树枝状丙烯酸酯的分子设计与性能研究
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摘要
树枝状大分子(Dendrimer)是一类新型的功能大分子化合物，它的特点是可以在分子水平上进行分子的大小、形状、功能基团的设计。根据树枝状大分子结构本身的特点，系统地开展分子结构与性能方面的研究。开发具有新型末端基的功能大分子是一个重要的研究方向。树枝状大分子的表面末端基都可以进行功能基转化，目前已报道的功能基有胺基、羟基、羧基、酯基、酰胺基、金属螯合物等；由于树枝状大分子的中心以及内部存在活性点，在药物输送、催化反应、基因治疗、金属纳米复合材料及膜材料等方面都显示了良好的应用前景。
本论文在对树枝状大分子的结构和性能进行了简要的介绍，并系统地回顾了树枝状大分子在合成和功能化方面的最新研究进展的基础上，提出了一种新的树枝状大分子末端基转化的方法，通过分子设计将具有功能性的基团经过迈克尔加成反应及酰胺化缩合反应接枝到树枝状大分子上，合成了一系列聚酰胺—胺树枝状大分子，设计并首次成功地合成了以乙二胺为核心的一类新型的树枝状丙烯酸酯。通过元素分析、红外光谱以及核磁共振实验对新型的树枝状大分子的结构进行了表征，证明了合成树枝状大分子的结构与设计目标分子的结构相符。
本论文根据树枝状大分子的结构特点，对首次合成的树枝状大分子的性能作了初步探索。通过滴体积法对半代的聚酰胺—胺和0.5代树枝状十二酯在丙酮中的表面活性进行了研究，重点讨论了半代聚酰胺—胺和0.5代树枝状长链酯在70℃时对稠油的降粘效果，发现这两类大分子在丙酮中都不具有表面活性，半代聚酰胺—胺和0.5代树枝状长链酯对稠油都具有降粘性能，在浓度为0.6％时降粘性能最佳，0.5代、1.5代和2.5代PAMAM的降粘率分别为24.5％、26.0％和28.2％，0.5代辛酯、十二酯和十八酯的降粘率分别为26.2％、28.3％和32.4％。此外，还对1.5代树枝状丙烯酸长链酯对稠油的降粘性能作了初步探讨，在浓度为0.6％时降粘性能最佳，降粘率为30.6％。根据树枝状大分子对稠油降粘性能的评价，探讨了稠油的降粘机理与降粘剂分子结构的关系，为设计和合成具有新型结构的单一原油降粘剂奠定基础。本论文的创新之处是首次将树枝状大分子应用于降粘领域，拓宽了新型树枝状大分子的应用领域。
Dendrimer is a new-type function macromolecule chemical compound whose specialties are to design the molecular size.shape and functional group at the molecular level. According to its own specialties, studying systematacially the molecular structure and performance, developing the function macromolecule with new-type terminal group is an important research direction. The surface terminal group can carry on function transform. There are amido, hydroxyl, carboxyl, ester base, acylamino group , metal chelate compound etc that have already been reported at present. Because there are active sites among the center and inside of dendrimers.,Those make this kind of macromolecule have well enough application prospects in drug deliver, catalyst carrier, gene therapy, metal millimicron composite and membrane material etc.
The thesis has introduced briefly the structure and performance of dendrimers, and has reviewed the newest progress in synthesizing and functional of dendrmers systematically. A new method of terminal group transforms of dendrimers was put forward. The method is that functional groups were grafted into dendrimers with Michael addition reaction and amidation condensation reaction by molecule design. Firstly a new-type dendritic twelve esters with ethylenediamine as core has been synthesized successfully. The molecular structures of the product have been characterized by means of element analysis, infrared spectrum(IR) and nuclear magnetic resonance(NMR). The validity of the molecular structure of dendrimer was proved tomatch with the designing target molecular
This thesis has explored tentatively the performance of dendrimers synthesized firstly, by the structure characteristics of dendrimers. The surface tensions of 0.5Gpoly(amidoamine)(PAMAM) and 0.5G dendritic twelve esters in the acetone were measured by drop-volume method. The viscosity-reducing result of half generation PAMAM and 0.5G dendritic longchain esters on oil was discussed emphatically. That these two kinds of dendrimers do not have surface activation basically in the acetone was found. Half generation PAMAM and 0. 5 generation dendritic longchain esters have viscidity of dropping to the thick oil, At the concentration of 0.6%, the viscosity-reducing result is best. The viscosity-reducing rates of 0.5 G PAMAM, 1.5G PAMAM and 2.5G PAMAM are respectively 25.4%, 26.0% and 28.2%. The rates of 0.5G dendritic eight esters, twelve esters and eighteen esters are 24 respectively 26.2%, 28.3% and 32.4%. In addition, the viscosity-reducing result of 1.5G dendritic twelve esters on oil was dicussed. The rate is 30.6% at the concentration of 0.6%.The relation of the thick-oil viscosity-reducing mechanism and the structure of viscosity reducer was explored. Those were the base of designing and synthesizing a new-type and single oil-viscosity reducer. The innovation of this thesis that dendrimers were applied to the viscosity-reducing fields firstly, and widened the applying fields of the new-type dendrimers.
本论文在对树枝状大分子的结构和性能进行了简要的介绍，并系统地回顾了树枝状大分子在合成和功能化方面的最新研究进展的基础上，提出了一种新的树枝状大分子末端基转化的方法，通过分子设计将具有功能性的基团经过迈克尔加成反应及酰胺化缩合反应接枝到树枝状大分子上，合成了一系列聚酰胺—胺树枝状大分子，设计并首次成功地合成了以乙二胺为核心的一类新型的树枝状丙烯酸酯。通过元素分析、红外光谱以及核磁共振实验对新型的树枝状大分子的结构进行了表征，证明了合成树枝状大分子的结构与设计目标分子的结构相符。
本论文根据树枝状大分子的结构特点，对首次合成的树枝状大分子的性能作了初步探索。通过滴体积法对半代的聚酰胺—胺和0.5代树枝状十二酯在丙酮中的表面活性进行了研究，重点讨论了半代聚酰胺—胺和0.5代树枝状长链酯在70℃时对稠油的降粘效果，发现这两类大分子在丙酮中都不具有表面活性，半代聚酰胺—胺和0.5代树枝状长链酯对稠油都具有降粘性能，在浓度为0.6％时降粘性能最佳，0.5代、1.5代和2.5代PAMAM的降粘率分别为24.5％、26.0％和28.2％，0.5代辛酯、十二酯和十八酯的降粘率分别为26.2％、28.3％和32.4％。此外，还对1.5代树枝状丙烯酸长链酯对稠油的降粘性能作了初步探讨，在浓度为0.6％时降粘性能最佳，降粘率为30.6％。根据树枝状大分子对稠油降粘性能的评价，探讨了稠油的降粘机理与降粘剂分子结构的关系，为设计和合成具有新型结构的单一原油降粘剂奠定基础。本论文的创新之处是首次将树枝状大分子应用于降粘领域，拓宽了新型树枝状大分子的应用领域。
Dendrimer is a new-type function macromolecule chemical compound whose specialties are to design the molecular size.shape and functional group at the molecular level. According to its own specialties, studying systematacially the molecular structure and performance, developing the function macromolecule with new-type terminal group is an important research direction. The surface terminal group can carry on function transform. There are amido, hydroxyl, carboxyl, ester base, acylamino group , metal chelate compound etc that have already been reported at present. Because there are active sites among the center and inside of dendrimers.,Those make this kind of macromolecule have well enough application prospects in drug deliver, catalyst carrier, gene therapy, metal millimicron composite and membrane material etc.
The thesis has introduced briefly the structure and performance of dendrimers, and has reviewed the newest progress in synthesizing and functional of dendrmers systematically. A new method of terminal group transforms of dendrimers was put forward. The method is that functional groups were grafted into dendrimers with Michael addition reaction and amidation condensation reaction by molecule design. Firstly a new-type dendritic twelve esters with ethylenediamine as core has been synthesized successfully. The molecular structures of the product have been characterized by means of element analysis, infrared spectrum(IR) and nuclear magnetic resonance(NMR). The validity of the molecular structure of dendrimer was proved tomatch with the designing target molecular
This thesis has explored tentatively the performance of dendrimers synthesized firstly, by the structure characteristics of dendrimers. The surface tensions of 0.5Gpoly(amidoamine)(PAMAM) and 0.5G dendritic twelve esters in the acetone were measured by drop-volume method. The viscosity-reducing result of half generation PAMAM and 0.5G dendritic longchain esters on oil was discussed emphatically. That these two kinds of dendrimers do not have surface activation basically in the acetone was found. Half generation PAMAM and 0. 5 generation dendritic longchain esters have viscidity of dropping to the thick oil, At the concentration of 0.6%, the viscosity-reducing result is best. The viscosity-reducing rates of 0.5 G PAMAM, 1.5G PAMAM and 2.5G PAMAM are respectively 25.4%, 26.0% and 28.2%. The rates of 0.5G dendritic eight esters, twelve esters and eighteen esters are 24 respectively 26.2%, 28.3% and 32.4%. In addition, the viscosity-reducing result of 1.5G dendritic twelve esters on oil was dicussed. The rate is 30.6% at the concentration of 0.6%.The relation of the thick-oil viscosity-reducing mechanism and the structure of viscosity reducer was explored. Those were the base of designing and synthesizing a new-type and single oil-viscosity reducer. The innovation of this thesis that dendrimers were applied to the viscosity-reducing fields firstly, and widened the applying fields of the new-type dendrimers.
引文
[1] 李建波，梁发书，郭川梅等．稠油降粘剂的合成及其作用机理分析．西南石油学院学报．2001，23(1)：40-43
[2] 吴本芳，张敏涛．复配型特稠原油降粘剂研究．洛阳师范学院学报．2003，2(3)：45-49
[3] 赵秉臣，李栋林，于萍．一种复合型高粘原油降粘降凝剂．沈阳化工学院学报．1999，13(3)：227-230
[4] 郭东红，江龙．辽河超稠原油的流变性质及其乳化降粘．化学通报．2002，10(5)：692-965
[5] 吴本芳，沈本贤，杨允明．辽河特稠油降粘研究．油气储运．2003，22(6)：27-32
[6] 范洪富，刘永建等．国内首例井下水热裂解催化降粘开采稠油现场试验．石油钻采工艺．2001，23(3)：42-44
[7] 张付生，谢会专等．原油降凝降粘剂在原油开采和集输中的应用．精细石油化工．1999，6(2)：27-30
[8] 张毅，赵明方．马来酸酐—苯乙烯—丙烯酸高级酯稠油降粘剂MSA的研制．油田化学，2000，17(2)：136-139
[9] 周凤山，吴瑾光．稠油化学降粘技术研究进展．油田化学．2001，18(2)：121-126
[10] 吴本芳，郭金波．稠油油溶性降粘剂研究进展概况．油气储运．2003，22(2)：1-6
[11] 胡合贵，高建厂等．不同分子结构星型降凝剂对油品降凝、降粘性能的影响．石油学报．2000，16(1)：40-46
[12] 周凤山，赵明方等．一种稠油降粘剂的研制与应用．西安石油学院学报．2000，15(2)：52-54
[13] 梁发书，肖超等．稠油降粘剂的室内研究．石油与天然气化工．2001，30(2)：87-89
[14] 于萍，蒋维，赵秉臣．一种高粘原油降粘剂的合成．沈阳化工学院学报．2001，15(3)：183-186
[15] 王世虎，孙克己，麻金海等．用化学方法改进稠油开采效果的技术．油田化学．2002，19(3)：210-213
[16] 王彪，谢会专，黄丽坚等．一种含极性基的三元共聚物及含该共聚物的组合物．油田化学．1997，4：458-462
[17] 何曼君，陈维孝，董西侠．高分子物理．修订版．上海：复旦大学出版社，1990，1
[18] 潘祖仁．高分子化学．第二版．北京：化学工业出版社，1997，10
[19] 何天白，胡汉杰．功能高分子与新技术．化学工业出版社，2001，7
[20] Tomalia D A, Naylor A M, Goddard Ⅲ W A. Angew Chem Int Ed Engl, 1990, 29:138-175
[21] Tomalia D A, Durst H D. Top Curr Chem, 1993, 165:193-313
[22] Matthews O A, Shipway A N, Stoddart J F. Prog Polym Sci, 1998, 23:1-56
[23] Bhleier E, Wehener W. A V(?)gtle F. "Cascade"and "Nonskid-chain-like"Syntheses of Molecular Cavity Topologies. Synthesis 1987, 155-158
[24] 陈亚雄．一类新的多分枝大分子．有机化学．1990，10：289-297
[25] Tomalia D A, Baker H, Deward J et al.A New Class of Polymers:Starburst-Dendritic Macromolecules. Polym. J. 1985, 17:117-132
[26] Newkome G R, Yao Z Q, Baker G R et al. Cascade Molecules: A New Approach to Micelles Arborol J. Org. Chem. 1985, 50:2003-2004
[27] 陈永明，陈传福，习复．树枝状大分子的新进展．化学通报．1995，10：1-10
[28] Hawker C J, Frechet J M J. Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approch to Dendritic Macromoecules. J. Am. Chem. Soc. 1990, 112:7638-7647
[29] Serroni S, Denci G, Gampagha S. Arborols from luminescent and redox-active transition metal
complex fragments. Angew. Chem. Int. Ed. Engl. 1992, 31(11): 1493-1495
[30] 李于飞．一类新型的呈树状支化的合成高分子．高分子通报．1993，3：155-164
[31] Tomalia D A, Naylor A M, Goddard Ⅲ W A. Starburst Dendrimers: Molecular-level Control of Size Shape, Surface Chemistry, Topology, and Flexibility from Atoms to Macroscopic Matter. Angew Chem. Int. Ed. Engl. 1990, 29:138-175
[32] Matthews O A, Shipway A N, Stoddart J F. Dendrimers-branching out from curiosities into new techchnologies. Prog. Polym. Sci. 1998,23(1): 1-56
[33] Frechet J M J. Functional polymers and dendrimers: reactivity, molecular architecture, and interfacial energy Science. 1994, 263(5154): 1710-1715
[34] Malmstroem M, Johansson M, Hult, A. Hyperbranched Aliphatic Polyesters. Macromolecules 1995,28 (5):1698-1703
[35] 宁春花，徐冬梅，张可达等．具有分子识别功能的树状大分子．化学研究与应用．2002，14(5)：520-524
[36] Hawaker C J, Malmstrom E E, Frank C W et al. Exact Linear Analogs of Dendritic Polyether Macromolecules: Design, Synthesis, and Unique Properties. J. Am. Chem. Soc. 1997, 119:9903-9904
[37] Wells M, Crooks R M. Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe Molecules.10.Preparation and Properties of Chemically Sensitive Dendrimer Surfaces. J. Am. Chem. Soc. 1996, 118:3988-3989
[38] Tsukruk VV, Rinderspacher F, Bliznyuk VN. Langmuir, 1997, 13:2171-2178
[38] 崔光磊，李于飞．树状大分子研究在超分子化学领域中的拓展．大学化学，1999，14(3)：29-38
[39] 徐敏，谭克等．树状高分子的功能化进展．功能高分子学报．2001，14：481-487
[40] C.J. Hawker, J. M. J. Frechet, Unmolecular micelles and globular amphiphiles: Dendritic macromolecules as novel recyclable solubilization agents, J. Chem. Soc. Perkin Trans. 1993, 1:1287-1297
[41] Johan F.G.A. Jansen, E. W. Meijer, Encapsulation of guest molecules into a dendritic box, Science 1994, 266:1226-1229
[42] Turro, N. J. et al. Molecular recognition and chemistry in restricted reaction spaces. Acc. Chem.Res. 1991, 24:332-340
[43] Pelta, J. et al. DNA aggregation induced by polyamines and cobalthexamine. J. Biol. Chem. 1996,271:5656-5662
[44] Tam, J.P. Synthetic peptide vaccine design-synthesis and properties of a high-density multiple antigenic peptide system. Proc. Natl. Acad. Sci. USA, 1988, 85:5409-5413
[45] 王金风，贾欣茹等．树枝状大分子的自组装超薄膜．高等学校化学学报，2001，22(10)：1773-1775
[46] 沙耀武，武力．树枝状大分子的研究进展与应用前景．湖南化工．2000，30：1-5
[47] 侯昭升，张其震等．金属配位树状大分子的研究进展．化学进展．2002，14(6)：469-476
[48] 王金凤，贾欣如，金钟等．聚酰胺-胺型树枝状化合物与四氯化钛的配合及其催化作用初步研究高等学校化学学报．2001，22：709-711
[49] 徐敏，严晓虎，余学海．树枝状高分子PPI水溶液性质的研究[J]．高等学校化学学报，2001，22(4)703-705
[50] 朱鸣岗，张其震，侯昭升．树枝状聚合物合成方法的新进展．高分子通报．2002，4：32-40
[51] Wells M, Crooks R M. Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe. Molecules 10.Preparation and Properties of Chemically Sensitive Dendrimer Surfaces. J. Am.Chem. Soc. 1996,118:3988-3989
[52] Wooley K L, Hawker C J, Frechet J M J. Hyperbranched Macromolecules via a Novel Double-Stage Convergent Growth Approach. J. Am. Chem.Soc. 1991, 113:4252-4261
[53] Marquardt T, Luning U. Towards golfball shaped reagents: dendrimer fixed concave pyridines. Chem. Commun. 1997, 17:1681-1682
[54] 王国杰，王晓工．含偶氮苯生色团的树枝状大分子的研究进展．高分子通报．2002，3：19-23
[55] Niu Y, Yeung L K, Crooks R M. Size-Selective Hydrogenation of Olefins by Dendrimer-Encapsulated Palladium Nanoparticles. J. Am. Chem. Soc. 2001, 123, 6840-6846
[56] Alper H, Arya P, Bourque S et al. Heck reaction using palladium complexed to dendrimers on silica. Can. J. Chem. 2000, 78(6): 920-924
[57] 吴文娟，徐冬梅，宁春花等．聚酰胺-胺树状大分子的应用．高分子通报．2003，4：67-72
[58] Mingiun Liu,Kenji Kono, Jean M J Frechet, Watersoluble dendritic unimolecular micelles: Their potential as drug delivery agents. J Controlled Release, 2000, 65:121-131
[59] 扈金萍，刘永利，张锦楠．纳米生物材料—聚酰胺-胺树状大分子．首都医科大学学报．2002，23(3)：284-286
[60] Kollner C, Pugin B, Togni A. Dendrimers Containing Chiral Ferrocenyl Diphosphine Ligands for Asymmetric Catalysis. J. Am. Chem. Soc. 1998,120:10274-10275
[61] Dagani R.树枝状高分子化合物的功能研究．化工新型材料，1997(9)：21-23
[62] Hawker C J, Frechet J M J. Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approach to Dendritic Macromolecules. J. Am. Chem. Soc. 1990, 112:7638-7647
[63] 陈明亮．树枝状高聚物的合成概况．广州化学．1999，1：49-57
[64] 王俊，杨锦宗，陈红侠等．发散法合成树枝状高分了聚酰胺-胺[J]．台成化学，2001，9：62-64
[65] 丁伟，李柏林，肖翠玲等．丙烯酸十八酯的合成．大庆石油学院学报．1998，22：79-81
[66] 赵文宽，方程，贺飞等．仪器分析．高等教育出版社．2001，6
[67] 赵瑶兴，孙祥玉编著．有机分子结构光谱鉴定．科学出版社．2003，3
[68] 宁永成．有机化合物结构鉴定与有机波谱学．科学出版社．2000，1
[69] 李学尔，张锡鹏．丙烯酸高级酯的合成．石油化工高等学校学报．1996，9：18-22
[70] 朱步瑶，赵国玺．液体表面张力的测定．化学通报．1981，6：21-26
[2] 吴本芳，张敏涛．复配型特稠原油降粘剂研究．洛阳师范学院学报．2003，2(3)：45-49
[3] 赵秉臣，李栋林，于萍．一种复合型高粘原油降粘降凝剂．沈阳化工学院学报．1999，13(3)：227-230
[4] 郭东红，江龙．辽河超稠原油的流变性质及其乳化降粘．化学通报．2002，10(5)：692-965
[5] 吴本芳，沈本贤，杨允明．辽河特稠油降粘研究．油气储运．2003，22(6)：27-32
[6] 范洪富，刘永建等．国内首例井下水热裂解催化降粘开采稠油现场试验．石油钻采工艺．2001，23(3)：42-44
[7] 张付生，谢会专等．原油降凝降粘剂在原油开采和集输中的应用．精细石油化工．1999，6(2)：27-30
[8] 张毅，赵明方．马来酸酐—苯乙烯—丙烯酸高级酯稠油降粘剂MSA的研制．油田化学，2000，17(2)：136-139
[9] 周凤山，吴瑾光．稠油化学降粘技术研究进展．油田化学．2001，18(2)：121-126
[10] 吴本芳，郭金波．稠油油溶性降粘剂研究进展概况．油气储运．2003，22(2)：1-6
[11] 胡合贵，高建厂等．不同分子结构星型降凝剂对油品降凝、降粘性能的影响．石油学报．2000，16(1)：40-46
[12] 周凤山，赵明方等．一种稠油降粘剂的研制与应用．西安石油学院学报．2000，15(2)：52-54
[13] 梁发书，肖超等．稠油降粘剂的室内研究．石油与天然气化工．2001，30(2)：87-89
[14] 于萍，蒋维，赵秉臣．一种高粘原油降粘剂的合成．沈阳化工学院学报．2001，15(3)：183-186
[15] 王世虎，孙克己，麻金海等．用化学方法改进稠油开采效果的技术．油田化学．2002，19(3)：210-213
[16] 王彪，谢会专，黄丽坚等．一种含极性基的三元共聚物及含该共聚物的组合物．油田化学．1997，4：458-462
[17] 何曼君，陈维孝，董西侠．高分子物理．修订版．上海：复旦大学出版社，1990，1
[18] 潘祖仁．高分子化学．第二版．北京：化学工业出版社，1997，10
[19] 何天白，胡汉杰．功能高分子与新技术．化学工业出版社，2001，7
[20] Tomalia D A, Naylor A M, Goddard Ⅲ W A. Angew Chem Int Ed Engl, 1990, 29:138-175
[21] Tomalia D A, Durst H D. Top Curr Chem, 1993, 165:193-313
[22] Matthews O A, Shipway A N, Stoddart J F. Prog Polym Sci, 1998, 23:1-56
[23] Bhleier E, Wehener W. A V(?)gtle F. "Cascade"and "Nonskid-chain-like"Syntheses of Molecular Cavity Topologies. Synthesis 1987, 155-158
[24] 陈亚雄．一类新的多分枝大分子．有机化学．1990，10：289-297
[25] Tomalia D A, Baker H, Deward J et al.A New Class of Polymers:Starburst-Dendritic Macromolecules. Polym. J. 1985, 17:117-132
[26] Newkome G R, Yao Z Q, Baker G R et al. Cascade Molecules: A New Approach to Micelles Arborol J. Org. Chem. 1985, 50:2003-2004
[27] 陈永明，陈传福，习复．树枝状大分子的新进展．化学通报．1995，10：1-10
[28] Hawker C J, Frechet J M J. Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approch to Dendritic Macromoecules. J. Am. Chem. Soc. 1990, 112:7638-7647
[29] Serroni S, Denci G, Gampagha S. Arborols from luminescent and redox-active transition metal
complex fragments. Angew. Chem. Int. Ed. Engl. 1992, 31(11): 1493-1495
[30] 李于飞．一类新型的呈树状支化的合成高分子．高分子通报．1993，3：155-164
[31] Tomalia D A, Naylor A M, Goddard Ⅲ W A. Starburst Dendrimers: Molecular-level Control of Size Shape, Surface Chemistry, Topology, and Flexibility from Atoms to Macroscopic Matter. Angew Chem. Int. Ed. Engl. 1990, 29:138-175
[32] Matthews O A, Shipway A N, Stoddart J F. Dendrimers-branching out from curiosities into new techchnologies. Prog. Polym. Sci. 1998,23(1): 1-56
[33] Frechet J M J. Functional polymers and dendrimers: reactivity, molecular architecture, and interfacial energy Science. 1994, 263(5154): 1710-1715
[34] Malmstroem M, Johansson M, Hult, A. Hyperbranched Aliphatic Polyesters. Macromolecules 1995,28 (5):1698-1703
[35] 宁春花，徐冬梅，张可达等．具有分子识别功能的树状大分子．化学研究与应用．2002，14(5)：520-524
[36] Hawaker C J, Malmstrom E E, Frank C W et al. Exact Linear Analogs of Dendritic Polyether Macromolecules: Design, Synthesis, and Unique Properties. J. Am. Chem. Soc. 1997, 119:9903-9904
[37] Wells M, Crooks R M. Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe Molecules.10.Preparation and Properties of Chemically Sensitive Dendrimer Surfaces. J. Am. Chem. Soc. 1996, 118:3988-3989
[38] Tsukruk VV, Rinderspacher F, Bliznyuk VN. Langmuir, 1997, 13:2171-2178
[38] 崔光磊，李于飞．树状大分子研究在超分子化学领域中的拓展．大学化学，1999，14(3)：29-38
[39] 徐敏，谭克等．树状高分子的功能化进展．功能高分子学报．2001，14：481-487
[40] C.J. Hawker, J. M. J. Frechet, Unmolecular micelles and globular amphiphiles: Dendritic macromolecules as novel recyclable solubilization agents, J. Chem. Soc. Perkin Trans. 1993, 1:1287-1297
[41] Johan F.G.A. Jansen, E. W. Meijer, Encapsulation of guest molecules into a dendritic box, Science 1994, 266:1226-1229
[42] Turro, N. J. et al. Molecular recognition and chemistry in restricted reaction spaces. Acc. Chem.Res. 1991, 24:332-340
[43] Pelta, J. et al. DNA aggregation induced by polyamines and cobalthexamine. J. Biol. Chem. 1996,271:5656-5662
[44] Tam, J.P. Synthetic peptide vaccine design-synthesis and properties of a high-density multiple antigenic peptide system. Proc. Natl. Acad. Sci. USA, 1988, 85:5409-5413
[45] 王金风，贾欣茹等．树枝状大分子的自组装超薄膜．高等学校化学学报，2001，22(10)：1773-1775
[46] 沙耀武，武力．树枝状大分子的研究进展与应用前景．湖南化工．2000，30：1-5
[47] 侯昭升，张其震等．金属配位树状大分子的研究进展．化学进展．2002，14(6)：469-476
[48] 王金凤，贾欣如，金钟等．聚酰胺-胺型树枝状化合物与四氯化钛的配合及其催化作用初步研究高等学校化学学报．2001，22：709-711
[49] 徐敏，严晓虎，余学海．树枝状高分子PPI水溶液性质的研究[J]．高等学校化学学报，2001，22(4)703-705
[50] 朱鸣岗，张其震，侯昭升．树枝状聚合物合成方法的新进展．高分子通报．2002，4：32-40
[51] Wells M, Crooks R M. Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe. Molecules 10.Preparation and Properties of Chemically Sensitive Dendrimer Surfaces. J. Am.Chem. Soc. 1996,118:3988-3989
[52] Wooley K L, Hawker C J, Frechet J M J. Hyperbranched Macromolecules via a Novel Double-Stage Convergent Growth Approach. J. Am. Chem.Soc. 1991, 113:4252-4261
[53] Marquardt T, Luning U. Towards golfball shaped reagents: dendrimer fixed concave pyridines. Chem. Commun. 1997, 17:1681-1682
[54] 王国杰，王晓工．含偶氮苯生色团的树枝状大分子的研究进展．高分子通报．2002，3：19-23
[55] Niu Y, Yeung L K, Crooks R M. Size-Selective Hydrogenation of Olefins by Dendrimer-Encapsulated Palladium Nanoparticles. J. Am. Chem. Soc. 2001, 123, 6840-6846
[56] Alper H, Arya P, Bourque S et al. Heck reaction using palladium complexed to dendrimers on silica. Can. J. Chem. 2000, 78(6): 920-924
[57] 吴文娟，徐冬梅，宁春花等．聚酰胺-胺树状大分子的应用．高分子通报．2003，4：67-72
[58] Mingiun Liu,Kenji Kono, Jean M J Frechet, Watersoluble dendritic unimolecular micelles: Their potential as drug delivery agents. J Controlled Release, 2000, 65:121-131
[59] 扈金萍，刘永利，张锦楠．纳米生物材料—聚酰胺-胺树状大分子．首都医科大学学报．2002，23(3)：284-286
[60] Kollner C, Pugin B, Togni A. Dendrimers Containing Chiral Ferrocenyl Diphosphine Ligands for Asymmetric Catalysis. J. Am. Chem. Soc. 1998,120:10274-10275
[61] Dagani R.树枝状高分子化合物的功能研究．化工新型材料，1997(9)：21-23
[62] Hawker C J, Frechet J M J. Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approach to Dendritic Macromolecules. J. Am. Chem. Soc. 1990, 112:7638-7647
[63] 陈明亮．树枝状高聚物的合成概况．广州化学．1999，1：49-57
[64] 王俊，杨锦宗，陈红侠等．发散法合成树枝状高分了聚酰胺-胺[J]．台成化学，2001，9：62-64
[65] 丁伟，李柏林，肖翠玲等．丙烯酸十八酯的合成．大庆石油学院学报．1998，22：79-81
[66] 赵文宽，方程，贺飞等．仪器分析．高等教育出版社．2001，6
[67] 赵瑶兴，孙祥玉编著．有机分子结构光谱鉴定．科学出版社．2003，3
[68] 宁永成．有机化合物结构鉴定与有机波谱学．科学出版社．2000，1
[69] 李学尔，张锡鹏．丙烯酸高级酯的合成．石油化工高等学校学报．1996，9：18-22
[70] 朱步瑶，赵国玺．液体表面张力的测定．化学通报．1981，6：21-26