127
[29]Meng X, Natansohn A, Rochon P, et al Azo polymers for reversible optical storage.11 poly{4,4-(1-methylethylidene)bisphenylene,3-[4-(4-nitrophenylazo)phenyl]-3-aza-pentanedioa te[J]. Polymer,1998,38:2677-2682.
[30]Toru F J, Masashi S, Yoshihito I, et al. Synthesis of Helical Poly(N-propargyl-amides) Carrying AzobenzeneMoieties in Side Chains. Reversible Arrangement-Disarran-gement ofHelical Side Chain Arrays upon Photoirradiation Keeping HelicalMain Chain Intact[J].Macromolecules,2007,40:7079-7088
[31]谭 克,杨国春,杨贵福,等.螺旋双芴体系二阶非线性光学性质的ZINDO-SOS理论研究[J].分子科学学报,2005,21(3)：17
[32]Christof J K, Nils K, et al. Wojciech P, First Synthesis of Isotactic Poly(9-alkyll-9-alky 12flu-orene) via Directed Aryl-Aryl Coupling of Chiral AB-Type Monomers[J]. Macromol-ecules,2009,42:3483-3488
[33]Li Z A, Yu G, Li Z, et al. "H"-shape second order NLO polymers:synthesis and characterizationw[J]. Polymer,2008,49:901-905.
[1]李晟.硕士论文.新型有机-无机杂化非线性光学材料的制备与性能研究[D].合肥：安徽大学,2007.
[2]Maxime R, Mario L. New Base-Doped Polyfluorene Derivatives[J]. Macromolecules,1999,32: 3306-3313.
[3]邓继勇,谢治民,袁涌.2,7-二溴-9,9-二辛基芴的合成工艺改进[J].化学试剂,2007,29(2)：117-118
[4]Bruce A, Reinhardt, Lawrence L, et al. Highly Active Two-Photon Dyes:Design, Synthesis, and Characterization toward Application[J]. Chem. Mater.1998,10:1863-1874.
[5]Zuev P V, Zgonnik L D, Turkova L A. Shibaev. Thermal degradation of poly-p-nitrostyrene[J]. Polymer Degradation and Stability.1999,63:15-17.
[6]陈建海,陈清元,沈家瑞.偶氮聚合物的偶联剂-对二乙烯偶氮苯的合成与表征[J].高分子材料科学与工程,2004,20(6)：102-105.
[7]陈清元,游文玮,周益民,等.二乙烯基偶氮苯的合成[J].第一军医大学学报,2003,23：273-276.
[8]Stephen P. Jacober, Robert P. Hanzlik. Carbon-13 and Oxygen-18 Kinetic Isotope Effects on Methanolysis of p-Nitrostyrene Oxide[J]. J.Am.Chem.Soc.1986,108:1594-1597.
[9]张华西,陈浩,李瑛,等.新型烷基芴共聚物的合成及电致发光性质[J].高分子材料科学与工程,2006,22(2)：71-74.
[10]Neil G P, Uwe H F, Bunz. Poly(fluorenyleneethynylene)s by Alkyne Metathesis:Optical Properties and Aggregation Behavior[J], Macromolecules 2000,33,3961-3963.
[11]Yu C, Yasuyuki A, James D, et al. Synthesis, Characterization, and Optoelectronic Properties of a Novel Polyfluorene/Poly(p-Phenylenevinylene) Copolymer[J]. Chem. Mater.2005,17: 1661-1666.
[12]Jaehyung H, Eung G K, Jie H, et al. Photoelectron Spectroscopic Study of the Electronic
Band Structure of Polyfluorene and Fluorene-Arylamine Copolymers at Interfaces[J]. J. Phys. Chem. C 2007,111:1378-1384
[13]Zhao L, Ma J, Sun. Z Z, et al. Preliminary kinetic study on the degradation of nitrobenzene by modified ceramic honeycomb-catalytic ozonation in aqueous solution[J]. Journal of Hazardous Materials,2009,161:988-994
[14]Po-Jung. J H, Cameron T S, AmitabhJ. Synthesis of 2,2-dialkyl-3-dialkyl amino-2, 3-dihydro-1Hnaphtho[2,1-b]pyrans[J].Tetrahedron Letters,2009,50:51-54
[15]Ma W B, Wu Y Q, Han J H. Gan. Enhancement of three-photon absorption cross-sections in a novel class of symmetrical charge transfer fluorene-based molecules[J]. Chemical Physics Letters,2005,410:282-287
[16]Lars V S, Matthias M E, Hermann E, et al. Elastic Properties of Photosw-itc hable Azobenzene Polymers from Molecular Dynamics Simulations[J]. Angew. Chem. Int. Ed, 2007,46:2232-2237
[17]Shen. X Q, Liu H W, Li Y S, et al. Click-Together Azobenzene Dendrons:Synthesis and Characterization[J]. Macromolecules,2008,41:2421-2425
[18]Matthew V, Pau G,. Stephanie S. Reversibly Caged Glutamate:A Photo-chromic Agonist of lonotropic Glutamate Receptors[J]. J. Am. Chem. Soc,2007,129,260-262
[19]Marcos M, Serrano J L, Sierra T. Ferroelectric metallomesogenic palladium (Ⅱ) complexes derived from bidentate Schiff bases[J]. Chem. Mater,1993,5 (9):1332-1337.
[20]Victor J M, Patrick G A, Craig B F, et al. AFM Images of Complexes between Amylose and Aspergillus niger Glucoamylase Mutants, Native and Mutant Starch Binding Domains:A Model forthe Action of Glucoamylase[J]. Starch/Starke,2005,57:1-7
[21]Gao F B, Guo S J. The molecular mechanism of HDAC inhibitors in anticancer effects[J]. Cell Mol Immunol,2006,3(4):285-290.
[22]徐洪耀,沈娟,光善仪,等.2,5-二芳基取代基-1,3,4-噁二唑类衍生物的合成与表征[J].合成化学,2006,14(1)：14-17.
[23]Kang H, Facchetti A, Jiang H, et al. Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores:Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies[J]. J.Am.Chem.Soc.2007,129(11):3267-3286.
[24]Kurtz S K, Perry T T. A powder technique for the evaluation of nonlinear optical materials[J]. J Appl Phys,1968,39(8):3798-3813.
[25]Yao S C, Lu J M, Li N J, et al. Synthesis and Three-order Nonlinear Optical Properties of Polyamic Acid Modified with Azo Side-chain[J]. Journal of Chemical Engineering of Chinese Universities,2005,19(3):344-348.
[26]Cui X, Li Z, Tao C Z, et al. N,N-Dimethyl-β-Alanine as an Inexpensive and Efficient Ligand for Palladium-Catalyzed Heck Reaction [J] Org. Lett.,2006,12(8):2467-2470.
[1]马建标.功能高分子材料[M].北京化学工业出版社,2000,234-236
[2]余志滨,杨洲,和亚宁,等.异氰酸酯交联的环氧树脂基二阶非线性光学聚合物[J].高分子学报,2004,(3)：345-349
[3]Yin S C, Xu H Y, Shi W F, et al. Preparation and Optical Properties of Poly(4-Ethynyl-4'-[N,N-Diethylamino]Azobenzene-co-Phenylace-tylene)[J]. Dyes Pigmen ts., 2007,72:119-123
[4]Sheik B M, Said A A, Vanstryland E W. High-sensitivity, single-beam n2 measurements[J]. Opt. Lett,1989,17,14:955-957.
[5]Sun X B, Wang Y L, Ren Q, et al. Study on nonlinear optical properties of two novel dmit2-salts by Z-scan technique[J]. Optical Materials,2007,29:1305-1309.
[6]Dertinger T, vonder H I, Benda A, et al. Surface Sticking and Lateral Diffusion of Lipids in Supported Bilayers[J]. Langmuir,2006,22,22:9339-9344.
[7]Belfield K D, Bondar M V, Hernandez F E, et al. Two-Photon Absorption Cross Section Determination for Fluorene Derivatives:Analysis of the Methodology and Elucidation of the Origin of the Absorption Processes[J]. J Phys Chem B,2007,111 (44):12723-12729.
[8]Jacinto C, Messias D N, Andrade A A, et al. Thermal lens and Z-scan measurements:Thermal and optical properties of laser glasses-A review[J]. Journal of Non-Crystalline Solids,2006, 352:3582-3597
[1]Caouthar A, Roger P, Tessier M, el al. Synthesis and characterization of new polyamides derived from di(4-cyanophenyl)isosorbide[J]. European Polymer Journal,2007,43:220-230
[2]Liu B, Huang W. Novel Deep Blue Fluorescent Fluorene-Based Copolymer Containing Hole-Transporting Arylamine Segments [J]. Thin Solid Films,2002,417(1-2):206-210.
[3]Sirajuddin, Bhanger M I, Niaz A, et al. Ultra-trace level determination of hydroquinone in waste photographic solutions by UV-vis spectrophotometry [J]. Talanta,2007,72(2):546-553.
[4]Gidden J, Jackson A T, Bowers M T, et al. Gas-phase conformations of cationized poly(styrene)oligomers[J].J Am Soc Mass Spectr,2002,13:499-505
[5]Cheun H,Liu X, Himpsel F.H Polarized Optical Absorption Spectroscopy, NEXAFS, and GIXRD Measurements of Chain Alignment in Polyfluorene Thin Films[J]. Macromolecules 2008,41:6463-6472
[6]Pyun T E, Matyjaszewski K.Copper(Ⅰ)-catalyzed atom transfer radical polymerization[J].Acc Chem Res,1999,32:895-903
[7]Lee J, Chao H J, Jung B J, et al. Stabilized Blue Luminescent Polyfluorenes:Introducing Polyhedral Oligomeric Silsesquioxane [J]. Macromolecules,2006,37:8523-8529
[8]Franklin A, Umamaheswari V, David F B. Determination of the Structure and Orientation of Organic Molecules Tethered to Flat Graphitic Carbon by ATR-FT-IR and Raman Spectroscopy[J]. Anal. Chem.2006,78:3104-3112
[9]Friberg S R, Smith P W. Nonlinear Optical Glass for Ultrafast Optical Switches [J]. Quantum Electronics,1987,23 (12):2089-2094.
[10]Chen M, Cui L, Li C H, et al. Adsorption, desorption and condensation of nitrobenzene solution from active carbon:A comparison of two cyclodextrins and two surfactants[J]. Journal of Hazardous Materials 2009,162:23-28
[II]Sepuri A, Maravajhala V. Cunninghamella-A microbial model for drug metabolism studies-A review[J],Biotechnology Advances 2009,27:16-29
[12]盂令芝,龚淑玲,何永炳.有机波普分析[M].武汉大学出版社,2003
[13]Enzo M, Vittorio B, Piero S. Use of biosurfactants from urban wastes compost in textile dyeing and soil remediation[J]. Waste Management 2009 29:383-389
[14]Liu Z, Robinson J T, Sun X N. PEGylated Nano-Graphene Oxide for Delivery of Water-Insoluble Cancer Drugs[J]. J. Am. Chem. Soc.2008,130:10876-1087
[15]胡益林,董跃,刘建平.差示扫描量热法(DSC)在UPVC异型材中的应用[J].加工应用,2006,10：40-42.
[16]王书军,高文远,陈海霞,等.热分析(TG,DTA)方法在鉴别贝母类中药材中的应用[J].中国中药杂志,2007,32(4)：296-299.
[17]张会旗,甘湘萍,万绍隆,等.含偶氮基团的聚酯型高分子非线性光学材料的合成与表征[J].高分子材料科学与工程,2000,4：37-39
[18]张其震,殷晓颖,李爱香,等.端基含4个丁氧基苯介晶基元光致变色液晶树状物的合成、结构及液晶性研究[J].高等学校化学学报,2004,25(1)：170-173.
[19]郑世军,张晓静,张淑媛,等.含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成[J].应用化学,2006,23(1)：12-17.
[2]Ye G, Xu G Q, Yu Z Q, et al.Frustrated Molecular Packing in Highly Ordered Smectic Phase of Side-Chain Liquid Crystalline Polymer with Rigid Polyacetylene Backbone[J].J. Am. Chem. Soc.2005,127:7668-7669
[3]Lai L M, Jacky W Y, Qin A J, et al.Synthesis, Helicity, and Chromism of Optically Active Poly(phenylacetylene)s Carrying Different Amino Acid Moieties and Pendant Terminal Groups[J].J. Phys. Chem. B,2006,110:11128-11138
[4]Dmitri V T, Charles T B, Cherie R K, et al.Alignment, Electronic Properties, Doping, and On-Chip Growth of Colloidal PbSe Nanowires[J].J. Phys. Chem. C 2007,111:13244-13249
[5]Jacky W Y, Qin A J, Dong Y P, et al. Functional Disubstituted Polyacetylenes:Synthesis, Liquid Crystallinity, Light Emission, and Fluorescent Photopatterning of Biphenyl-Containing Poly(1-phenyl-octyne)s with Different Functional Bridges[J]. J. Phys. Chem. B,2006,110 (43): 21613-21622
[6]Naarmann N, Theophilou N. New Properties for the Production of Metal-Like, Stable Polyacetylene[J]. Synth.Met.1987,22:1-8.
[7]Toshio M,Tang B Z, Akira T, et al. Mechanical Properties of Substituted Polyacetylenes [J]. Macromolecules,1986,19:1459-1464
[8]Kong X X, Jacky W, Tang B Z. et al. Synthesis, Mesomorphism, Isomerization, and Aromatization of Stereoregular Poly{[4-({[6-({[4(?)-(heptyl)oxy-4-biphenylyl] carbonyl} oxy)-hexyl]oxy}carbonyl)phenyl]acetylene}[J].Macromolecules,1999,32:1722-1730
[9]Chen J W, Peng H, Charles C. et al.W.Hyperbranched Poly(phenylenesilolene)s:Synthesis, Thermal Stability,Electronic Conjugation, Optical Power Limiting, and Cooling-Enhanced Light Emission[J]. Macromolecules,2003,36:4319-4327
[10]Tang B Z, Kong X, Wan X. et al. Synthesis and Properties of Stereoregular Polyacetylenes Containing Cyano Groups, Poly[[4-[[n-[(4'-Cyano-4-biphenylyl)
-oxy]alkyl]oxy]carbonyl]phenyl]acetylenes[J]. Macromolecules,1997,30: 5620-5628
[11]Tang B Z, Leung S M, Peng H. Direct Fullerenation of Polycarbonate via Simple Polymer Reactions[J].Macromolecules,1997,30:2848-2852
[12]Lam W Y, Kong X, Tang B Z, et al.Synthesis and Mesomorphic Properties of A Side Chain Liquid Crystalline Poly acetylene Containing Phenyl Benzoate Mesogens[J]. Polymer.Mater.Sci.Eng.1999,80(15):9-16
[13]Sergei S S, Brent S. S, et al. Krzysztof M, Cylindrical molecular brushes:Synthesis, characterization, and properties[J]. Progress in Polymer Science,2008,33:759-785
[14]Katrien V. B, Filip E, Du P, et al.Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques[J]. Prog. Polym. Sci,2006,31:671-722
[15]Yu SY, Atilla T M. Mechanistic transformations involving living and controlled/living polymerization methods[J].Prog. Polym. Sci.2006,31:1133-1170
[16]Liu J H, Yan J J, Chen E Q, et al. Chain helicity of a poly(phenylacetylene) with chiral centers between backbone and mesogenic groups on side chains [J]. Polymer,2008,49: 3366-3370
[17]Sergei S S, Brent S S, Krzysztof M, et al. Cylindrical molecular brushes:Synthesis, characterization, and properties[J].Progress in Polymer Science,2008,33:759-785
[18]Cho M J, Choia D H, Philip A, et al. Recent progress in second-order nonlinear optical polymers and dendrimers[J]. Progress in Polymer Science,2008,33:1013-1058
[19]Jeffery T, Ferber B. One-pot palladium-catalyzed highly chemo-,regio-, and stereoselective synthesis of trans-stilbene derivatives.A concise and convenient synthesis of resveratrol[J]. Tetrahedron Lett,2002,44:193-197.
[20]Raimundo J M, Blanchard P, Gallego P N, et al. Design and synthesis of push-pull chromophores for second-order nonlinear optics derived from rigidified thiophene-based-conjugating spacers[J]. J Org Chem,2002,67:205-208.
[21]Rau H. Photochromism:Molecules and system (eds. Durr H, Laurent H B)[J]. Amterdam: Elsevier Press,1990,8:165-192
[22]王建营,冯长根,胡文祥.光致变色聚合物研究进展[J].化学进展,2006,18：288-307
[23]Rao V P, Jen A Y, Chandrasekhar J, et al. The important role of heteroaromatics in the design of efficient second-order nonlinear optical molecules:theoretical investigation on push-pull heteroaromatic stilbenes[J]. J Am Chem Soc,1996,118:12443-12448.
[24]Agolini F, Gay F P. Synthesis and Properties of Azoaromatic Polymers[J]. Macromolecules, 1970,3 (3):349-351.
[25]HempelR, Vida H, Morgenstem J, et al. Effects of cereal harvest on abundance and spatial distribution of the rodent Akodon azarae in central Argentina[J]. Prak. Chem.1976,318 (6): 983-992
[26]Haitjema H J, Morgen G L, Tan Y, et al. Photoresponsive Behavior of Azobenzene-Based (Meth)acrylic (Co)polymers in Thin Films[J]. Macromolecules,1994,27:6201-6206
[27]Meng X, Natanson A, Rochon P, et al Azo Polymers for Reversible Optical Storage.10. Cooperative Motion of Polar Side. Groups in Amorphous Polymers[J]. Macromolecules,1996, 29(3):946-952
[28]Ho M S, Natansohn A, Rochon P, et al Azo Polymers for Reversible Optical Storage.7. The Effect of the Size of the Photochromic Groups[J]. Macromolecules,1995,28 (18):6124-6127
[29]Meng X, Natansohn A, Rochon P, et al Azo polymers for reversible optical storage.11 poly{4,4-(1-methylethylidene)bisphenylene,3-[4-(4-nitrophenylazo)phenyl]-3-aza-pentanedioa te[J]. Polymer,1998,38:2677-2682.
[30]Toru F J, Masashi S, Yoshihito I, et al. Synthesis of Helical Poly(N-propargyl-amides) Carrying AzobenzeneMoieties in Side Chains. Reversible Arrangement-Disarran-gement ofHelical Side Chain Arrays upon Photoirradiation Keeping HelicalMain Chain Intact[J].Macromolecules,2007,40:7079-7088
[31]谭 克,杨国春,杨贵福,等.螺旋双芴体系二阶非线性光学性质的ZINDO-SOS理论研究[J].分子科学学报,2005,21(3)：17
[32]Christof J K, Nils K, et al. Wojciech P, First Synthesis of Isotactic Poly(9-alkyll-9-alky 12flu-orene) via Directed Aryl-Aryl Coupling of Chiral AB-Type Monomers[J]. Macromol-ecules,2009,42:3483-3488
[33]Li Z A, Yu G, Li Z, et al. "H"-shape second order NLO polymers:synthesis and characterizationw[J]. Polymer,2008,49:901-905.
[1]李晟.硕士论文.新型有机-无机杂化非线性光学材料的制备与性能研究[D].合肥：安徽大学,2007.
[2]Maxime R, Mario L. New Base-Doped Polyfluorene Derivatives[J]. Macromolecules,1999,32: 3306-3313.
[3]邓继勇,谢治民,袁涌.2,7-二溴-9,9-二辛基芴的合成工艺改进[J].化学试剂,2007,29(2)：117-118
[4]Bruce A, Reinhardt, Lawrence L, et al. Highly Active Two-Photon Dyes:Design, Synthesis, and Characterization toward Application[J]. Chem. Mater.1998,10:1863-1874.
[5]Zuev P V, Zgonnik L D, Turkova L A. Shibaev. Thermal degradation of poly-p-nitrostyrene[J]. Polymer Degradation and Stability.1999,63:15-17.
[6]陈建海,陈清元,沈家瑞.偶氮聚合物的偶联剂-对二乙烯偶氮苯的合成与表征[J].高分子材料科学与工程,2004,20(6)：102-105.
[7]陈清元,游文玮,周益民,等.二乙烯基偶氮苯的合成[J].第一军医大学学报,2003,23：273-276.
[8]Stephen P. Jacober, Robert P. Hanzlik. Carbon-13 and Oxygen-18 Kinetic Isotope Effects on Methanolysis of p-Nitrostyrene Oxide[J]. J.Am.Chem.Soc.1986,108:1594-1597.
[9]张华西,陈浩,李瑛,等.新型烷基芴共聚物的合成及电致发光性质[J].高分子材料科学与工程,2006,22(2)：71-74.
[10]Neil G P, Uwe H F, Bunz. Poly(fluorenyleneethynylene)s by Alkyne Metathesis:Optical Properties and Aggregation Behavior[J], Macromolecules 2000,33,3961-3963.
[11]Yu C, Yasuyuki A, James D, et al. Synthesis, Characterization, and Optoelectronic Properties of a Novel Polyfluorene/Poly(p-Phenylenevinylene) Copolymer[J]. Chem. Mater.2005,17: 1661-1666.
[12]Jaehyung H, Eung G K, Jie H, et al. Photoelectron Spectroscopic Study of the Electronic
Band Structure of Polyfluorene and Fluorene-Arylamine Copolymers at Interfaces[J]. J. Phys. Chem. C 2007,111:1378-1384
[13]Zhao L, Ma J, Sun. Z Z, et al. Preliminary kinetic study on the degradation of nitrobenzene by modified ceramic honeycomb-catalytic ozonation in aqueous solution[J]. Journal of Hazardous Materials,2009,161:988-994
[14]Po-Jung. J H, Cameron T S, AmitabhJ. Synthesis of 2,2-dialkyl-3-dialkyl amino-2, 3-dihydro-1Hnaphtho[2,1-b]pyrans[J].Tetrahedron Letters,2009,50:51-54
[15]Ma W B, Wu Y Q, Han J H. Gan. Enhancement of three-photon absorption cross-sections in a novel class of symmetrical charge transfer fluorene-based molecules[J]. Chemical Physics Letters,2005,410:282-287
[16]Lars V S, Matthias M E, Hermann E, et al. Elastic Properties of Photosw-itc hable Azobenzene Polymers from Molecular Dynamics Simulations[J]. Angew. Chem. Int. Ed, 2007,46:2232-2237
[17]Shen. X Q, Liu H W, Li Y S, et al. Click-Together Azobenzene Dendrons:Synthesis and Characterization[J]. Macromolecules,2008,41:2421-2425
[18]Matthew V, Pau G,. Stephanie S. Reversibly Caged Glutamate:A Photo-chromic Agonist of lonotropic Glutamate Receptors[J]. J. Am. Chem. Soc,2007,129,260-262
[19]Marcos M, Serrano J L, Sierra T. Ferroelectric metallomesogenic palladium (Ⅱ) complexes derived from bidentate Schiff bases[J]. Chem. Mater,1993,5 (9):1332-1337.
[20]Victor J M, Patrick G A, Craig B F, et al. AFM Images of Complexes between Amylose and Aspergillus niger Glucoamylase Mutants, Native and Mutant Starch Binding Domains:A Model forthe Action of Glucoamylase[J]. Starch/Starke,2005,57:1-7
[21]Gao F B, Guo S J. The molecular mechanism of HDAC inhibitors in anticancer effects[J]. Cell Mol Immunol,2006,3(4):285-290.
[22]徐洪耀,沈娟,光善仪,等.2,5-二芳基取代基-1,3,4-噁二唑类衍生物的合成与表征[J].合成化学,2006,14(1)：14-17.
[23]Kang H, Facchetti A, Jiang H, et al. Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores:Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies[J]. J.Am.Chem.Soc.2007,129(11):3267-3286.
[24]Kurtz S K, Perry T T. A powder technique for the evaluation of nonlinear optical materials[J]. J Appl Phys,1968,39(8):3798-3813.
[25]Yao S C, Lu J M, Li N J, et al. Synthesis and Three-order Nonlinear Optical Properties of Polyamic Acid Modified with Azo Side-chain[J]. Journal of Chemical Engineering of Chinese Universities,2005,19(3):344-348.
[26]Cui X, Li Z, Tao C Z, et al. N,N-Dimethyl-β-Alanine as an Inexpensive and Efficient Ligand for Palladium-Catalyzed Heck Reaction [J] Org. Lett.,2006,12(8):2467-2470.
[1]马建标.功能高分子材料[M].北京化学工业出版社,2000,234-236
[2]余志滨,杨洲,和亚宁,等.异氰酸酯交联的环氧树脂基二阶非线性光学聚合物[J].高分子学报,2004,(3)：345-349
[3]Yin S C, Xu H Y, Shi W F, et al. Preparation and Optical Properties of Poly(4-Ethynyl-4'-[N,N-Diethylamino]Azobenzene-co-Phenylace-tylene)[J]. Dyes Pigmen ts., 2007,72:119-123
[4]Sheik B M, Said A A, Vanstryland E W. High-sensitivity, single-beam n2 measurements[J]. Opt. Lett,1989,17,14:955-957.
[5]Sun X B, Wang Y L, Ren Q, et al. Study on nonlinear optical properties of two novel dmit2-salts by Z-scan technique[J]. Optical Materials,2007,29:1305-1309.
[6]Dertinger T, vonder H I, Benda A, et al. Surface Sticking and Lateral Diffusion of Lipids in Supported Bilayers[J]. Langmuir,2006,22,22:9339-9344.
[7]Belfield K D, Bondar M V, Hernandez F E, et al. Two-Photon Absorption Cross Section Determination for Fluorene Derivatives:Analysis of the Methodology and Elucidation of the Origin of the Absorption Processes[J]. J Phys Chem B,2007,111 (44):12723-12729.
[8]Jacinto C, Messias D N, Andrade A A, et al. Thermal lens and Z-scan measurements:Thermal and optical properties of laser glasses-A review[J]. Journal of Non-Crystalline Solids,2006, 352:3582-3597
[1]Caouthar A, Roger P, Tessier M, el al. Synthesis and characterization of new polyamides derived from di(4-cyanophenyl)isosorbide[J]. European Polymer Journal,2007,43:220-230
[2]Liu B, Huang W. Novel Deep Blue Fluorescent Fluorene-Based Copolymer Containing Hole-Transporting Arylamine Segments [J]. Thin Solid Films,2002,417(1-2):206-210.
[3]Sirajuddin, Bhanger M I, Niaz A, et al. Ultra-trace level determination of hydroquinone in waste photographic solutions by UV-vis spectrophotometry [J]. Talanta,2007,72(2):546-553.
[4]Gidden J, Jackson A T, Bowers M T, et al. Gas-phase conformations of cationized poly(styrene)oligomers[J].J Am Soc Mass Spectr,2002,13:499-505
[5]Cheun H,Liu X, Himpsel F.H Polarized Optical Absorption Spectroscopy, NEXAFS, and GIXRD Measurements of Chain Alignment in Polyfluorene Thin Films[J]. Macromolecules 2008,41:6463-6472
[6]Pyun T E, Matyjaszewski K.Copper(Ⅰ)-catalyzed atom transfer radical polymerization[J].Acc Chem Res,1999,32:895-903
[7]Lee J, Chao H J, Jung B J, et al. Stabilized Blue Luminescent Polyfluorenes:Introducing Polyhedral Oligomeric Silsesquioxane [J]. Macromolecules,2006,37:8523-8529
[8]Franklin A, Umamaheswari V, David F B. Determination of the Structure and Orientation of Organic Molecules Tethered to Flat Graphitic Carbon by ATR-FT-IR and Raman Spectroscopy[J]. Anal. Chem.2006,78:3104-3112
[9]Friberg S R, Smith P W. Nonlinear Optical Glass for Ultrafast Optical Switches [J]. Quantum Electronics,1987,23 (12):2089-2094.
[10]Chen M, Cui L, Li C H, et al. Adsorption, desorption and condensation of nitrobenzene solution from active carbon:A comparison of two cyclodextrins and two surfactants[J]. Journal of Hazardous Materials 2009,162:23-28
[II]Sepuri A, Maravajhala V. Cunninghamella-A microbial model for drug metabolism studies-A review[J],Biotechnology Advances 2009,27:16-29
[12]盂令芝,龚淑玲,何永炳.有机波普分析[M].武汉大学出版社,2003
[13]Enzo M, Vittorio B, Piero S. Use of biosurfactants from urban wastes compost in textile dyeing and soil remediation[J]. Waste Management 2009 29:383-389
[14]Liu Z, Robinson J T, Sun X N. PEGylated Nano-Graphene Oxide for Delivery of Water-Insoluble Cancer Drugs[J]. J. Am. Chem. Soc.2008,130:10876-1087
[15]胡益林,董跃,刘建平.差示扫描量热法(DSC)在UPVC异型材中的应用[J].加工应用,2006,10：40-42.
[16]王书军,高文远,陈海霞,等.热分析(TG,DTA)方法在鉴别贝母类中药材中的应用[J].中国中药杂志,2007,32(4)：296-299.
[17]张会旗,甘湘萍,万绍隆,等.含偶氮基团的聚酯型高分子非线性光学材料的合成与表征[J].高分子材料科学与工程,2000,4：37-39
[18]张其震,殷晓颖,李爱香,等.端基含4个丁氧基苯介晶基元光致变色液晶树状物的合成、结构及液晶性研究[J].高等学校化学学报,2004,25(1)：170-173.
[19]郑世军,张晓静,张淑媛,等.含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成[J].应用化学,2006,23(1)：12-17.