香豆素类光敏聚合物及支化聚合物的合成与研究
|
摘要
本论文总共分为两大部分,第一部分内容为：香豆素类光敏聚合物的合成与性能研究,1)：设计、合成了含二硫键的香豆素衍生物(C-S-S-C),并以其与三丁基膦/水的复合体系为链转移剂,偶氮二异丁腈(AIBN)为引发剂,自由基聚合法制备了链端含香豆素光敏感基元的双亲性遥爪聚N-异丙基丙烯酰胺(C-PNIPAAm); 2):设计、合成了含三个溴原子ATRP引发点的引发剂(C-Br3),以甲基丙烯酸-N,N-二甲氨基乙酯(DMAEMA)、苯乙烯(St)为单体合成了两种双亲性光敏星形聚合物——聚(甲基丙烯酸-N,N-二甲氨基乙酯)C-(PDMAEMA)3和聚苯乙烯-b-聚(甲基丙烯酸-N,N-二甲氨基乙酯)C-(PSt-b-PDMAEMA)3。用傅里叶变换红外光谱仪(FT-IR)、紫外-可见光分光光度计(UV-vis)、凝胶渗透色谱仪(GPC)、液相质谱联用仪(LC-MS)和核磁共振仪('H-NMR)对C-S-S-C、C-Br3及其中间产物以及三种聚合物进行结构表征,并对三种聚合物胶束的光敏性能、形态大小及光控释放行为进行研究。结果表明,C-PNIPAAm在水中可以自组装成胶束,且可通过光开关来控制水溶液中胶束的形态,因香豆素基元的可逆光二聚作用,经波长为365nm紫外光照射后形成中空球状结构,再经波长为254nm紫外光照射后由于二聚体中四元环的断裂而又重新形成最初的胶束结构,用动态激光光散射仪(DLS)和透射电镜(TME)可对这种纳米聚集体形态变化的现象进行跟踪监测。结果表明,在第一个光照循环中30-50 nm直径的胶束,经光照后可形成直径在200-350 nm之间的大囊泡结构,而经光解交联后又重新形成直径为30-50 nm的胶束结构；以荧光素为疏水性分子,当对包覆有荧光素的聚合物胶束溶液进行波长大于310 nm的紫外光照时,端基的香豆素基元发生光二聚,胶束结构发生改变,使得胶束中疏水荧光素有效地释放到水中,且DLS表明胶束的平均半径从56.6 nm增大到101.0nm。另外,经初步研究,C-(PDMAEMA)3和C-(PSt-b-PDMAEMA)3两种聚合物的胶束也表现出较优良的光响应性能。
第二部分内容为：支化聚合物合成新方法的探索,设计、合成了含二硫键的苯乙烯单体(St-S-S-St),并以其为支化单体、苯乙烯(St)为聚合主单体,二氧六环为溶剂,AIBN为引发剂,在三丁基膦/水存在下,自由基聚合法合成了系列支化聚苯乙烯BPSt.用FT-IR,1H-NMR, GPC,三检测器、差示扫描量热仪(DSC)等对聚合物进行一系列结构和性能的表征。结果表明,随着聚合时支化单体加入量的增加,聚合物的重均分子量Mw逐渐增加,而其Tg呈下降趋势,说明通过该方法可成功引入支化结构。另外,通过该方法合成了支化的聚N-异丙基丙烯酰胺BPNIPAAm。
There are two parts in this paper, first:synthesis and properties of photo-sensitive telechelic polymer and star polymers. For the telechelic polymer:a coumarin derivative containing disulfide bond (C-S-S-C) was designed and synthesized, which can be used as chain transfer agent in the prescence of tributylphosphine (Bu3P) and water (H2O), to prepare the amphiphilic photo-sensitive telechelic polymer coumarin-poly(N-Isopropyl acrylamide) (C-PNIPAAm). And for star polymers:a three armed ATRP initiator (C-Br3) containing coumarin group was designed and synthesized, which was used to prepare amphiphilic photo-sensitive star polymers, poly(dimethylaminoethyl methacrylate) C-(PDMAEMA)3 and polystyrene-b-poly(dimethylaminoethyl methacrylate) C-(PSt-b-PDMAEMA)3. The structures of C-S-S-C, C-Br3 and polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), gel permeation chromatography (GPC), liquid chromatography-mass spectrometry (LC-MS) and proton nuclear magnetic resonance spectroscopy (1H-NMR), then photo-sensitive properties, size and photo-controlled release of three polymer micelles were studied. It was found that C-PNIPAAm can form micelles in aqueous solution, and the micellar morphology in aqueous solution can be photo-switched into hollow spheres according to the photo-dimerization of coumarin end groups upon 365 nm irradiation and reform the micellar morphology after the subsequent photo-scission of dimers upon 254 nm. This instantly morphology changing phenomenon was successfully monitored by dynamic laser light scattering (DLS) and transmission electron microscopy (TEM) measurements. It was shown that the small spherical shape of micelles with diameter at 30-50 nm before photo-crosslinking, the big vesicles with diameter at 200-350 nm after photo-crosslinking and the small micelles with diameter at 30-50 nm after the subsequent photo-de-crosslinking in the first irradiation cycle. And using fluorescein as a hydrophobic encapsulation, when irradiated by UV light (λ＞310 nm), the hydrophobic fluorescein was effectively released to the water. DLS showed that the average radius of the micelles increased from 56.6 nm to 101.0 nm after irradiation. In addition, it was found that the micelles prepared by two star polymers, C-(PDMAEMA)3 and C-(PSt-b-PDMAEMA)3, have good photo-sensitive property, respectively.
Second:the new approach to branched polymers. A styrene monomer containing disulfide bond (St-S-S-St) was designed and synthesized, which can be used as branched monomer in the presence of Bu3P and H2O, and using St as main monomer, dioxane as solvent, AIBN as initiator, to prepare branched polystyrene (BPSt). The polymers were characterized by FT-IR,1H-NMR, GPC, and DSC analysis. It was found that the molecular weight (Mw) of BPSt increased exponentially with the increasing molar dosage of St-S-S-St, while the glass transient temperature (Tg) decreased, which meaned that the BPSt can be obtained through the copolymerization of St-S-S-St and St. In addition, branched poly(N-Isopropyl acrylamide) (BPNIPAAm) was synthesized.
第二部分内容为：支化聚合物合成新方法的探索,设计、合成了含二硫键的苯乙烯单体(St-S-S-St),并以其为支化单体、苯乙烯(St)为聚合主单体,二氧六环为溶剂,AIBN为引发剂,在三丁基膦/水存在下,自由基聚合法合成了系列支化聚苯乙烯BPSt.用FT-IR,1H-NMR, GPC,三检测器、差示扫描量热仪(DSC)等对聚合物进行一系列结构和性能的表征。结果表明,随着聚合时支化单体加入量的增加,聚合物的重均分子量Mw逐渐增加,而其Tg呈下降趋势,说明通过该方法可成功引入支化结构。另外,通过该方法合成了支化的聚N-异丙基丙烯酰胺BPNIPAAm。
There are two parts in this paper, first:synthesis and properties of photo-sensitive telechelic polymer and star polymers. For the telechelic polymer:a coumarin derivative containing disulfide bond (C-S-S-C) was designed and synthesized, which can be used as chain transfer agent in the prescence of tributylphosphine (Bu3P) and water (H2O), to prepare the amphiphilic photo-sensitive telechelic polymer coumarin-poly(N-Isopropyl acrylamide) (C-PNIPAAm). And for star polymers:a three armed ATRP initiator (C-Br3) containing coumarin group was designed and synthesized, which was used to prepare amphiphilic photo-sensitive star polymers, poly(dimethylaminoethyl methacrylate) C-(PDMAEMA)3 and polystyrene-b-poly(dimethylaminoethyl methacrylate) C-(PSt-b-PDMAEMA)3. The structures of C-S-S-C, C-Br3 and polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), gel permeation chromatography (GPC), liquid chromatography-mass spectrometry (LC-MS) and proton nuclear magnetic resonance spectroscopy (1H-NMR), then photo-sensitive properties, size and photo-controlled release of three polymer micelles were studied. It was found that C-PNIPAAm can form micelles in aqueous solution, and the micellar morphology in aqueous solution can be photo-switched into hollow spheres according to the photo-dimerization of coumarin end groups upon 365 nm irradiation and reform the micellar morphology after the subsequent photo-scission of dimers upon 254 nm. This instantly morphology changing phenomenon was successfully monitored by dynamic laser light scattering (DLS) and transmission electron microscopy (TEM) measurements. It was shown that the small spherical shape of micelles with diameter at 30-50 nm before photo-crosslinking, the big vesicles with diameter at 200-350 nm after photo-crosslinking and the small micelles with diameter at 30-50 nm after the subsequent photo-de-crosslinking in the first irradiation cycle. And using fluorescein as a hydrophobic encapsulation, when irradiated by UV light (λ＞310 nm), the hydrophobic fluorescein was effectively released to the water. DLS showed that the average radius of the micelles increased from 56.6 nm to 101.0 nm after irradiation. In addition, it was found that the micelles prepared by two star polymers, C-(PDMAEMA)3 and C-(PSt-b-PDMAEMA)3, have good photo-sensitive property, respectively.
Second:the new approach to branched polymers. A styrene monomer containing disulfide bond (St-S-S-St) was designed and synthesized, which can be used as branched monomer in the presence of Bu3P and H2O, and using St as main monomer, dioxane as solvent, AIBN as initiator, to prepare branched polystyrene (BPSt). The polymers were characterized by FT-IR,1H-NMR, GPC, and DSC analysis. It was found that the molecular weight (Mw) of BPSt increased exponentially with the increasing molar dosage of St-S-S-St, while the glass transient temperature (Tg) decreased, which meaned that the BPSt can be obtained through the copolymerization of St-S-S-St and St. In addition, branched poly(N-Isopropyl acrylamide) (BPNIPAAm) was synthesized.
引文
1. Yourick J J, Bronaugh R L. Percutaneous Absorption and Metabolism of Coumarin in Human and Rat Skin [J]. Journal of Applied Toxicology,1997,17(3):153-158
2. Yamazaki M, Tanaka M, Shimada T. Highly sensitive high-performance liquid chromatographic assay for coumarin 7-hydroxylation and 7-ethoxycoumarin O-deethylation by human liver cytochrome P450 enzymes [J]. Journal of Chromatography B,1999,721: 13-19
3. FernaAndez Izquierdo M E, Quesada Granados J, VillaloAn Mir M, et al. Comparison of methods for determining coumarins in distilled beverages [J]. Food Chemistry,2000,70: 251-258
4. Cohen B, Huppert D. Excited State Proton-Transfer Reactions of Coumarin 4 in Protic Solvents [J]. Journal of Physical Chemistry A,2001,105:7157-7164
5. Trenor S R, Shultz A R, Love B J, et al. Coumarins in Polymers:From Light Harvesting to Photo-Cross-Linkable Tissue Scaffolds[J]. Chemical Reviews,2004,104:3059-3077
6. Chen Y, Geh J L. Copolymers derived from 7-acryloyloxy-4-methylcoumarin and acrylates:1. Copolymerizability and photocrosslinking behaviours [J]. Polymer,1996,37(20): 4473-4480
7. Chen Y, Jean C S. Polyethers Containing Coumarin Dimer Components in the Main Chain.Ⅱ. Reversible Photocleavage and Photopolymerization [J]. John Wiley & Sons,1997, 1759-1768
8. Chujo Y, Sada Y, Saegusa T. Polyoxazoline Having a Coumarin Moiety as a Pendant Group. Synthesis and Photogelation [J]. Macromolecules,1990,23:2693-2697
9. Chen Y, Geh J L. Copolymers derived from 7-acryloyloxy-4-methylcoumarin and acrylates:2. Reversible photocrosslinking and photocleavage [J]. Polymer,1996,37(20): 4481-4486
10. Chen Y, Chen K H. Synthesis and Reversible Photocleavage of Novel Polyurethane Containing Coumarin Dimer Components [J]. Journal of Polymer Science:Part A:Polymer Chemistry,1997,35,613-624
11. Chen Y, Hong R T. Photopolymerization of 7,7'-Coumarinyl Polymethylene Dicarboxylates:Fluorescence and Kinetic Study [J]. Journal of Polymer Science:Part A: Polymer Chemistry,1997,35:2999-3008
12.张传智,蒋春霞,王旭等.含香豆素功能基聚合物的合成及荧光性能[J].高分子材料科学与工程,2007,23(6)：85-88
13. Wang B Y, Guan X L, Hu Y L, et al. Preparation and fluorescent properties of poly(vinyl alcohol) bearing coumarin [J]. Polymers for Advanced Technologies,2007,18:529-534
14. Wang B Y, Liu X Y, Hu Y L, et al. Synthesis and photophysical behavior of a water-soluble coumarin-bearing polymer for proton and Ni2+ ion sensing [J]. Polymer International,2009,58:703-709
15. Ren B Y, Zhao D L, Liu S S, et al. Synthesis and Characterization of Poly(ferrocenylsilanes) with Coumarin Side Groups and Their Photochemical Reactivity and Electrochemical Behavior[J]. Macromolecules,2007,40(13):4501-4508
16. Zhao D L, Ren B Y, Liu S S, et al. A novel photoreversible poly(ferrocenylsilane) with coumarin side group:synthesis, characterization and electrochemical activities [J]. Chemical Communications,2006,779-781
17. Fu Q, Cheng L L, Zhang Y, et al. Preparation and reversible photo-crosslinking/photo-cleavage behavior of 4-methylcoumarin functionalized hyperbranched polyester [J]. Polymer,2008,49:4981-4988
18.傅祺.超支化聚酯的合成与表面修饰及其光敏性能研究[D]：[硕士学位论文].中国科技大学高分子科学与工程系,2009
19. Fujiwara M, Shiokawa K, Kawasaki N, et al. Photodimerization of Coumarin-Derived Pentacyclo[9.5.1.1.1.1]octasiloxane to Fabricate a Three-Dimensional Organic-Inorganic Hybrid Material [J], Advanced Functional Materials,2003,13(5):371-376
20. Mal N K, Fujiwara M, Tanaka Y. Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica [J]. Nature,2003,421:350-353
21. Mal N K, Fujiwara M, Tanaka Y, et al. Photo-Switched Storage and Release of Guest Molecules in the Pore Void of Coumarin-Modified MCM-41 [J].Chemistry of Materials,2003, 15(17):3385-3394
22. Matsuda T, Mizutani M. Molecular Design of Photocurable Liquid Biodegradable Copolymers.2. Synthesis of Coumarin-Derivatized Oligo(methacrylate)s and Photocuring [J]. Macromolecules,2000,33(3):791-794
23. Matsuda T, Mizutani M, Arnold S C. Molecular Design of Photocurable Liquid Biodegradable Copolymers.1. Synthesis and Characteristics Photocuring [J]. Macromolecules,2000,33(3):795-800
24. Mizutani M, Matsuda M. Liquid photocurable biodegradable copolymers:In vivo degradation of photocured poly(ε-caprolactone-co-trimethylene carbonate) [J].2002 Wiley Periodicals, Inc.54-60
25. Mizutani M, Matsuda T. Photocurable Liquid Biodegradable Copolymers:In Vitro Hydrolytic Degradation Behaviors of Photocured Films of Coumarin-Endcapped Poly(ε-caprolactone-co-trimethylene carbonate) [J]. Biomacromolecules,2002,3(2):249-255
26. Tian Y Q, Kong X X, Nagase Y, et al. Photocrosslinkable Liquid-Crystalline Block Copolymers with Coumarin Units Synthesized with Atom Transfer Radical Polymerization [J]. Journal of Polymer Science:Part A:Polymer Chemistry,2003,41:2197-2206
27. Trenor S R, Long T E, Love B J. Photoreversible Chain Extension of Poly(ethylene glycol) [J]. Macromolecular Chemistry and Physics,2004,205:715-723
28. Trenor S R, Long T E, Love B J. Crystallization of photo-chain extended poly(ethylene glycol) [J]. European Polymer Journal,2005,41:219-224
29. Trajkovska A, Kim C, Marshall K L, et al. Photoalignment of a Nematic Liquid Crystal Fluid and Glassy-Nematic Oligofluorenes on Coumarin-Containing Polymer Films [J]. Macromolecules,2006,39(20):6983-6989
30. Kim C, Trajkovska A, Wallace J U, et al. New Insight into Photoalignment of Liquid Crystals on Coumarin-Containing Polymer Films [J]. Macromolecules,2006,39(11): 3817-3823
31. Kim C, Wallace J U, Chen S H, et al. Effects of Dilution, Polarization Ratio and Energy Transfer on Photoalignment of Liquid Crystals Using Coumarin-Containing Polymer Films [J]. Macromolecules,2008,41(9):3075-3080
32. Kim C, Marshall K L, Wallace J U, et al. Novel Cholesteric Glassy Liquid Crystals Comprising Benzene Functionalized with Hybrid Chiral-Nematic Mesogens [J]. Chemistry of Materials,2008,20(18):5859-5868
33. Stoiljkovic A, Agarwal S. Short Electrospun Fibers by UV Cutting Method [J]. Macromolecular Materials and Engineering,2008,293:895-899
34. Sinkel C, Greiner A, Agarwal S. Synthesis, Characterization and Properties Evaluation of Methylcoumarin End-Functionalized Poly(methyl methacrylate) for Photoinduced Drug Release [J]. Macromolecules,2008,41(10):3460-3467
35. Sinkel C, Greiner A, Agarwal S. A Polymeric Drug Depot Based on 7-(2'-Methacryloyloxyethoxy)-4-methylcoumarin Copolymers for Photoinduced Release of 5-Fluorouracil Designed for the Treatment of Secondary Cataracts [J]. Macromolecular Chemistry and Physics,2010,211:1857-1867
36. Zhao Y. Rational Design of Light-Controllable Polymer Micelles [J]. The Chemical Record,2007,7:286-294
37. Jiang J Q, Qi B, Lepage M, et al. Polymer Micelles Stabilization on Demand through Reversible Photo-Cross-Linking [J]. Macromolecules,2007,40(4):790-792
38. Dahmane S, Lasia A, Zhao Y. Electrochemically Active Block Copolymer Micelles Containing Coumarin Moieties [J]. Macromolecular Chemistry and Physics,2008,209:1065-1072
39. Babin J, Lepage M, Zhao Y. "Decoration" of Shell Cross-Linked Reverse Polymer Micelles Using ATRP:A New Route to Stimuli-Responsive Nanoparticles [J]. Macromolecules,2008,41(4):1246-1253
40. He J, Zhao Y, Zhao Y. Photoinduced bending of a coumarin-containing supramolecular polymer [J]. Soft Matter,2009,5:308-310
41. Zhao Y, Bertrand J, Tong X, et al. Photo-Cross-Linkable Polymer Micelles in Hydrogen-Bonding-Built Layer-by-Layer Films [J]. Langmuir,2009,25(22):13151-13157
42. He J, Tong X, Zhao Y. Photoresponsive Nanogels Based on Photocontrollable Cross-Links[J]. Macromolecules,2009,42(13):4845-4852
43. He J, Tong X, Tremblay L, et al. Corona-Cross-Linked Polymer Vesicles Displaying a Large and Reversible Temperature-Responsive Volume Transition [J]. Macromolecules,2009, 42(19):7267-7270
44. He J, Zhao Y. Light-responsive polymer micelles,nano-and microgels based on the reversible photodimerization of coumarin [J]. Dyes and Pigments,2010:1-6
45.杨淑丽,刘晓亚,杨成等.聚合物溶液自组装胶束的研究进展[J].日用化学工业,2003,33(3)：164-166
46.朱蕙,刘世勇,潘全名等.窄分布两亲性嵌段共聚物的合成及其胶束化行为研究[J].高等学校化学学报,2002,21(1)：138-142
47.刘世勇,江明.高分子胶束化的新途径及胶束的结构演化[J].高等学校化学学报, 2001,22(6)：1066-1072
48.刘琼,吴文辉,陈颖等.荧光探针法研究疏水改性聚丙烯酰胺溶液的疏水缔合行为[J].功能高分子学报,2005,18(1)：22-27
49.严峰,王显光,曹绪龙等.荧光法测定N-(α-烷苯氧基)十四酰基牛磺酸钠的临界胶束浓度[J].感光科学与光化学,2007,25(2)：115-122
50. Flory P J. Molecular Size Distribution in Three Dimensional Polymers Ⅵ.Branched Polymers Containing A-R-Bf-1 Type Units [J]. Journal of the American Chemical Society, 1952,74(11):2718-2723
51. Kim Y H, Webster O W. Water-Soluble Hyperbranched Polyphenylene:"A Unimolecular Micelle"? [J]. Journal of the American Chemical Society,1990,112:4593-4594
52. Kang S H, Luo J D, Ma H, et al. A Hyperbranched Aromatic Fluoropolyester for Photonic Applications [J]. Macromolecules,2003,36(12):4355-4359
53. Yan D Y, Gao C. Hyperbranched Polymers Made from A2 and BB'2 Type Monomers.1. Polyaddition of 1-(2-Aminoethyl)piperazine to Divinyl Sulfone [J]. Macromolecules,2000, 33(21):7693-7699
54.唐黎明,方宇,由虎等.端丙烯酸酯基超支化聚(酯-胺)的结构分析及光固化[J].高分子学报,2005,2(2)：301-304
55. Wang D, Zheng Z J, Chunyan Hong, et al. Michael Addition Polymerizations of Difunctional Amines (AA') and Triacrylamides (B3) [J]. Journal of Polymer Science:Part A: Polymer Chemistry,2006,44:6226-6242
56. Satoh T, Imai T, Ishihara H, et al. Synthesis of Hyperbranched Polysaccharide by Thermally Induced Cationic Polymerization of 6-Anhydro-β-D-mannopyranose [J]. Macromolecules,2003,36(17):6364-6370
57. Mao J, Ni P, Mai Y Y, et al. Multicompartment Micelles from Hyperbranched Star-Block [J]. Langmuir,2007,23(9),5127-5134
58.高超,钱卉,王寿柏等.用ATRP法构筑核壳型梯度极性的多羟基多臂星状超支化聚合物及聚合物刷——三层聚合物刷的合成与表征[J].高分子学报,2004,6(6)：884-888
59.胡晖,曹中林,范晓东.环境敏感性超支化聚合物的合成及药物的控制释放[J].高分子材料科学与工程,2005,21(2)：102-105
60. Hua F J, Ruckenstein E. Hyperbranched Sulfonated Polydiphenylamine as a Novel Self-Doped Conducting Polymer and Its pH Response [J]. Macromolecules,2005,38(3): 888-898
61. Liu B L, Kazlauciunas A, Guthrie J T, et al. One-Pot Hyperbranched Polymer Synthesis Mediated by Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization [J]. Macromolecules,2005,38(6):2131-2136
62. Dong W Y, Zhou Y F, Yan D Y, et al. Honeycomb-Structured Microporous Films Made from Hyperbranched Polymers by the Breath Figure Method [J]. Langmuir,2009,25(1): 173-178
63.潘祖仁主编.高分子化学[M]：第三版.北京：化学工业出版社,2006,144
64. Kitajyo Y, Kinugawa Y, Tamaki M, et al. Synthesis, Characterization and Functionalization of Hyperbranched Poly(3,4-epoxycyclohexanemethanol) [J]. Macromolecules,2007,40(26),9313-9321
65. Lin Y, Liu X H, Dong Z M, et al. Amphiphilic Core-Shell Nanocarriers Based On Hyperbranched Poly(ester amide)-star-PCL:Synthesis,Characterization and Potential as Efficient Phase Transfer Agent [J]. Biomacromolecules,2008,9(10):2629-2636
66. Kainthan R K, Zou Y Q, Chiao M, et al. Self-Assembled Monothiol-Terminated Hyperbranched Polyglycerols on a Gold Surface:A Comparative Study on the Structure, Morphology and Protein Adsorption Characteristics with Linear Poly(ethylene glycol)s [J]. Langmuir,2008,24(9),4907-4916
67. Jia Z F, Chen H, Zhu X Y, et al. Backbone-Thermoresponsive Hyperbranched Polyethers [J]. Journal of the American Chemical Society,2006,128(25):8144-8145
68. Frechet J M J, Henmi M, Gitsov I, et al. Self-Condensing Viny Polymerization:An Approach to Dendritic Materials [J]. Science,1995,269:1081-1083
69. Weimer M W, Frechet J M J, Gitsov I. Importance of Active-Site Reactivity and Reaction Conditions in the Preparation of Hyperbranched Polymers by Self-Condensing Vinyl Polymerization:Highly Branched vs.Linear Poly[4-(chloromethyl)styrene] by Metal-Catalyzed "Living" Radical Polymerization [J]. Journal of Polymer Science:Part A: Polymer Chemistry,1998,36:955-970
70. Baskaran D. Hyperbranched polymers from divinylbenzene and 1,3-diisopropenylbenzene through anionic self-condensing vinyl polymerization [J]. Polymer, 2003,44:2213-2220
71.贾志峰,陈皞,颜德岳.通过自缩合乙烯基氧阴离子聚合制备超支化聚甲基丙烯酸羟丙酯[J].化学学报,2005,63(20)：1861-1865
72. Muthukrishnan S, Erhard D P, Mori H, et al. Synthesis and Characterization of Surface-Grafted Hyperbranched Glycomethacrylates [J]. Macromolecules,2006,39(8): 2743-2750
73. Tian L F, Shu X, Zhu J. A Hyperbranched, Highly Deliquescent Polymer [J]. Advanced Materials,2007,19:4548-4551
74. Li X, Hong C Y, Pan C Y. Preparation and characterization of hyperbranched polymer grafted mesoporous silica nanoparticles via self-condensing atom transfer radical vinyl polymerization [J]. Polymer,2010,51:92-99
75. Humphrey R E, Hawkins J M. Reduction of Aromatic Disulfides with Triphenylphosphine [J]. Journal of Analytical Chemistry,1964,36:1812-1814
76. Humphrey R E, Potter J L. Reduction of Disulfides with Tributylphosphine [J]. Journal of Analytical Chemistry,1965,37:164-165
77. Tsarevsky N V, Matyjaszewski K. Combining Atom Transfer Radical Polymerization and Disulfide/Thiol Redox Chemistry:A Route to Well-Defined (Bio)degradable Polymeric Materials[J]. Macromolecules,2005,38(8):3087-3092
78. Sonavane S U, Chidambaram M, Khalil S, et al. Synthesis of cyclic disulfides using didecyldimethylammonium bromide as phase transfer catalyst [J]. Tetrahedron Letters,2008, 49:520-522
79. Harrisa J R, Roosb C, Djalali R,et al. Application of the negative staining technique to both aqueous and organic solvent solutions of polymer particles [J]. Micron,1999,30: 289-298
80. Wang J S, Matyjaszewski K. Controlled/"Living" Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process [J]. Macromolecules,1995,28(23):7901-7910
81. Wang J S, Matyjaszewski K. Control led"Living" Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes [J]. Journal of the American Chemical Society,1995,117(20):5614-5615
82.江明,A.艾森伯格,刘国军,张希等著.大分子自组装[M]：北京：科学出版社,2006.3-4
83.谭惠民,罗运军著.超支化聚合物[M]：北京：化学工业出版社,2005.73-121,209-212
84. Irfan M, Seiler M. Encapsulation Using Hyperbranched Polymers:From Research and Technologies to Emerging Applications [J]. Industrial & Engineering Chemistry Research, 2010,49(3):1169-1196
85. Yates C R, Hayes W. Synthesis and applications of hyperbranched polymers [J]. European Polymer Journal,2004,40:1257-1281
86. Kishore K, Ganesh K. Synthesis, Characterization and Thermal Degradation Studies on Group VIA Derived Weak-Link Polymers [J]. Macromolecules,1993,26(17):4700-4705
87.何曼君,陈维孝,董西侠.高分子物理[M]：复旦大学出版社,2006,226-260
88. Kim Y H, Webster O W. Hyperbranched polyphenylenes [J]. Macromolecules,1992,25(21)：5561-5572
89.洪玲,王新灵,赵喜安等.多检测凝胶渗透色谱技术在超支化聚氨酯表征中的应用[J].上海交通大学学报,2003,37(5)：629-631
2. Yamazaki M, Tanaka M, Shimada T. Highly sensitive high-performance liquid chromatographic assay for coumarin 7-hydroxylation and 7-ethoxycoumarin O-deethylation by human liver cytochrome P450 enzymes [J]. Journal of Chromatography B,1999,721: 13-19
3. FernaAndez Izquierdo M E, Quesada Granados J, VillaloAn Mir M, et al. Comparison of methods for determining coumarins in distilled beverages [J]. Food Chemistry,2000,70: 251-258
4. Cohen B, Huppert D. Excited State Proton-Transfer Reactions of Coumarin 4 in Protic Solvents [J]. Journal of Physical Chemistry A,2001,105:7157-7164
5. Trenor S R, Shultz A R, Love B J, et al. Coumarins in Polymers:From Light Harvesting to Photo-Cross-Linkable Tissue Scaffolds[J]. Chemical Reviews,2004,104:3059-3077
6. Chen Y, Geh J L. Copolymers derived from 7-acryloyloxy-4-methylcoumarin and acrylates:1. Copolymerizability and photocrosslinking behaviours [J]. Polymer,1996,37(20): 4473-4480
7. Chen Y, Jean C S. Polyethers Containing Coumarin Dimer Components in the Main Chain.Ⅱ. Reversible Photocleavage and Photopolymerization [J]. John Wiley & Sons,1997, 1759-1768
8. Chujo Y, Sada Y, Saegusa T. Polyoxazoline Having a Coumarin Moiety as a Pendant Group. Synthesis and Photogelation [J]. Macromolecules,1990,23:2693-2697
9. Chen Y, Geh J L. Copolymers derived from 7-acryloyloxy-4-methylcoumarin and acrylates:2. Reversible photocrosslinking and photocleavage [J]. Polymer,1996,37(20): 4481-4486
10. Chen Y, Chen K H. Synthesis and Reversible Photocleavage of Novel Polyurethane Containing Coumarin Dimer Components [J]. Journal of Polymer Science:Part A:Polymer Chemistry,1997,35,613-624
11. Chen Y, Hong R T. Photopolymerization of 7,7'-Coumarinyl Polymethylene Dicarboxylates:Fluorescence and Kinetic Study [J]. Journal of Polymer Science:Part A: Polymer Chemistry,1997,35:2999-3008
12.张传智,蒋春霞,王旭等.含香豆素功能基聚合物的合成及荧光性能[J].高分子材料科学与工程,2007,23(6)：85-88
13. Wang B Y, Guan X L, Hu Y L, et al. Preparation and fluorescent properties of poly(vinyl alcohol) bearing coumarin [J]. Polymers for Advanced Technologies,2007,18:529-534
14. Wang B Y, Liu X Y, Hu Y L, et al. Synthesis and photophysical behavior of a water-soluble coumarin-bearing polymer for proton and Ni2+ ion sensing [J]. Polymer International,2009,58:703-709
15. Ren B Y, Zhao D L, Liu S S, et al. Synthesis and Characterization of Poly(ferrocenylsilanes) with Coumarin Side Groups and Their Photochemical Reactivity and Electrochemical Behavior[J]. Macromolecules,2007,40(13):4501-4508
16. Zhao D L, Ren B Y, Liu S S, et al. A novel photoreversible poly(ferrocenylsilane) with coumarin side group:synthesis, characterization and electrochemical activities [J]. Chemical Communications,2006,779-781
17. Fu Q, Cheng L L, Zhang Y, et al. Preparation and reversible photo-crosslinking/photo-cleavage behavior of 4-methylcoumarin functionalized hyperbranched polyester [J]. Polymer,2008,49:4981-4988
18.傅祺.超支化聚酯的合成与表面修饰及其光敏性能研究[D]：[硕士学位论文].中国科技大学高分子科学与工程系,2009
19. Fujiwara M, Shiokawa K, Kawasaki N, et al. Photodimerization of Coumarin-Derived Pentacyclo[9.5.1.1.1.1]octasiloxane to Fabricate a Three-Dimensional Organic-Inorganic Hybrid Material [J], Advanced Functional Materials,2003,13(5):371-376
20. Mal N K, Fujiwara M, Tanaka Y. Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica [J]. Nature,2003,421:350-353
21. Mal N K, Fujiwara M, Tanaka Y, et al. Photo-Switched Storage and Release of Guest Molecules in the Pore Void of Coumarin-Modified MCM-41 [J].Chemistry of Materials,2003, 15(17):3385-3394
22. Matsuda T, Mizutani M. Molecular Design of Photocurable Liquid Biodegradable Copolymers.2. Synthesis of Coumarin-Derivatized Oligo(methacrylate)s and Photocuring [J]. Macromolecules,2000,33(3):791-794
23. Matsuda T, Mizutani M, Arnold S C. Molecular Design of Photocurable Liquid Biodegradable Copolymers.1. Synthesis and Characteristics Photocuring [J]. Macromolecules,2000,33(3):795-800
24. Mizutani M, Matsuda M. Liquid photocurable biodegradable copolymers:In vivo degradation of photocured poly(ε-caprolactone-co-trimethylene carbonate) [J].2002 Wiley Periodicals, Inc.54-60
25. Mizutani M, Matsuda T. Photocurable Liquid Biodegradable Copolymers:In Vitro Hydrolytic Degradation Behaviors of Photocured Films of Coumarin-Endcapped Poly(ε-caprolactone-co-trimethylene carbonate) [J]. Biomacromolecules,2002,3(2):249-255
26. Tian Y Q, Kong X X, Nagase Y, et al. Photocrosslinkable Liquid-Crystalline Block Copolymers with Coumarin Units Synthesized with Atom Transfer Radical Polymerization [J]. Journal of Polymer Science:Part A:Polymer Chemistry,2003,41:2197-2206
27. Trenor S R, Long T E, Love B J. Photoreversible Chain Extension of Poly(ethylene glycol) [J]. Macromolecular Chemistry and Physics,2004,205:715-723
28. Trenor S R, Long T E, Love B J. Crystallization of photo-chain extended poly(ethylene glycol) [J]. European Polymer Journal,2005,41:219-224
29. Trajkovska A, Kim C, Marshall K L, et al. Photoalignment of a Nematic Liquid Crystal Fluid and Glassy-Nematic Oligofluorenes on Coumarin-Containing Polymer Films [J]. Macromolecules,2006,39(20):6983-6989
30. Kim C, Trajkovska A, Wallace J U, et al. New Insight into Photoalignment of Liquid Crystals on Coumarin-Containing Polymer Films [J]. Macromolecules,2006,39(11): 3817-3823
31. Kim C, Wallace J U, Chen S H, et al. Effects of Dilution, Polarization Ratio and Energy Transfer on Photoalignment of Liquid Crystals Using Coumarin-Containing Polymer Films [J]. Macromolecules,2008,41(9):3075-3080
32. Kim C, Marshall K L, Wallace J U, et al. Novel Cholesteric Glassy Liquid Crystals Comprising Benzene Functionalized with Hybrid Chiral-Nematic Mesogens [J]. Chemistry of Materials,2008,20(18):5859-5868
33. Stoiljkovic A, Agarwal S. Short Electrospun Fibers by UV Cutting Method [J]. Macromolecular Materials and Engineering,2008,293:895-899
34. Sinkel C, Greiner A, Agarwal S. Synthesis, Characterization and Properties Evaluation of Methylcoumarin End-Functionalized Poly(methyl methacrylate) for Photoinduced Drug Release [J]. Macromolecules,2008,41(10):3460-3467
35. Sinkel C, Greiner A, Agarwal S. A Polymeric Drug Depot Based on 7-(2'-Methacryloyloxyethoxy)-4-methylcoumarin Copolymers for Photoinduced Release of 5-Fluorouracil Designed for the Treatment of Secondary Cataracts [J]. Macromolecular Chemistry and Physics,2010,211:1857-1867
36. Zhao Y. Rational Design of Light-Controllable Polymer Micelles [J]. The Chemical Record,2007,7:286-294
37. Jiang J Q, Qi B, Lepage M, et al. Polymer Micelles Stabilization on Demand through Reversible Photo-Cross-Linking [J]. Macromolecules,2007,40(4):790-792
38. Dahmane S, Lasia A, Zhao Y. Electrochemically Active Block Copolymer Micelles Containing Coumarin Moieties [J]. Macromolecular Chemistry and Physics,2008,209:1065-1072
39. Babin J, Lepage M, Zhao Y. "Decoration" of Shell Cross-Linked Reverse Polymer Micelles Using ATRP:A New Route to Stimuli-Responsive Nanoparticles [J]. Macromolecules,2008,41(4):1246-1253
40. He J, Zhao Y, Zhao Y. Photoinduced bending of a coumarin-containing supramolecular polymer [J]. Soft Matter,2009,5:308-310
41. Zhao Y, Bertrand J, Tong X, et al. Photo-Cross-Linkable Polymer Micelles in Hydrogen-Bonding-Built Layer-by-Layer Films [J]. Langmuir,2009,25(22):13151-13157
42. He J, Tong X, Zhao Y. Photoresponsive Nanogels Based on Photocontrollable Cross-Links[J]. Macromolecules,2009,42(13):4845-4852
43. He J, Tong X, Tremblay L, et al. Corona-Cross-Linked Polymer Vesicles Displaying a Large and Reversible Temperature-Responsive Volume Transition [J]. Macromolecules,2009, 42(19):7267-7270
44. He J, Zhao Y. Light-responsive polymer micelles,nano-and microgels based on the reversible photodimerization of coumarin [J]. Dyes and Pigments,2010:1-6
45.杨淑丽,刘晓亚,杨成等.聚合物溶液自组装胶束的研究进展[J].日用化学工业,2003,33(3)：164-166
46.朱蕙,刘世勇,潘全名等.窄分布两亲性嵌段共聚物的合成及其胶束化行为研究[J].高等学校化学学报,2002,21(1)：138-142
47.刘世勇,江明.高分子胶束化的新途径及胶束的结构演化[J].高等学校化学学报, 2001,22(6)：1066-1072
48.刘琼,吴文辉,陈颖等.荧光探针法研究疏水改性聚丙烯酰胺溶液的疏水缔合行为[J].功能高分子学报,2005,18(1)：22-27
49.严峰,王显光,曹绪龙等.荧光法测定N-(α-烷苯氧基)十四酰基牛磺酸钠的临界胶束浓度[J].感光科学与光化学,2007,25(2)：115-122
50. Flory P J. Molecular Size Distribution in Three Dimensional Polymers Ⅵ.Branched Polymers Containing A-R-Bf-1 Type Units [J]. Journal of the American Chemical Society, 1952,74(11):2718-2723
51. Kim Y H, Webster O W. Water-Soluble Hyperbranched Polyphenylene:"A Unimolecular Micelle"? [J]. Journal of the American Chemical Society,1990,112:4593-4594
52. Kang S H, Luo J D, Ma H, et al. A Hyperbranched Aromatic Fluoropolyester for Photonic Applications [J]. Macromolecules,2003,36(12):4355-4359
53. Yan D Y, Gao C. Hyperbranched Polymers Made from A2 and BB'2 Type Monomers.1. Polyaddition of 1-(2-Aminoethyl)piperazine to Divinyl Sulfone [J]. Macromolecules,2000, 33(21):7693-7699
54.唐黎明,方宇,由虎等.端丙烯酸酯基超支化聚(酯-胺)的结构分析及光固化[J].高分子学报,2005,2(2)：301-304
55. Wang D, Zheng Z J, Chunyan Hong, et al. Michael Addition Polymerizations of Difunctional Amines (AA') and Triacrylamides (B3) [J]. Journal of Polymer Science:Part A: Polymer Chemistry,2006,44:6226-6242
56. Satoh T, Imai T, Ishihara H, et al. Synthesis of Hyperbranched Polysaccharide by Thermally Induced Cationic Polymerization of 6-Anhydro-β-D-mannopyranose [J]. Macromolecules,2003,36(17):6364-6370
57. Mao J, Ni P, Mai Y Y, et al. Multicompartment Micelles from Hyperbranched Star-Block [J]. Langmuir,2007,23(9),5127-5134
58.高超,钱卉,王寿柏等.用ATRP法构筑核壳型梯度极性的多羟基多臂星状超支化聚合物及聚合物刷——三层聚合物刷的合成与表征[J].高分子学报,2004,6(6)：884-888
59.胡晖,曹中林,范晓东.环境敏感性超支化聚合物的合成及药物的控制释放[J].高分子材料科学与工程,2005,21(2)：102-105
60. Hua F J, Ruckenstein E. Hyperbranched Sulfonated Polydiphenylamine as a Novel Self-Doped Conducting Polymer and Its pH Response [J]. Macromolecules,2005,38(3): 888-898
61. Liu B L, Kazlauciunas A, Guthrie J T, et al. One-Pot Hyperbranched Polymer Synthesis Mediated by Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization [J]. Macromolecules,2005,38(6):2131-2136
62. Dong W Y, Zhou Y F, Yan D Y, et al. Honeycomb-Structured Microporous Films Made from Hyperbranched Polymers by the Breath Figure Method [J]. Langmuir,2009,25(1): 173-178
63.潘祖仁主编.高分子化学[M]：第三版.北京：化学工业出版社,2006,144
64. Kitajyo Y, Kinugawa Y, Tamaki M, et al. Synthesis, Characterization and Functionalization of Hyperbranched Poly(3,4-epoxycyclohexanemethanol) [J]. Macromolecules,2007,40(26),9313-9321
65. Lin Y, Liu X H, Dong Z M, et al. Amphiphilic Core-Shell Nanocarriers Based On Hyperbranched Poly(ester amide)-star-PCL:Synthesis,Characterization and Potential as Efficient Phase Transfer Agent [J]. Biomacromolecules,2008,9(10):2629-2636
66. Kainthan R K, Zou Y Q, Chiao M, et al. Self-Assembled Monothiol-Terminated Hyperbranched Polyglycerols on a Gold Surface:A Comparative Study on the Structure, Morphology and Protein Adsorption Characteristics with Linear Poly(ethylene glycol)s [J]. Langmuir,2008,24(9),4907-4916
67. Jia Z F, Chen H, Zhu X Y, et al. Backbone-Thermoresponsive Hyperbranched Polyethers [J]. Journal of the American Chemical Society,2006,128(25):8144-8145
68. Frechet J M J, Henmi M, Gitsov I, et al. Self-Condensing Viny Polymerization:An Approach to Dendritic Materials [J]. Science,1995,269:1081-1083
69. Weimer M W, Frechet J M J, Gitsov I. Importance of Active-Site Reactivity and Reaction Conditions in the Preparation of Hyperbranched Polymers by Self-Condensing Vinyl Polymerization:Highly Branched vs.Linear Poly[4-(chloromethyl)styrene] by Metal-Catalyzed "Living" Radical Polymerization [J]. Journal of Polymer Science:Part A: Polymer Chemistry,1998,36:955-970
70. Baskaran D. Hyperbranched polymers from divinylbenzene and 1,3-diisopropenylbenzene through anionic self-condensing vinyl polymerization [J]. Polymer, 2003,44:2213-2220
71.贾志峰,陈皞,颜德岳.通过自缩合乙烯基氧阴离子聚合制备超支化聚甲基丙烯酸羟丙酯[J].化学学报,2005,63(20)：1861-1865
72. Muthukrishnan S, Erhard D P, Mori H, et al. Synthesis and Characterization of Surface-Grafted Hyperbranched Glycomethacrylates [J]. Macromolecules,2006,39(8): 2743-2750
73. Tian L F, Shu X, Zhu J. A Hyperbranched, Highly Deliquescent Polymer [J]. Advanced Materials,2007,19:4548-4551
74. Li X, Hong C Y, Pan C Y. Preparation and characterization of hyperbranched polymer grafted mesoporous silica nanoparticles via self-condensing atom transfer radical vinyl polymerization [J]. Polymer,2010,51:92-99
75. Humphrey R E, Hawkins J M. Reduction of Aromatic Disulfides with Triphenylphosphine [J]. Journal of Analytical Chemistry,1964,36:1812-1814
76. Humphrey R E, Potter J L. Reduction of Disulfides with Tributylphosphine [J]. Journal of Analytical Chemistry,1965,37:164-165
77. Tsarevsky N V, Matyjaszewski K. Combining Atom Transfer Radical Polymerization and Disulfide/Thiol Redox Chemistry:A Route to Well-Defined (Bio)degradable Polymeric Materials[J]. Macromolecules,2005,38(8):3087-3092
78. Sonavane S U, Chidambaram M, Khalil S, et al. Synthesis of cyclic disulfides using didecyldimethylammonium bromide as phase transfer catalyst [J]. Tetrahedron Letters,2008, 49:520-522
79. Harrisa J R, Roosb C, Djalali R,et al. Application of the negative staining technique to both aqueous and organic solvent solutions of polymer particles [J]. Micron,1999,30: 289-298
80. Wang J S, Matyjaszewski K. Controlled/"Living" Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process [J]. Macromolecules,1995,28(23):7901-7910
81. Wang J S, Matyjaszewski K. Control led"Living" Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes [J]. Journal of the American Chemical Society,1995,117(20):5614-5615
82.江明,A.艾森伯格,刘国军,张希等著.大分子自组装[M]：北京：科学出版社,2006.3-4
83.谭惠民,罗运军著.超支化聚合物[M]：北京：化学工业出版社,2005.73-121,209-212
84. Irfan M, Seiler M. Encapsulation Using Hyperbranched Polymers:From Research and Technologies to Emerging Applications [J]. Industrial & Engineering Chemistry Research, 2010,49(3):1169-1196
85. Yates C R, Hayes W. Synthesis and applications of hyperbranched polymers [J]. European Polymer Journal,2004,40:1257-1281
86. Kishore K, Ganesh K. Synthesis, Characterization and Thermal Degradation Studies on Group VIA Derived Weak-Link Polymers [J]. Macromolecules,1993,26(17):4700-4705
87.何曼君,陈维孝,董西侠.高分子物理[M]：复旦大学出版社,2006,226-260
88. Kim Y H, Webster O W. Hyperbranched polyphenylenes [J]. Macromolecules,1992,25(21)：5561-5572
89.洪玲,王新灵,赵喜安等.多检测凝胶渗透色谱技术在超支化聚氨酯表征中的应用[J].上海交通大学学报,2003,37(5)：629-631