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標題: 線性與高分歧化磷系高分子之合成與其性質探討
Synthesis and Properties of Phosphorus-containing Linear and Hyperbranched Polymers
作者: 呂亞欣
Lyu, Ya-Sin
關鍵字: hyperbranched polymer;高分歧化;azomethine;phosphorus;聚醯胺;含磷高分子
出版社: 化學工程學系所
引用: 1.Banerjee, S.; Pranav, K.; Saxena, C. J. Polym. Sci Part A Polym Chem 1995, 33,1719 2.Banerjee, S.; Pranav, K.; Saxena, C. Designed Monmer and Polym 1999, 2, 135 3.Park, K.; Tani, T.; Kakimoto, M.; Imai, Y.; Macromol. Chem. Phys. 1998, 199, 1029 4.Miyaji, T.; Azuma, C. J. Polym. Sci Part A Polym Chem 2000, 38,1064 5.Jikei, M. ; Kakimoto, M. J. Polym. Sci Part A Polym Chem 2004, 42, 1293 6.Chang, Y.; Shu, C. Macromolecules 2003, 36, 661 7.Okamoto, K. I.; Fang, J.; Kita, H. Macromolecules 2000, 33, 4639 8.Yang, G.; Jikei, M.; Kakimoto, M. Macromolecules 1998, 31, 5964 9.Yang, G.; Jikei, M.; Kakimoto, M. Macromolecules 1999, 32, 2215 10.Jikei, M.; Sung-Hyun Chon; Kakimoto, M. Macromolecules 1999, 32, 2061 11.C. H. Lin, S. X. Cai, J. Polym. Sci Part A Polym Chem 2005, 43,5971 12.Y. L. Liu, C. S. Wu, K. Y. Hsu, T. C. Chang, J. Polym. Sci Part A Polym Chem 2002, 40, 2329 13.C. J. Hawker, R. Lee, J. M. J. Frechet, J. Am. Chem. Soc. 1991, 113, 4583 14.D. Holter, A. Burgath, H Fery, Acta Polymer. 1997, 48,30
本論文分為兩個部份,第一部分是利用一步法由imine鍵結合成一系列線性磷系高分子,其具有較高的Tg、Td 值,且擁有較好的溶解度。由實驗結果得知添加LiCl可提升聚合物之分子量,但添加p-TSA的多寡與反應時的壓力對聚合物之分子量影響不大,而Dopo加入與polyazomethine反應後,促使反應平衡向右,因此一步法合成的高分子分子量高於兩步法合成的高分子。由GPC、NMR及FTIR分析可知aldehyde與amine的反應性比aldehyde與Dopo的反應性好;此外,親核加成反應Dopo與azomethine的反應性高於Dopo與aldehyde。
第二部分是利用Dopotiramine與二酸(ODAc、6FAc、TPAc、IPAc) 於溶劑NMP、縮合劑TPP、Pyridine及縮合助劑CaCl2的存在下,直接聚縮合成高分歧化磷系聚醯胺。主要是探討以不同單體進行反應時,避免發生凝膠化的濃度,以及藉由磷光譜計算出高分歧化磷系聚醯胺的分歧度(DB),其値大約在0.54-0.57之間,並且得知分歧度(DB)不受到反應濃度不同而有所變化,此外,高分歧化磷系聚醯胺皆能溶於amine系的溶劑。

In the first part, several new phosphorus-containing polymers with high Tg and Td were successfully synthesized by one-step approach via azomethine structure at room temperature. According to the experimental data, LiCl is crucial to the high molecular weight of new polymers, while p-TSA and pressure only have little effect on molecular weight in the presence of LiCl. The equilibrium of polyazomethine formation shifted to right after Dopo reacted with azomethine, resulting in the molecular weight of polymers by one-step approach is higher than that of polymers by two -step approach. According to the molecular weight, NMR and FT-IR characterization of phosphorus-containing linear polymers, the reaction rate between aldehyde and amine is higher than that of aldehyde and Dopo. Besides, the reaction rate of nucleiphilic addition between Dopo and azomethine is higher than that of Dopo and aldehyde.
In the second part, a series of hyperbranched polyamides were successfully synthesized via polycondensation of dopotriamine and four aromatic diacids in the presence of condensing agents such as triphenyl phosphite and pydrdine. The degrees of branching of hyperbranched polyamides were estimated from 31P NMR spectra, and the degrees of branching were independent of reaction concentration. Hyperbranched polyamides were soluble in amide solvents and HB-IV was even soluble in pyridine.
其他識別: U0005-0808200717264500
Appears in Collections:化學工程學系所

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