Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3836
標題: 使用聚乳酸二元酸和4,4’-二苯基甲烷二異氰酸鹽為原料透過連續自我反覆反應 (SSRR)合成聚醯胺高分子
Polyamides Prepared from MDI and Lactic Acid Based Diacid through SSRR Mechanism
作者: 周敬樸
Chou, Ching-Pu
關鍵字: Lactic Acid Based Diacid
聚乳酸二元酸
Polyamide
SSRR
聚醯胺高分子
連續自我反覆反應
出版社: 化學工程學系所
引用: 1. Erwin T. H. Vink, Karl R. Rabago, David A. Glassner and Patrick R. Gruber ,“ Applications of life cycle assessment to NatureWorks™ polylactide (PLA) production”, Polymer Degradation and Stability ,Volume 80, Issue 3, 2003, Pages 403-419. 2. Niju Narayanan, Pradip K. Roychoudhury, Aradhana Srivastava,“ L (+) lactic acid fermentation and its product polymerization.”, Electronic Journal of Biotechnology, ISSN: 0717-3458, Vol.7 No.2. 3. Rajeev Mehta, Vineet Kumar, Haripada Bhunia, and S. N. Upadhyay,“ Synthesis of Poly(Lactic Acid): A Review.”, Polymer Reviews 45:4,325 — 349. 4. David. P. Mobley,” Plastics from Microbes”, Hanser Gardner Publications edition ,Hardcover in English, April 1994 5. 吳志恆,” Acylurea的合成及應用”, 國立中興大學化學工程所,碩士論文,臺中(2001) 6. Kari Hiltunen, and Jukka V. Seppala,” The use of different diols in the synthesis of low-molecular weight lactic-acid-based telechelic prepolymers.”, J. Appl. Polym. Sci. 1998, 67: 1017–1023. 7. Kari Hiltunen, Mika Harkonen, Jukka V. Seppala, and Taito Vaananen,“ Synthesis and Characterization of Lactic Acid Based Telechelic Prepolymers.”, Macromolecules 1996, 29, 8677-8682 8. J. L. Espartero, I. Rashkov, S. M. Li, N. Manolova, and M. Vert,“ NMR Analysis of Low Molecular Weight Poly(lactic acid)s.”, Macromolecules 1996, 29, 3535-3539. 9. Kuan-Liang Wei, Chih-Heng Wu, Wei-Hsiang Huang, Jiang-Jen Lin, and Shenghong A. Dai,“ N-Aryl Acylureas as Intermediates in Sequential Self-Repetitive Reactions To Form Poly(amide-imide)s”, Macromolecules 2006, 39, 12-14. 10. Bernard Loev, Broomall Pa.,” Method of Preparation of Heterocyclic Compounds.” US Patent US3149106. 11. M. Robba and D. Maume, Ct. R. Acad. Sci. C272, 475 (1971) 437. 12. ASTM D4662-08:Standard Test Methods for Polyurethane Raw Materials: Determination of Acid and Alkalinity Numbers of Polyols 13. E. M. Filachione, and C. H. Fisher,” Lactic acid condensation polymers.”, Ind. Eng. Chem 1944, 36: 223–228.
摘要: 在本論文中,研究以乳酸單體製備L型聚乳酸二元酸之合成方法,係由添加不同量之1,6-己二酸作為起始劑,在反應條件:溫度150-160℃、壓力5cmHg,能夠合成出分子量(1800-3000)之L型聚乳酸二元酸(PLLA-diacid),其產率皆大於90%。且根據分子量增加,Tg也會隨著增大。 將合成之L型聚乳酸二元酸與4,4’-MDI進行聚縮合反應,應用本實驗室先前所發展之SSRR反應,在溫度150-160℃、CDI生成觸媒,DMPO,催化下,可以成功地製備出聚醯胺高分子(PLLA-PA),但其性質硬脆,無法成膜。 為改善PLLA-PAs之柔韌性與成膜性,以添加軟鍊聚二元醇,先與4,4’-MDI合成NCO結尾之預聚物,再加入L型聚乳酸二元酸進行SSRR反應。此方法對於PLLA-PA的柔韌性有大幅的改善,多數的配方能夠製備可成膜之PLLA-PAU,其中以PTMEG系列之PLLAPAU具有較佳的表現。
In this research, we have studied the synthesis of L-lactic acid based –diacid (PLLA-diacid) of 1,800 to 3,000 molecular weights by using different quantities of adipic acid as initiator to condense with L-lactic acid. Under the reaction temperature of 150-160℃ and the vacuum pressure from 10 cm-Hg in the beginning reducing slowly to 5 cmHg at the end to remove water, we could obtain PLLA-diacids with high yields above 90%. These PLLA-diacids exhibit different Tgs deponding upon their molecular weights. Poly-condensation of PLLA-diacids to methylenediphenylene diisocyanate (MDI) were then carried out at temperature of 150-160℃with a carbodiimide catalyst, DMPO, to make PLLA-polyamides (PLLA-PA). this polymerization was based on the procedures and mechanism of Sequential Self-Repetitive Reaction (SSRR) developed previously in our laboratory. We could successfully synthesize PLLA-PAs, but they were still brittle to make films. To improve flexibilities and film forming properties of PLLA-PAs, isocyanate-terminated prepolymer (NCO prepolymer) of 4,4'-MDI with both polytetramethylene (PTMEG-2000) and polyethylene-butylene adipate (Polyester-2000, RS956) were prepared first, and then the NCO –prepolymers were reacted with PLLA-diacid again under “SSRR” conditions. These formulas modifications (PLLA-PAU) did substantially improve flexbilities of PLLA-PAs. Particularity; the formulation based on PTMEG-NCO-prepolymers gives the over best result.
URI: http://hdl.handle.net/11455/3836
其他識別: U0005-2008201021171200
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2008201021171200
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