臺灣博碩士論文加值系統

聚胺基甲酸酯(Polyurethane, PU)具有優良的堅韌性質與耐衝擊性質，其質地柔軟且易於生產製造，故在工業上為良好的彈性體高分子材料；然而，雖然具有良好的性質與廣泛的用途，但卻因其機械性質與耐燃性不佳，而使得應用範圍受到限制。酚醛樹脂(Phenol-Formaldehyde Resin, PFR)則具有較優異的耐燃性質，其質地堅硬且亦容易生產製造，故在工業上亦是良好的高分子材料。
本研究利用具有耐燃特性的酚醛樹脂(PFR)、磷化物改質的酚醛樹脂(P-PFR)及硼化物與磷化物改質的酚醛樹脂(B,P-PFR)來改質PU，製備出不同比例的PU/PFR、PU/P-PFR及PU/B,P-PFR複合材料，藉以改善其熱性質、機械性質及耐燃性，做為火箭發動機阻燃層膠合劑，另以旋轉塗佈法將上述複合材料披覆在鋁合金(AA-6061-T6)上，做為耐燃防腐蝕塗料。同時藉由紅外線光譜儀(FTIR)、凝膠滲透層析儀(GPC)、原子力顯微鏡(AFM)、掃描式電子顯微鏡(SEM)、熱重損失分析儀(TGA)、極限氧指數(L.O.I.)、氫氧焰燒蝕測試、動態機械分析儀(DMA)、熱機械分析儀(TMA)、電化學交流阻抗頻譜(EIS)及鹽霧試驗，探討PU/PFR、PU/P-PFR及PU/B,P-PFR複合材料的光譜特性、熱性質、機械性質、耐腐蝕性等，期望能成為一種新型阻燃層膠料及航空器防蝕材料。

A series of polyurethane/phenol-formaldehyde resin (PU/PFR), polyurethane/phosphonic-modified phenol-formaldehyde resin (PU/P-PFR) and polyurethane/boron, phosphonic-modified phenol-formaldehyde resin (PU/B,P-PFR) composites were prepared through a copolymerization technique and then curing. The objective of the study was to develop and evaluate a unique polyurethane elastomer containing PFR molecules as molecular reinforcements in the hard segment that acted as binder of insulator for rocket motor. Hydroxy-terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), PFR, P-PFR and B,P-PFR were used as precursors for these composites. The effects induced by the media material structure, type and ratio on the thermal, mechanical properties, flame resistance and burn resistance of composites were investigated. The FTIR spectra suggested successful bonding of PFR and PU. The homogeneous dispersion of PFR in the PU matrices was evidenced by scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Thermal and mechanical properties of these PU/PFR composites have been improved over the pure PU analyzed by dynamic mechanical analysis (DMA), Limit Oxygen Index (L.O.I.), thermomechanical analysis (TMA) and thermal gravimetric analysis (TGA). Moreover, these composite films were deposited via spin coating onto aluminum alloy (6061-T6) in order to improve the corrosion protection. Potentio-dynamic and salt-spray analysis revealed that the composite films provided an exceptional barrier and corrosion protection in comparison with PU and untreated aluminum alloy substrates.

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 iv
表目錄 vii
圖目錄 vii
1. 緒論 1
1.1 前言 1
1.2 文獻探討 2
1.2.1聚胺基甲酸酯發展起源 2
1.2.2聚胺基甲酸酯之熱性質 6
1.2.3 聚胺基甲酸脂之相分離 7
1.2.4 聚胺基甲酸脂之原料 7
1.2.5 聚胺基甲酸脂之應用 11
1.2.6 HTPB膠燃料簡介 12
1.2.7 酚醛樹脂 14
1.2.8阻燃層 20
1.3 研究動機及目的 29
2. 實驗 31
2.1 實驗材料 31
2.2 實驗儀器及裝置 33
2.3 鑑定儀器 33
2.4 實驗架構與流程 34
2.5 鋁合金試片前處理與塗層製備 35
2.6 材料特性鑑定方法與原理 40
3. 結果與討論 43
3.1 結構及型態分析 43
3.2 熱性質分析 51
3.4 動態機械性質分析(DMA)及熱機械性質分析(TMA) 56
3.5 機械性質分析 59
3.6 電化學測試 60
3.7 鹽霧試驗 67
4. 結論 69
參考文獻 71
自傳 78

[1]蔡志偉，“阻燃層之奈米複合膠料製備與應用研究”，碩士論文，國防大學理工學院應用化學研究所，桃園，第2頁，2007。
[2]楊傳瑾，“有機-無機混成塗層作為航空器鋁合金基材表面抗腐蝕研究”，碩士論文，國防大學理工學院應用化學研究所，桃園，第1頁，2006。
[3]Suzwki, I., Hisamatsu, Y., and Masuko, N., “Nature of Atmospheric Rust on Iron,” Journal of the Electrochemical Society, Vol. 127, pp. 2210-2215, 1980.
[4]王宗櫚，“聚合物合成與鑑定法”，再版，復文書局，第10-13頁，2000。
[5]林金川，“以橡膠改質環氧樹脂提升交聯樹脂薄膜撓曲性之研究”，碩士論文，南台科技大學化學工程研究所，台南，第20頁，2004。
[6]李宗銘，“耐熱性聚氨酯(PU)樹酯之合成與應用”，工業材料，第90期，第92-95頁，1994。
[7]吳振亮，“以ε-Caprolactone改質軟質段末端及新型嵌段式PU之開發”，碩士論文，國立中央大學化學工程與材料工程研究所，桃園，第1-3頁，2005。
[8]Bruin, P. F., “Polyurethane Technology,” Interscience Publishers, New York, pp. 1-18, 1979.
[9]洪子迪，“Organic-Inorganic Hybrid Electrolytes Based on PPG-PEG-PPG Diamine,Alkoxysilanes, and Lithium Perchlorate”，碩士論文，國立中央大學化學研究所，桃園，第8-11頁，2007。
[10]黃俊賓，“多面體矽氧烷寡聚物(POSS)/聚胺基甲酸酯有機無機奈米複合材料的製備與物性之研究”，碩士論文，國立雲林科技大學化學工程研究所，雲林，第14頁，2004。
[11]Bengtson, B., Fegger, C., Macknight, W. J., and Schnieder, N. S., “Thermal and mechanical properties of solution polymerized segmented polyurethanes with butadiene soft segments,” Polymer, Vol. 26, pp. 895-900, 1985.
[12]Brunette, C. M., Hsu, S. L., Rossman, M., Macknight, W. J., and Schneider, N. S., “Thermal and Mechanical Properties of Linear Segmented Polyurethanes with Butadiene Soft Segments,” Polymer Engineering and Science, Vol. 21, No. 11, pp. 668-674, 1981.
[13]Chang, V. S C., and Kennedy, J. P., “Gas Permeability, Water Absorption, Hydrolytic Stability and Air-Oven Aging of Polyisobutylene-Based Polyurethane Networks,” Polymer Bulletin, Vol. 8, pp. 69-74, 1982.
[14]Speckhard, T. A., Gibson, P. E., Cooper, S. L., Chang, V. S. C., and Kennedy, J. P., “Properties of polyisobutylene polyurethane block copolymers: 2. Macroglycols produced by the inifer technique,” Polymer, Vol. 26, pp. 55-69, 1985.
[15]Speckhard, T. A., Gibson, P. E., Cooper, S. L., Chang, V. S. C., and Kennedy, J. P., “Properties of polyisobutylene polyurethane block copolymers: 3. Hard segments based on 4,4'-dicyclohexyl metha ne diisocyanate (H12MDI) and butane diol,” Polymer, Vol. 26, pp. 70-78, 1985.
[16]李國銘，“硬質鏈上巨大基團對防水性polyester PU的影響”，碩士論文，國立中央大學化學工程與材料工程學系，桃園，第3頁，2010。
[17]Ballistreri, A., Foti, S., Maravigna, P., Montaudo, G., and Scamporrino E., “Mechanism of Thermal Degradation of Polyurethanes Investigated by Direct Pyrolysis in the Mass Spectrometer,” Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pp. 1923-1931, 1980.
[18]Petrovic, Z. S., Zavargo, Z., Flynn, J. H., and Macknight, W. J., “Thermal Degradation of Segmented Polyurethanes,” Journal of Applied Polymer Science, Vol. 51, pp. 1087-1095, 1994
[19]Ferguson, J., and Petrovic, Z., “Thermal Stability of Segmented Polyurethanes,” European Polymer Journal, Vol. 12, pp. 177-181, 1975.
[20]張欣程，“矽氧烷-氨基甲酸酯共聚合體之合成及物理性質”，博士論文，逢甲大學紡織工程研究所，台中，第5-6頁，2008。
[21]Cooper, S. L., and Tobolsky, A. V., “Properties of Linear Elastomeric Polyurethanes,” Journal of Applied Polymer Science, Vol. 10, pp. 1837-1844, 1966.
[22]Van Bogart, J. W. C., Lilaonitkul, A., and Cooper, S. L., “Morphology and Properties of Segmented Copolymers,” Advances in Chemistry Series, Vol. 176, pp. 3-30, 1979.
[23]Estes, G. M., Cooper, S. L., and Tobolsky, A. V., “Block Polymers and Related Heterophase Elastomers,” Journal of Macromolecular Science - Reviews in Macromolecular Chemistry and Physics, Vol. 4, pp. 313-366, 1970.
[24]Schneider, N. S., Desper, C. R., Illinger, J. L., and King, A. O., “Structural Studies of Crystalline MDI-Based Polyurethanes,” Journal of Macromolecular Science-Physics, Vol. 11, pp. 527-552, 1975.
[25]Van Bogart, J. W. C., Lilaonitkul, A., and Cooper, S. L., “Morphology and properties of short segment block copolymers,” Journal of Macromolecular Science-Physics, Vol. 17, pp. 267-301, 1980.
[26]de Zea Bermudez, V., Carlos, L. D., and Alca’cer, L., “Sol-Gel Derived Urea Cross-Linked Organically Modified Silicates. 1. Room Temperature Mid-Infrared Spectra,” Chemistry of Materials, Vol. 11, pp. 569-580, 1999.
[27]Carlos, L. D., de Zea Bermudez, V., Sa’ Ferreira, R. A., Marques, L., and Assuncao, M., “Sol-Gel Derived Urea Cross-Linked Organically Modified Silicates. 2. Blue-Light Emission,” Chemistry of Materials, Vol. 11, pp. 581-588, 1999.
[28]Groselj, N., Gaberscek, M., Opara Krasovec, U., Orel, B., Drazic, G., and Judeinstein, P., “Electrical and IR spectroscopic studies of peroxopolytungstic acid/organic–inorganic hybrid gels, ” Solid State Ionics, Vol. 125, pp. 125-133, 1999.
[29]Bekiari, V., and Lianos, P., “Optimization of the Intensity of Luminescence Emission from Silica/Poly(ethylene oxide) and Silica/Poly(propylene oxide) Nanocomposite Gels,” Chemistry of Materials, Vol. 12, pp. 3095-3099, 2000.
[30]Brankova, T., Bekiari, V., and Lianos, P., “Photoluminescence from Sol-Gel Organic/Inorganic Hybrid Gels Obtained through Carboxylic Acid Solvolysis,” Chemistry of Materials, Vol.15, pp.1855-1859, 2003.
[31]Bekiari, V., and Lianos, P., “Ureasil Gels as a Highly Efficient Adsorbent for Water Purification,” Chemistry of Materials, Vol. 18, pp.4142-4146, 2006.
[32]Silva, M.M., Nunes, S.C., Barbosa, P.C., Evansa, A., de Zea Bermudez, V., Smith, M. J., and Ostrovskii, D., “Sol–gel preparation of a di-ureasil electrolyte doped with lithium perchlorate,” Electrochimica Acta, Vol. 52, pp.1542-1548, 2006.
[33]何明展，“具增燃性膠燃料之接枝合成研究”，碩士論文，中原大學化學學系，桃園，第4頁，2002。
[34]伍德馨、楊祖印，“ HTPB反應特性機構及應用之探討”，火藥技術，第4卷，第1期，第92頁，1988。
[35]www.sartomer.com
[36]賴耀祥，“聚胺基甲酸酯/無機物混成複合材料製備及應用研究”，博士論文，國防大學理工學院國防科學研究所，桃園，第9-10頁，2010。
[37]Mottram, J. T., Geary, B., and Taylor, R., “Thermal expansion of phenolic resin and phenolic-fibre composites,” Journal of Materials Science, Vol. 27, pp. 5015-5026, 1992.
[38]邱伯寧，“原位聚合固態電解質”，碩士論文，國立中央大學化學研究所，桃園，第29頁，2004。
[39]Meier, J. F., JR, E. M. B., and Frank, P. P., “Preparation and Properties of Phenolic Resin Laminates. I. Laboratory Evaluation,” Journal of Applied Polymer Science, Vol. 21, pp. 1383-1394, 1977.
[40]Michot, T., Nishimoto, A., and Watanabe, M., “Electrochemical properties of polymer gel electrolytes based on poly(vinylidene fluoride) copolymer and homopolymer,” Electrochimica Acta, Vol. 45, pp. 1347-1360, 2000.
[41]Boudin, F., Andrieu, X., Jehoulet, C., and Olsen, I.I., “Microporous PVdF gel for lithium-ion batteries,” Journal of Power Sources, Vol. 81-82, pp. 804-807, 1999.
[42]Li, J., and Khan, I. M., “Highly Conductive Solid Polymer Electrolytes Prepared by Blending High Molecular Weight Poly(ethy1ene oxide), Poly(2- or 4-vinylpyridine), and Lithium Perchlorate,” Macromolecules, Vol. 26, pp. 4544-4550, 1993.
[43]http://psdn.pidc.org.tw/ike/doclib/2003/2003doclib/2003ike31-0/2003ike31-0-307.asp
[44]http://www.amazon.com/Principles-Polymerization-3rd-George-Odian/dp/0471610208#reader_0471610208
[45]陳韋任，“燃料電池用導電雙極板之碳奈米管/酚醛樹脂奈米複合材料備製及其性質研究”，碩士論文，中原大學機械工程學系，桃園，第30-33頁，2004。
[46]馬振基，“國防軍事用防火、難燃、低煙、無毒複合材料研究之製程與檢測”，國立清華大學自強科學研究中心委託合作研究計畫總結報告，NSC 91-CS-7-007-001，新竹，第8頁，2003。
[47]何宗漢，“含磷芳烷基氰酸酯之合成及物性研究”，國立高雄應用科技大學化學工程系，5th KUAS Symp，高雄，285，2005。
[48]Gao, J. G., Liu, Y. F., and Yang, L. T., “Thermal stability of boron-containing phenol formaldehyde resin,” Polymer Degradation and Stability, Vol. 63, pp. 19-22, 1999.
[49]Abdalla, M. O., Ludwick, A., and Mitchell, T., “Boron-modified phenolic resins for high performance applications,” Polymer, Vol. 44, pp. 7353-7359, 2003
[50]Kumpinsky, E., “A Study on Resol-Type Phenol-Formaldehyde Runaway Reactions,” Industrial and Engineering Chemistry Research, Vol. 33, pp. 285-291, 1994.
[51]Marie-Florence Grenier-Loustalot, Larroque, S., Grenier, P., Leca, J. P., and Bedel, D., “Phenolic resins: 1. Mechanisms and kinetics of phenol and of the first polycondensates towards formaldehyde in solution,” Polymer, Vol. 35, pp. 3046-3054, 1994.
[52]Marie-Florence Grenier-Loustalot, Larroque, S., and Grenier, P., “Phenolic resins: 5. Solid-state physicochemical study of resoles with variable F/P ratios,” Polymer, Vol. 37, No. 4, pp. 639-650, 1996.
[53]Marie-Florence Grenier-Loustalot, Larroque, S., Grenier, P., and Bedel, D., “Phenolic resins: 2. Influence of catalyst type on reaction mechanisms and kinetics,” Polymer, Vol. 37, No. 8, pp. 1363-1369, 1996.
[54]陳仁益，“共聚酯之熔融行為、紅外線光譜研究與阻燃層之開發”，碩士論文，國立中山大學材料科學研究所，高雄，第81-82頁，2002。
[55]Strauss, E. L., “Development and Characterization of a Radio Frequency-Transparent Ablator,” Journal of Macromolecular Science Pure and Applied Chemistry, Vol. 3, pp. 735-761, 1969.
[56]呂信賢，“矽橡膠複合材料經高溫/高壓後之表面及內層化學成分分析”，碩士論文，國立中山大學材料科學研究所 ，高雄，第1-4頁，2001。
[57]余鳳兒，“改質聚氨酯/聚矽氧烷耐燒蝕材料研究”，博士論文，國立中山大學材料科學研究所，高雄，第1-16頁，2004。
[58]鍾鎔聲，“高分子之 IPN 及 semi-IPN 結構之形成及物性相關性之研究”，博士論文，國立臺灣科技大學高分子工程研究所 ，台北，第3-9頁，2006。
[59]Baqar, M., Agag, T., Ishida, H., and Qutubuddin, S., “Poly(benzoxazine-co-urethane)s: A new concept for phenolic/urethane copolymers via one-pot method,” Polymer, Vol. 52, pp. 307-317, 2011.
[60]Wang, D. C., Chang, G. W., and Chen, Y., “Preparation and thermal stability of boron-containing phenolic resin/clay nanocomposite,” Polymer Degradation and Stability, Vol. 93, pp. 125-133, 2008.
[61]Liaw, D. J., and Lin, S. P., “Phosphorus-containing polyurethane based on bisphenol-S, prepared by N-Alkylation,” European Polymer Journal, Vol. 32, pp. 1377-1380, 1996.
[62]Chang, T. C., Shen, W. S., Chiu, Y. S., and Ho, S. Y., “Thermo-oxidative degradation of phosphours-containing polyurethane,” Polymer Degradation and Stability, Vol. 49. pp. 353-360. 1995.