AB+A_f型星状支化高分子的结构参数研究
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摘要
本文主要以AB+A_f型星状支化聚合反应体系为例，利用反应统计理论对该反应体系的结构参数进行了研究。首先，利用统计理论给出了该反应体系的构象数分解公式，并对分解公式中各项的物理意义给出明确的解释。接着，利用分解公式，得到了AB+A_f型星状支化聚合反应体系的回转半径。对分子量分布平均后，给出了反应体系的重均和Z-均回转半径的精确表达式。
本文进一步探讨了该体系中的Z-均方回转半径随反应程度的变化规律。结果表明，该反应体系和由AB_f型单体缩聚形成的超支化聚合物反应体系有很大的不同，在反应接近完成时，AB+A_f型星状支化高分子的平均尺度将出现极值点，而由AB_f型单体缩聚反应得到超支化高分子的平均尺度将趋于无穷大。理论上，通过改变A_f型多官能团核的数目，就可以有效控制反应体系的平均尺度和平均支化度。本文给出了支化高分子结构参数和实验上可以测量的物理量—反应程度之间的明确关系，将为揭示支化高分子的结构与性能的关系，全面研究支化聚合物的反应机理奠定基础。
This dissertation for M.S. degree is mainly concerning some theoretical investigations for the star-branched polymer formed by AB + Af type
polycondensation.
Firstly, the statistical method was used to give the number of bonds formed for the star-branched polymer chains made by the AB + Af polymerization. With
the help of the kinetic model described by the Smoluchowski-like coagulation equation, the mean square radii of gyration were given analytically.
Furthermore, the z- and the weight average mean square radii of gyration were investigated explicitly. The results were much different from that of the hyperbranched polymers made by the ABf type monomers, where the former had
the finite values when the reaction was quantitatively completed, and the latter reached the infinite values. In principle, by varying the number of the Af type
multifunctional core moieties, the average sizes, as well as the average degrees, can be controlled effectively. With the detailed discussions of polymerization process, the conversion dependence of the mean size of star-branched polymers are undertaken, and hence some of results given by this dissertation are able to provide a new way of investigating highlybranched polymer in a deep level.
本文进一步探讨了该体系中的Z-均方回转半径随反应程度的变化规律。结果表明，该反应体系和由AB_f型单体缩聚形成的超支化聚合物反应体系有很大的不同，在反应接近完成时，AB+A_f型星状支化高分子的平均尺度将出现极值点，而由AB_f型单体缩聚反应得到超支化高分子的平均尺度将趋于无穷大。理论上，通过改变A_f型多官能团核的数目，就可以有效控制反应体系的平均尺度和平均支化度。本文给出了支化高分子结构参数和实验上可以测量的物理量—反应程度之间的明确关系，将为揭示支化高分子的结构与性能的关系，全面研究支化聚合物的反应机理奠定基础。
This dissertation for M.S. degree is mainly concerning some theoretical investigations for the star-branched polymer formed by AB + Af type
polycondensation.
Firstly, the statistical method was used to give the number of bonds formed for the star-branched polymer chains made by the AB + Af polymerization. With
the help of the kinetic model described by the Smoluchowski-like coagulation equation, the mean square radii of gyration were given analytically.
Furthermore, the z- and the weight average mean square radii of gyration were investigated explicitly. The results were much different from that of the hyperbranched polymers made by the ABf type monomers, where the former had
the finite values when the reaction was quantitatively completed, and the latter reached the infinite values. In principle, by varying the number of the Af type
multifunctional core moieties, the average sizes, as well as the average degrees, can be controlled effectively. With the detailed discussions of polymerization process, the conversion dependence of the mean size of star-branched polymers are undertaken, and hence some of results given by this dissertation are able to provide a new way of investigating highlybranched polymer in a deep level.
引文
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[2]Newkome, G. R.; He, Enfei; Moorefield, C. N. Chem. Rev. 1999, 99, 1689.
[3]Kim,Y. H. J. Polym. Science: PartA: Polym. Chem. 1998, 36, 1685.
[4]Volt. B. J. Polym. Science: PartA: Polym. Chem. 1998, 38, 2505.
[5]Yong H. Kim, Owen W. Webster; Water soluble hyperbranched poly-phenytene:" a unimolecular micelle?" J.Am. Chem. Soc.,1990, 112(11): 4592
[6]Mario Gauthier, Martin Moeller; Uniform highly branched polymers by anionic grafting: arborescent graft polymers. Macromolecules, 1991,24(16): 4548
[7]B. Voit, D. Beyerlein, K. Eichhorn, K. Grundke. Functional Hyperbranched Polyesters for Application in Coatings and Thin Films. Chemie Ingenieur Technik. 2001, 73(6): 687
[8]Xu-Tang Tao, Ya-Dong Zhang, Tatuso Wada. Hyperbranched Polymers for Electroluminescence Application. Advance Material. 1998,10(3): 226
[9]W.M.Lackowski, J. G..Franchina, D.E. Bergbreiter. An Atomic Force Microscopy Study of the Surface Morphology of Hyperbranched Poly (acrylic acid) Thin Films. Advanced Materials. 1999, 11 (6): 1368
[10]Anthony A. Gorman, I. Hamblett, C. Lambert. Hydrogen transfer from
1-naphthol triplet to ground-state benzophenone: kinetic evidence against proposed exciplex intermediacy, J. Am. Chem. Soc, ;1987, 109(5): 1600
[11]Trollsas, M.; Hedrick, J. L. Dendrimer-like Star Polymers J.Am.Chem. Soc. 1998, 120(19)
[12]J.M.J.Prechet, M. Henmi, I. Gitsobv, et al. Science, 1995,269,1080
[13]H.Kim,O.W. Webster, J. Am. Chem. Soc. , 1990,12(4), 592
[14]T.M.Miller, T. X. Nennam, E. W. Kwock, et al. J. Am. Chem. Soc., 1993, 115,356
[15]Flory, P. J. d. Am. Chem. Soc. 1941, 63, 3083, 3089, 3096, 1952, 74, 2178.
[16]Vansheidt, A. A.; Mellnikova E. P.; Gladkovsku, G. A. Vysokomolekul. Soedin.,1962,4,1303
[17]Buhleier, E.; Wehner, W.; Vogtle, F. Synthesis, 1978, 155
[18]Newkome, G. R.; Yao, Z.;Baker, G..R.; Gupta, V. K. d. Org. Chem., 1985,50,20021
[19]Newkome, G. R.; Yao, Z.;Baker, G..R.; Gupta, V. K.;Russo,.P.S.; Saunders, M. J. J. Am. Chem. Soc., 1986,108, 849.
[20]Newkome, G. R.; Baker, G. R.Sauders, M. J.; Russo, P. S.; gupta, V. K.; Miller, J. E.; Boullioon, K. J. Chem. Soc., Chem. Commun.,1986,752
[21]Tomalia, D, A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder,J.; Smith, P. Polym. J. (Tokyo). 1985, 17, 117
[22]Tomalia, D, A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P. Macromolecules, 1986, 19, 2466
[23]Padias, A. B.; Hall, H. K.; Tomalia, D. A.; McConne11, S. R. J. Org. Chem.,
1987,52,5305.
[24]Frechet, J. M. J.; Jiang, Y.; Hawker, C. J.; Philippides, A. E. Proc. IUPAC Int. Syrup. "Molecular Design of Functional Polymers ", Seoul, 1989,19.
[25]Desimone, J. M. Science, 1995, 269, 1060
[26]Kim, Y. H.; Webster, O. W. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1988, 29(2), 310.
[27]Kim, Y. H.; Webster, O. W. J. Am. Chem. Soc. 1990, 112, 4592.
[28]Frechet, J.M.J.; Henmi, M.; Gitsov, I.; Aoshima, S.; Leduc, M. R.;Grubb, R. B. Science, 1995,269,1080
[29]D. Yan, A. H. E. Muller, Macromolecules,1997,30,7024
[30]Yan, D.; Zhou, Z.; Jiang, H.; Wang, G. Macromol. Theory Simul.1998, 7, 13
[31]D.Yan, Zh. Yongfeng, J. Hou, Science, 2004, 303, 65
[32]D. Lin, K. Huiguang, S. Wenfang, et al. J. Appl. Polym. Sci., 2001, 82, 1637
[33]唐黎明，H. R. Kricheldorf, 高等学校化学学报，2001， 22，1073
[34]Wang Xinling, Chen Jianjun, Hong ling, Tang Xiaozheng, J. of P. Sci. Part B, 2001,39,2225
[35]徐敏，严晓虎，程镕时，余学海，高分子学报，2001，4，476
[36]薄志山，张希，杨梅林，沈家骢，高等学校化学学报，1997，18，326
[37]Gordon, M. Proc. R. Soc. London 1963, A268, 240.
[38]Good, I. J. Proc. R. Soc. London, Ser. A 1963, 272, 54.
[39]Macosko, C. W.; Miller, D. R. Macromolecules 1976, 9, 199.
[40]Miller, D. R.; Macosko, C. W. Macromolecules 1976, 9, 206.
[41]Beginn, U.; Drohmann, C.; Moiler, M. Macromolecules 1997, 30, 4112.
[42]Hanselmann, R.; Holter, D.; Frey, H. Macromolecules 1998, 31, 3790.
[43]Cameron, C.; Fawcett, A. H.; Hetherington, C. R.; Mee, R. A. W.; Mcbride, F. V. Macromolecules 2000, 33, 6551.
[44]R. G. Denkewalter, J. Kolc, W. J. Lukasavage, U. S. Patent 4,289,872,Sept 15, 1981
[45]P. G. de Gennes and H. J. Hervet. Statistics of"Starburst" Polymers. J. Phys. Lett. (Paris) 1983,44:L351-L360
[46]P. Welch, et al, Tuning the Desity Profile of Dendritic Polyelectrolytes Macromolecules, 1998, 31(17), 5892-5897
[47]Stockmayer, W. H. J. Chem. Phys 1943,11,45,1944,12,125,1950,18,58
[48]Zimm B H; Stockmayer W H J. Chem. Phys .1949,17,1301
[49]Dobson,G R; Gordon, M.J. Chem.Phys. 1964,41 (8),2389
[50]Burchard, W.Adv.Polym.Sci. 1983, 48, 1.
[51]Burchard W; Schmidt M; Stockmayer W H. Macromolecules. 1980,13, 1265
[52]Li, Z. S.; Ba, X. W.; Sun, C. C.; Tang, X. Y.; Tang, A. C. Macromolecules, 1991, 24, 3696.
[53]Ba, X.; Wang, H.; Zhao, M.; Li, M.; Macromolecules, 2002, 35, 3306. 2002, 35, 4193.
[2]Newkome, G. R.; He, Enfei; Moorefield, C. N. Chem. Rev. 1999, 99, 1689.
[3]Kim,Y. H. J. Polym. Science: PartA: Polym. Chem. 1998, 36, 1685.
[4]Volt. B. J. Polym. Science: PartA: Polym. Chem. 1998, 38, 2505.
[5]Yong H. Kim, Owen W. Webster; Water soluble hyperbranched poly-phenytene:" a unimolecular micelle?" J.Am. Chem. Soc.,1990, 112(11): 4592
[6]Mario Gauthier, Martin Moeller; Uniform highly branched polymers by anionic grafting: arborescent graft polymers. Macromolecules, 1991,24(16): 4548
[7]B. Voit, D. Beyerlein, K. Eichhorn, K. Grundke. Functional Hyperbranched Polyesters for Application in Coatings and Thin Films. Chemie Ingenieur Technik. 2001, 73(6): 687
[8]Xu-Tang Tao, Ya-Dong Zhang, Tatuso Wada. Hyperbranched Polymers for Electroluminescence Application. Advance Material. 1998,10(3): 226
[9]W.M.Lackowski, J. G..Franchina, D.E. Bergbreiter. An Atomic Force Microscopy Study of the Surface Morphology of Hyperbranched Poly (acrylic acid) Thin Films. Advanced Materials. 1999, 11 (6): 1368
[10]Anthony A. Gorman, I. Hamblett, C. Lambert. Hydrogen transfer from
1-naphthol triplet to ground-state benzophenone: kinetic evidence against proposed exciplex intermediacy, J. Am. Chem. Soc, ;1987, 109(5): 1600
[11]Trollsas, M.; Hedrick, J. L. Dendrimer-like Star Polymers J.Am.Chem. Soc. 1998, 120(19)
[12]J.M.J.Prechet, M. Henmi, I. Gitsobv, et al. Science, 1995,269,1080
[13]H.Kim,O.W. Webster, J. Am. Chem. Soc. , 1990,12(4), 592
[14]T.M.Miller, T. X. Nennam, E. W. Kwock, et al. J. Am. Chem. Soc., 1993, 115,356
[15]Flory, P. J. d. Am. Chem. Soc. 1941, 63, 3083, 3089, 3096, 1952, 74, 2178.
[16]Vansheidt, A. A.; Mellnikova E. P.; Gladkovsku, G. A. Vysokomolekul. Soedin.,1962,4,1303
[17]Buhleier, E.; Wehner, W.; Vogtle, F. Synthesis, 1978, 155
[18]Newkome, G. R.; Yao, Z.;Baker, G..R.; Gupta, V. K. d. Org. Chem., 1985,50,20021
[19]Newkome, G. R.; Yao, Z.;Baker, G..R.; Gupta, V. K.;Russo,.P.S.; Saunders, M. J. J. Am. Chem. Soc., 1986,108, 849.
[20]Newkome, G. R.; Baker, G. R.Sauders, M. J.; Russo, P. S.; gupta, V. K.; Miller, J. E.; Boullioon, K. J. Chem. Soc., Chem. Commun.,1986,752
[21]Tomalia, D, A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder,J.; Smith, P. Polym. J. (Tokyo). 1985, 17, 117
[22]Tomalia, D, A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P. Macromolecules, 1986, 19, 2466
[23]Padias, A. B.; Hall, H. K.; Tomalia, D. A.; McConne11, S. R. J. Org. Chem.,
1987,52,5305.
[24]Frechet, J. M. J.; Jiang, Y.; Hawker, C. J.; Philippides, A. E. Proc. IUPAC Int. Syrup. "Molecular Design of Functional Polymers ", Seoul, 1989,19.
[25]Desimone, J. M. Science, 1995, 269, 1060
[26]Kim, Y. H.; Webster, O. W. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1988, 29(2), 310.
[27]Kim, Y. H.; Webster, O. W. J. Am. Chem. Soc. 1990, 112, 4592.
[28]Frechet, J.M.J.; Henmi, M.; Gitsov, I.; Aoshima, S.; Leduc, M. R.;Grubb, R. B. Science, 1995,269,1080
[29]D. Yan, A. H. E. Muller, Macromolecules,1997,30,7024
[30]Yan, D.; Zhou, Z.; Jiang, H.; Wang, G. Macromol. Theory Simul.1998, 7, 13
[31]D.Yan, Zh. Yongfeng, J. Hou, Science, 2004, 303, 65
[32]D. Lin, K. Huiguang, S. Wenfang, et al. J. Appl. Polym. Sci., 2001, 82, 1637
[33]唐黎明，H. R. Kricheldorf, 高等学校化学学报，2001， 22，1073
[34]Wang Xinling, Chen Jianjun, Hong ling, Tang Xiaozheng, J. of P. Sci. Part B, 2001,39,2225
[35]徐敏，严晓虎，程镕时，余学海，高分子学报，2001，4，476
[36]薄志山，张希，杨梅林，沈家骢，高等学校化学学报，1997，18，326
[37]Gordon, M. Proc. R. Soc. London 1963, A268, 240.
[38]Good, I. J. Proc. R. Soc. London, Ser. A 1963, 272, 54.
[39]Macosko, C. W.; Miller, D. R. Macromolecules 1976, 9, 199.
[40]Miller, D. R.; Macosko, C. W. Macromolecules 1976, 9, 206.
[41]Beginn, U.; Drohmann, C.; Moiler, M. Macromolecules 1997, 30, 4112.
[42]Hanselmann, R.; Holter, D.; Frey, H. Macromolecules 1998, 31, 3790.
[43]Cameron, C.; Fawcett, A. H.; Hetherington, C. R.; Mee, R. A. W.; Mcbride, F. V. Macromolecules 2000, 33, 6551.
[44]R. G. Denkewalter, J. Kolc, W. J. Lukasavage, U. S. Patent 4,289,872,Sept 15, 1981
[45]P. G. de Gennes and H. J. Hervet. Statistics of"Starburst" Polymers. J. Phys. Lett. (Paris) 1983,44:L351-L360
[46]P. Welch, et al, Tuning the Desity Profile of Dendritic Polyelectrolytes Macromolecules, 1998, 31(17), 5892-5897
[47]Stockmayer, W. H. J. Chem. Phys 1943,11,45,1944,12,125,1950,18,58
[48]Zimm B H; Stockmayer W H J. Chem. Phys .1949,17,1301
[49]Dobson,G R; Gordon, M.J. Chem.Phys. 1964,41 (8),2389
[50]Burchard, W.Adv.Polym.Sci. 1983, 48, 1.
[51]Burchard W; Schmidt M; Stockmayer W H. Macromolecules. 1980,13, 1265
[52]Li, Z. S.; Ba, X. W.; Sun, C. C.; Tang, X. Y.; Tang, A. C. Macromolecules, 1991, 24, 3696.
[53]Ba, X.; Wang, H.; Zhao, M.; Li, M.; Macromolecules, 2002, 35, 3306. 2002, 35, 4193.
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