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研究生: 吳珮宜
Pei-Yi Wu
論文名稱: Chitosan/MDI原位聚合反應發泡成型物之結構與性能之研究
A study on structure and properties of in-situ polymerization of Chitosan-MDI
指導教授: 邱顯堂
Hsien-Tang Chiu
口試委員: 李俊毅
Jiunn-Yih Lee
邱士軒
Shih-Hsuan Chiu
邱維銘
Wei-Ming Chiu
蕭耀貴
Yao-Kuei Hsiao
學位類別: 碩士
Master
系所名稱: 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年: 2006
畢業學年度: 94
語文別: 中文
論文頁數: 87
中文關鍵詞: 幾丁聚醣異氰酸酯原位聚合抗菌性
外文關鍵詞: In situ polymerization, Antimicrobial, Chitosan, Diisocyanate
相關次數: 點閱:201下載:1
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幾丁聚醣為一種生物性高分子,具有良好的生物相容性、無毒性、生物分解性、抗菌性,且在地球的蘊藏含量僅次於纖維素,而且可從廢棄的蝦蟹殼中大量取得等優點,所以被廣泛應用於醫用材料。
二苯基甲烷二異氫酸鹽(4,4- Diphenylmethane Diisocyanate,簡稱MDI)是最重要的聚胺酯原料之一,其機械性優異、反應快及易加工性特性。主要應用於製造聚氨酯彈性體、人造皮革、合成皮、織物塗層整飾劑,人體器官代用品等。
本文主旨在探討以天然高分子幾丁聚醣(Chitosan)與二苯基甲烷二異氰酸酯(MDI)依不同比例進行反應,於室溫下控制幾丁聚醣水溶液之不同濃度,直接進行反應,由於幾丁聚醣的化學結構,具有很多-OH官能基,故利用氫氧基團反應性,進行原位聚合發泡之反應,可簡易的獲得聚氨酯(PU)架橋發泡反應體。利用SEM、發泡倍率、密度、吸水性、水蒸氣透過率、應力應變等實驗,分別探討異氫酸鹽改質幾丁聚醣之反應性及物性之影響效應,得知MDI含量越多,造成薄膜孔洞越大,發泡倍率、吸水率提升,相對的密度、水蒸氣透過率及應力應變降低。同時藉由DMA及TGA了解,MDI對熱性質影響效應,MDI能有效的提升薄膜的耐熱性以及改善Chitosan的脆性剛性。並使用革蘭氏陽性菌(黃金葡萄球菌)和革蘭氏陰性菌(大腸桿菌)來進行外在環境之生物抗菌能力,以探討Chitosan/MDI配比對於抗菌性之影響效應,並得知Chitosan含量越多其抗菌率越高,抗菌效果也越好。


Chitosan is a biological polymer. It has good biological compatibility, avirulence, degradable and antibiotic. Besides, the storage on the earth is after cellulose. The advantage is that it can be obtained from the waste shell of shrimp and crab. Therefore, it is widely used on medical material.
MDI is one of the most important material for PU. The characteristics involve that the machinery is excellent, reaction is fast and processing is easy. It is mainly used to produce PU elastomer, artificial leather,synthesized skin, fabric coating dress down agent and human organ substitute.
The objective of this article is to discuss the reaction of nature Chritosan macromolecule and MDI with different proportion. The different concentration of Chitosan solution reacts directly under room temperature. The chemical structure of Chitosan contains many -OH base. Therefore, the reactivity of oxyhydrogen base is utilized to process in situ polymerization expansion reaction. The bridging expansion reaction agent of PU can easily be obtained. The experiments on SEM, expansion ratio, density, water absorption, and W.V.T and stress strain are used in order to study the effect of reactivity and physical property of Diisocyanate changed Chitosan. It is found that when the content of MDI is more, the size of hole on membrane is larger. The expansion ratio and hydroscopicity raise, and the relative density, vapor penetration rate and stress strain decrease. Besides, from the DMA and TGA, the effect of thermal property is found. MDI can effectively raise the thermostability of the membrane, and improve the brittleness and rigidity of Chitosan. The Staphylococcus andEscherichia are used to test the biological antiseptic ability in external environment in order to study the effect of Chitosan/MDI proportion on bacteria resistance. It is found that when the content of Chitpsan is more, the bacteria resistance is higher and the antiseptic result is better.

摘要 ……………………………………………………………………………..……I Abstract………………………………………………………………………………II 誌謝 ……………………………………………………………………………..… IV 目錄 …………………………………………………………………………….….. .V 圖索引 ………………………………………………………………………………Ⅶ 表索引 ……………………………………………………………………………....Ⅸ 第1章 序論 ………………………………………………………………………….1 第2章 文獻回顧 ……………………………………………………………………3 2.1 幾丁質與幾丁聚醣的特性與製備 ……………………………………3 2.1.1 幾丁質與幾丁聚醣的特性 ……………………………………3 2.1.2 幾丁質與幾丁聚醣的製備 ……………………………………5 2.1.3 去乙醯度測定 …………………………………………………7 2.1.4 幾丁質與幾丁聚醣性質………………………………………10 2.1.5 幾丁質與幾丁聚醣的應用……………………………………12 2.2 二異氰酸酯 …………………………………………………………18 2.2.1二異氰酸酯之特性 ……………………………………………18 2.2.二異氰酸酯之反應………………………………………………21 2.3 幾丁聚醣之抗菌機制 ………………………………………………22 2.4 參考文獻 ……………………………………………………………24 第3章 Chitosan/MDI原位聚合反應發泡成型物之結構與性能之研究 3.1 前言 …………………………………………………………………28 3.2 實驗 …………………………………………………………………30 3.2.1 材料 …………………………………………………………30 3.2.2 反應成型 ……………………………………………………31 3.2.3 測試 …………………………………………………………31 <1> 傅立葉紅外線光譜分析儀(FTIR) ………………………31 <2> 發泡倍率(Expansion ratio) ……………………………31 <3> 流動及指觸乾燥時間 ……………………………………31 <4> 密度(Density) ………………………………………… 32 <5> 吸水性試驗(Water absorption experiment) …………32 <6> 掃瞄式電子顯微鏡(SEM) ……………………………… 32 <7> 應力-應變測試(Stress-strain test) ………………33 <8> 水蒸氣透過率(WVT) …………………………………… 33 <9> 動態機械分析儀(DMA) ………………………………… 33 <10> 熱重量分析儀(TGA) …………………………………… 33 <11> 抗菌性測試(Antimicrobial efficacy) ………………34 3.3 結果與討論 …………………………………………………………35 <1> Chitosan/MDI之反應機制 ……………………………… 35 <2> 反應速率及Chitosan/MDI之發泡結構………………… 36 <3> Chitosan/MDI之分子間作用力 …………………………37 <4> Chitosan/MDI之應力應變 ………………………………40 <5> Chitosan/MDI之熱性質影響效應 ………………………41 <6> Chitosan/MDI之抗菌性質影響效應 ……………………42 3.4參考文獻 …………………………………………………………… 45 第4章 結論 ………………………………………………………………48

第二章
<1>Brine, C. J. and Austin , Comp.Biochem.Physiol, 69B, 283-286 , (1981)
<2>Knorr., D. Used of chitinous ploymers in food-A challenge for foodresearch and development. Food Technol, 1, 85-97, (1984)
<3>M.V. Deshpande, J. Sci.&Ind. Res., 45, 273-277, (1986)
<4>M. O‘brine and R.R. Colwell, Appl.and Envir. Microb., 53, 1718-1724, (1987)
<5>I.G. Cosio, R A. Fisher, and D.A. Carroad, J. Food Sci., 47, 901-905, (1982)
<6>C. H. Su et al., Biomaterials;18:1169,(1997)
<7>Ota S. Current Status of Irradiated Heat-Shrinkable Tubing in JapanRadiation Physics Chemistry. 18(1~2):81~87, (1981)
<8>Charlesby A. Atomic Radiation and Polymers, Chapter 9, London:Pergamon Press, 134~158, (1960)
<9>Austin, P. R., Brine, C. J., Castle, J. E. and Zikakis, J. P..Chitin:New facets of research. Science, 212, 15:749, (1981)
<10>Toei K., Kohara T. ,Anal. Chem. Acta., 83, 59, (1976)
<11>Holan Z., Voyruba J., J. Chromatography., 190, 67,(1980)
<12>Muzzarelli, P. A. A. Chitin. ThePolysaccharides 3:417-450,(1985)
<13>Muzzarelli, R. A. A. , Tanfani, F. , Scarpini, G. , and Laterza, G.J. Biochemical and Biophysical Methods.2:299,(1980)
<14>Alonso, I. G. , Peniche-Covas, C. and Nieto, J. M.
J. Thermal Analysis. 28:189, (1983)
<15>Domard A., and Rinaudo M., Int. J. Biol. Macromol., 5(2), 49-52, (1983)
<16>Stanley, W. L. , Watters, G. G. , Chan, B. G. and Mercer, J. M.Lactose and other enzymes bound to chitin wit glutaraldehyde.Bio htech. and Bioeng. XVII:315,(1975)
<17>Domszy, A. G. and Roberts, G. A. F. Evaluation of infraredspectroscopic techniques for analyzing chitosan. Makromol. Chem.186:1671,(1985)
<18>Toei K., Kohara T., “A conductometric method for colloid titrations”,Anal. Chem. Acta., 83, 59, (1976)
<19>Sannan, T. , Kurita, K. and Iwakura, Y. Polymer.19:458,(1978)
<20>Moore, G. K. and Roberts, G. A. F. J. Biol. Macromol. 2:115,(1980)
<21>K. M. Vàrum, M. W. Anthonsen, H. Grasdalen, O. Smidsrød,Carbohydrate Research, V211, 17-23, (1991)
<22>H. Saito, R. Tabeta, K. Ogawa, Progr. Biotechnol, V3, 267,(1987)
<23>Chatelet-C, Damour-O, Domard-A, ,Biomaterials, 22, 261-268, (2001)
<24>Kim K. J. Ko S. W. J. of Appl. Poly. Sci., (7): 6019, (1986)
<25>Struszczyk, M. H., Polymers, 47, 6, 396-403, (2002)
<26>Ota S. Current Status of Irradiated Heat-Shrinkable
Tubing in Japan Radiation Physics Chemistry.18(1~2):81~87, (1981)
<27>Kurita K, ,prog. polym. sci., 26, 1921, (2001)
<28 >Hirano S., Senda H., Yamamoto Y. and Watanabe A., in Chitin,Chitosan, and Related Enzymes, Academic Press, London, (1984)
<29>Chandy T., Sharma C.P., Biomat. Artif. Cells Artif. Organs, 18, 1,(1990)
<30>Lacy P.E., Sci. Amer., 50, 273, (1995)
<31>Darmadji, P. and Izumimoto, M. Effect of chitosan in meat preservation. Meat Sci. 38, 243, (1994)
<32>Schollenberger, C.S., and Stewart, F.D. Advanes in
urethane Science and Technology. Ed. Frisch, K.C.,
and Reegen, S.L., vol2, (1973)
<33>G. Oertel, Polyurethane Handbook, p7 ,(1985)
<34>W. M. Alvino, J. Appl. Polym. Sci., vol.19, p.2961 (1975)
<35>Leuba, J. L and P. Stossel, In R. Muzzarelli, C.Jeuniarx,andG.Gooday(ed.),Chitin in Nature Technology, Plenum Press, N.Y.:215,(1986)
<36>Young,D. H. and H. Kauss.,Plant Physiol.,73,698-702,(1983)

<37>Dunn, E. T., Grandmaison, E. W., Goosen, M. F. A. Applications andproperties of chitosan. In: Goosen, M.F.A. (Ed), Applications ofchitin and chitosan, Technomic Publishing, Lancaster, USA,3-29,(1997)
<38>Z. Jia, D. shen, W. Xu, Carbonhydrate Research, Vol. 333, 1-6, (2001)
<39> T. Chen, Present on the National Symposium on Nature MarineProduct and Nature Biological Medicine;
282-284, (1998)
<40>M. Simojon, K. Fukushima, Kichin Kitosan Kenku, V2, 90-91,(1996).
<41>S. Tokura, Y. Miuray, M. Johmen, N. Nishi, S. I. Nishimura, J.Control. Rel., V28, 235-241,(1994).
<42>Z. Jia, D. Shen, W. Xu, Carbohydrate Research, V333, 1-6,(2001)

第三章
<1>M. O‘brine and R.R. Colwell, Appl.and Envir. Microb., 53, 1718-1724, (1987)
<2>Su C. H. et al., Biomaterials. 18,1169,(1997)
<3>M. O`brine and R.R., Appl. and Envir. Microb. 53, 1718-1724, (1987)
<4>Wang Y C, Kao S H, Hsieh H J.Biomacromolecules,4(2),224-231, (2003)
<5>S. B. Rao, C. P. Sharma, Biomater. Appl.10, 136-143 , (1995)
<6>Rhoades J, Roller S. Applied and EnvironmentalMicrobiology; 66: 80-86,(2000)
<7>Ha W S, Park W H.Biomaterials, .16(16): 1211-6. (1995)
<8>R. A. A. Muzzarelli, G. Biagimi, A. Pugnaloni, Fillippini, V.Baldassarre, C. Castaldini, C. Rizzoli, Biomaterils, 10, 598 ,(1989)
<9>G. Kratz, C. Arnander, J. Swedenbrog, M. Back, C. Falk, I. Gouda, and O. Larm, Scandinavian J. Plastic and Reconstructive Surgery and Hand Surgery.31,119-123,(1997)
<10>G. Kratz, M. Back, C. Arnander, and O. Larm, Scandinavian J. Plastic and Reconstructive Surgery and Hand Surgery. 32,381-385,(1998)
<11>K. Oungbho, B. W. Miller, International Journal of Pharmaceutics,156, 229-237,(1997)
<12>Giunchedi P, Genta I, Conti B, Muzzarelli R. Biomaterials; 19,157-161,(1998)
<13> M.N. Tararel. A.Demard, Biomaterials, 14,928 (1993)
<14>Yoda,R.,“Elastomersfor biomedical applications", J. Biomater, Sci. Polymer Edn., 9,561-626<199>
<15>W.Y. Chuang,T.H. Young,C.H. Yao,W.Y. Chiu,Biomaterials,20,1479-1487,(1999)
<16> M.W. Huh, I. K. Kang, D. H. Lee, W. S. Kim, D. H. Lee, L. S. Park, K. E. Min,K. H. Seo,J.App Poly. Sci,81, 2769-2778, (2001)
<17>N. Shanmugasundaram et al.,Biomaterials, 22, 1943-1951 (2001)
<18>Alexeev, V. L.; Kelberg, E. A.; Evmenenko, G. A. and Bronnikov, S. V., Polym. Eng. Sci., 40, 5, 1211-1215,
(2000)
<19>Hua Zhang, Yumin Du,Jiahui Yu.,J.Appl.Polym.Sci.,80, 2588-2565 ,(2001)
<20>Haiqing Lin, Lina Zhang., J.Appl.Polym.Sci.,
82,3109-3117(2001)
<21>Ming Zeng,Lina Zhang., J.Appl.Polym.Sci.,
90,1233-1241(2003)
<22>Tomoe Koyano, Norihiko M., Masanobu N., Ken-ichi K., J.Biomed.Mater. Res., 39, 486 (1998)

<23>Kaminski, A. M., Marek, W., Journal of Coatings Technology, 69 ,873,(1997)
<24>Gum, W. F., Riese,W., and Ulrich, H., Reaction Polymers, 704-727
<25>Sundararajan VM,Howard WTM.Biomaterials,20,1133,<1999>
<26>Darmadji, P. and Izumimoto, M., “Effect of chitosan in meat preservation”, Meat Sci., 38,243,<1994>
<27>Z. Jia, D. shen, W. Xu, Carbonhydrate Research, . 333, 1-6, <2001>

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