臺灣博碩士論文加值系統

本研究旨在探討以聚矽氧烷樹脂改質酚醛樹脂之脆性並提高酚醛樹脂之抗熱氧化性。為改善酚醛樹脂與聚矽氧烷之相容性，本研究自行合成矽酮聚醯胺樹脂(Poly-dimethylsiloxane adipamide ; PDMSA)，藉由醯胺基加入聚矽氧烷主鏈，利用醯胺基與酚醛上的羥基形成氫鍵，以增加相容性。本研究內容即針對矽酮聚醯胺樹脂(PDMSA)之合成、PDMSA與Novolac type 酚醛樹脂相容性及PDMSA對Novolac type酚醛樹脂增韌效果及熱性質、燃燒性質之改善進行探討。 藉由1,3 Bis(3-aminopropyl)-1,1,3,3-Tetramethyl-disiloxane與己二酸反應形成醯胺或耐隆鹽(Amide or nylon salt)後經高溫熱融反應合成所需之矽酮聚醯胺樹脂(Poly-dimethylsiloxane adipamide ; PDMSA)，經由IR及H1 NMR、C13 NMR鑑定，證明其結構正確。 由微差熱掃瞄分析(DSC)及紅外線光譜的結果得知，Novolac type酚醛樹脂與自行合成之PDMSA分子間會產生極強的分子間氫鍵；若PDMSA之含量較低，利用Kwei equation對分子間氫鍵作用力的修正，可得到較佳的預測結果，而在含30﹪~70﹪之PDMSA時則實驗結果較趨近Gordon-Taylor 及Fox equation所預估之理論值；此外，由DSC的結果可證實Novolac type酚醛樹脂與PDMSA摻混系統具有良好的相容性。 摻混系統未硬化前的TGA測試結果顯示，PDMSA/Novolac type phenolic resin摻混系統是以PDMSA改善酚醛樹脂低溫的耐熱性質，而以酚醛樹脂改善PDMSA高溫的耐熱性質。 PDMSA與Novolac type酚醛樹脂摻混後以環氧樹脂為硬化劑、DBU為促進劑進行硬化反應，並製成試片，其機械性質（包括Flexural strength、flexural modulus及Notched Izad Impact strength）顯示，PDMSA對酚醛樹脂具有良好的增韌效果；當加入5 phr的PDMSA時，耐衝擊強度增加37%；抗折強度增加66%。 PDMSA改質酚醛樹脂硬化的試片在空氣中的TGA測試結果顯示，在兩階段的熱裂解過程中，PDMSA中的脂肪族鏈，造成第一階段熱裂解溫度的下降，而矽氧烷鏈段則提升了第二階段熱穩定性的上升，且PDMSA含量需高於5phr，其對酚醛樹脂熱性質之改善才較明顯。由UL-94及L.O.I之測試結果顯示，含不同比例PDMSA之硬化試片之L.O.I值均為35，UL-94測試達94V-1標準，可知，酚醛樹脂/PDMSA聚摻合物為一種難燃、低發煙量、使用安全性高之防火高分子材料。

The objective of this study is to improve the toughness and the thermo-oxidative resistance of the cured Novolac type phenolic resin modified with polysiloxane. In order to improve the miscibility between Novolac type phenolic resin and polysiloxane, poly-(dimethylsiloxane adipamide) ( PDMSA ) were synthsized. By the addition of amide group in the main chain, strong intermolecular hydrogen bonding interaction was formed, consequently, the miscibility between Novolac type phenolic resin and polysiloxane was improved. The subjects of this study include the synthesis of PDMSA, miscibility between Novolac type phenolic resin, the improvement of toughness of PDMSA modified Novolac type phenolic resin and the improvement of thermo-oxidative resistance and flame resistance properties.From the experimental results, the predicted structure can be synthesized by reacting 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl-disiloxane with adipic acid to form amide (nylon) salt, then was polymerized by melting reaction at 160 oC. By the investigations of IR, H1-NMR and C13-NNR, the molecular structure can be identified.Differential scanning calorymetric (DSC) and Infrared spectroscopic results show that there are strong intermolecular hydrogen bonding interactions existed between Novolac type phenolic resin and PDMSA. In the low PDMSA content regions, Kwei equation is feasible to the experimental Tg data; however, in the region between 30 wt.%~70 wt.% of PDMSA contents , the experimental Tg data closed to the prediction by Gordon-Taylor and Fox equations. furthermore, DSC results show great miscibility between Novolac type phenolic resin and PDMSA.TGA results of uncured Novolac/PDMSA blends show that PDMSA improves the thermo-resistance property of Novolac type phenolic resin at low temperature region, while Novolac type phenolic resin improved thermo-resistance property of PDMSA at high temperature region.Novolac type phenolic resin blended with PDMSA was cured by DGEBA type epoxy resin and using DBU as promotor The mechanical properties (include flexural strength, flexural modulus and Notched Izad impact strength) of Novolac type phenolic resin modified by PDMSA show great improvement. The flexural strength of cured resin specimen contains 5 phr PDMSA is 66% higher than that of neat phenolic resin. Flexural modulus of cured resin specimen contains 5 phr PDMSA is 3.6 times that of neat phenolic resin. Notched Izod impact strength of cured resin specimen contains 5 phr PDMSA is 37% higher than that of neat phenolic resin.TGA results of PDMSA modified Novolac penolic resin cured specimen in air show two step degradation. The addition of aliphatic chain of PDMSA to phenolic resin will decrease the first step degradation temperature of the cured resin specimens; however the siloxane chain will increase the second step degradation temperature.The flame resistance of the PDMSA modified novolac type phenolic resin cured specimens of UL-94 shows V-1 and its L.O.I is 35, which exhibit good flame resistance properties.

摘要………………………………………………………………Ⅰ英文摘要…………………………………………………………..Ⅲ謝誌………………………………………………………………..Ⅴ目錄………………………………………………………………..Ⅵ圖目錄……………………………………………………………Ⅷ表目錄…………………………………………………………..ⅩⅠ第一章 緒論………………………………………………………11-1 前言……………………………………………………..11-2 研究目的與內容………………………………………..41-1.1 研究目的…………………………………………………..41-1.2 研究內容…………………………………………………...5第二章 理論基礎…………………………………………………72-1 Novolac Type 酚醛樹脂之製備與特性………………72-2 Resole Type 酚醛樹脂之製備與特性………………...122-3 矽酮-酚醛樹脂之合成…………………………………142-4 利用DSC測量聚摻合物之玻璃轉移溫度之原理探討.…………………………………………………………162-5 利用IR觀察聚摻合物之OH吸收峰之變化…………..18第三章 文獻回顧………………………………………………193-1 酚醛樹脂改質的相關研究……………………………193-2 以矽化物改質酚醛樹脂的相關研究…………………31第四章 實驗方法………………………………………………..344-1 實驗藥品………………………………………………...344-2 實驗儀器及設備及其操作……………………………...364-3 實驗步驟………………………………………………...394-3.1 增韌劑poly-(dimethylsiloxane adipamide)之合成步驟…394-1.2 poly-(dimethylsiloxane adipamide) (PDMSA)與Novolac type phenolic resin摻混之實驗步驟……………………..424-1.3 試片製作與機械性質測試之實驗流程………………….444-1.4 測試分析………………………………………………….46第五章 結果與討論……………………………………………..505-1 Novolac type酚醛樹脂之合成結果分析……………505-2 poly-(dimethylsiloxane adipamide) (PDMSA)之合成結果分析………………………………………………….565-3 Novolac type酚醛樹脂與PDMSA摻混之DSC結果與分析…………………………………………………….675-4 Novolac type酚醛樹脂與PDMSA摻混之IR結果與分析……………………………………………………….735-5 Novolac type酚醛樹脂與PDMSA摻混之熱重量損失(TGA) 分析……………………………………………795-6 Novolac type phenolic resin / PDMSA摻合物硬化後之機械性質分析結果……………………………………905-6.1 加工條件探討………………………………………905-6.2 抗曲強度與抗曲模數測試結果分析………………945-6.3 耐衝擊強度測試結果分析…………………………...955-7 Novolac type phenolic resin / PDMSA摻合物硬化後之抗熱性質(TGA)結果分析……………………………1005-8 Novolac type phenolic resin / PDMSA摻合物硬化後之防火耐燃性質測試…………………………………1055-9.1 UL-94耐燃性測試…………………………………1055-9.2 極限需氧指數 ( L.O.I ) 測試………………………1055-9 Novolac type phenolic resin / PDMSA摻合物硬化後之型態學分析…………………………………………107第六章 結論…………………………………………………….111第七章 參考文獻………………………………………………114

1. A. Knop, L. A. Pilato, "Phenolic Resins: Chemistry, Application and Performance " Springer-Verlag, Berlin, pp1-4, 1985.2. T. Mottram, B. Geary, R. Taylor, "Thermal Expansion of Phenolic Resin and Phenolic-fiber Composites", Journal of Materials Science, Vol.27, 5015~5026, 1992.3. J. F. Meier, E. M. Bellott. JR, P. P. Frank, "Preparation and Properties of Phenolic Resin Laminates. I. Laboratory Evaluation ", Journal of Applied Polymer Science, Vol.21, 1383~1394, 1977.4. D. G. Roberts, M. S. Lloyd, S. P. Mainwaring, "Low Smoke and Fume Cables with Enhanced Fire Performance, Resistance to Moisture and Mechanical Properties. ", IEE Conference Publication, No.382, Publ by IEE, Michael Faraday House, Stevenage, Engl, pp179-183, 1993.5. U. Sorathia ; C. M. Rollhauser and W. A. Hughes, "Fire Safety of Composites for Naval Applications.", Fire and Materials, Vol.16,No.3., pp 119-125, 1992.6. Y. Zaks, Jeelenlo, D. Raucher, and E. M. Pearce, "Structure Property Relationships in Polymer Flammability : Studies of Phenolic-Derived Polymers", Journal of Applied Polymer Science, Vol.27, 913~930, 19827. 馬振基，楊正乾，「矽酮壓克力、環氧樹脂、酚醛樹脂等之製備與特性之研究」研究報告，國防科技發展專方 案學術合作協調小組，1996.8. "Compound -Register and Review" Petrarch Systems, Inc., Bristol, PA, U.S.A., 1984.9. G. Odian, "of Polymerization" 3rd Edition, Chapter 2, pp125-132, 1991.10. 村山新一著，洪純仁編譯 ，「酚醛樹脂」， 復文書局, pp53-54,198411. Enio Kumpinsky, "Process Design and Control: A Study on Resol Type Phenol-Formaldehyde Runaway Reactions " Ind. Eng. Chem. Res., Vol. 33,No. 2,285~291,199412. Marie-Florence Grenier-Loustalot, Stephane Larroque ; Philippe Grenier ; Jean-Paul Leca and Didier Bedel, "Phenolic Resins: 1.Mechanisms and Kinetics of Phenol and of The First Polycondensates Towards Formaldehyde in Solution ", Polymer., Vol.35, No.14,3046~3054,199413. Marie-Florence Grenier-Loustalot,Stephane Larroque and Philippe Grenier,"Phenolic Resins:5.Solid-State Physicochemical Study of Resoles with Variable F/P Ratios ", Polymer., Vol. 37, No.4, 639~650,199614. Marie-Florence Grenier-Loustalot, Stephane Larroque ; Philippe Grenier and Didier Bedel, "Phenolic Resins : 2. Influence of catalyst Type on Reaction Mechanisms and Kinetics" Polymer.,Vol. 37, No.8, 1363~1369, 199615. Hisashi Sugiyama, Takashi Inoue, and Kazuo Nate, "on Organosilicon Positive Resist. I. Syntheses and Characterization of Silsesquioxane, Siloxane, and Silmethylene Polymers with Phenolic Hydroxy Groups" J. of App. polym. Sci., Vol.44, pp1573-1582, 1992.16. Oonishi, Kyonobu; Hayase, Shuji; Horiguchi, Rumiko; Gokochi, Tooru, "containing ultraviolet photoresists" Jpn. Kokai Tokkyo Koho JP 01159638 [89159638] (IPC G03C-001/71), 22 Jun 1989, Appl. 87/317857, 16 Dec 1987, 10 pp.17. P. R Couchman; F. E. Karasz, "A Classical Thermodynamic Discussion of the Effect of Composition on Glass Transition Temperatures. " Macromolecules, vol. 11, 1156, 1978.18. L. A. Utracki, "The Glass-Transition of Linear Macromolecules." Advanced Polymer Technology, vol. 5, 33, 1985.19. J. M. Pochan, C. L. Beatty and D. F. Pochan, "Different Approach for the Correlation of the Tg of Mixed Amorphous System." Polyer, vol. 20, 879, 1979.20. M. Gordon and J. S. Taylor, "of Hydrogen Bonding on the Enthalpyof Mixing and the Composition Dependence of the Glass Transition Temperature in Polymer Blends." Journal of Applied Chemistry, vol. 2, 493, 1952.21. T. G. Fox, "Transition Temperature of Mesophase Macromolecules." Journal of Bulletin American Physical Society, vol. 1, 123, 1956.22. Eric J. Moskala, Stephan E. Howe, Paul C. Painter, and Michael M. Coleman,"the Role of Intermolecular Hydrogen Bonding in Miscible Polymer Blends." Macromolecules, vol. 17, 1671, 1984.23. G. Belorgey, M. Aubin, and R. E. Pruhhmme, "of Polyester Chlorinated Poly(Vinyl-chloride) Blends." Polymer, vol. 23, 1051, 1982.24. T. K. Kwei, "Effect fo Hydrogen-Bonding on the Glass Transition Temperatures of Polymer Mixtures." Journal of Polymer Science, Part C: Polymer Letters, vol. 22, 307, 1984.25. Union Carbide Corporation, "Aqueous Dispersions Based on Heat -Hardenable Phenolic Resins Containing a Gum Mixture Stabilizing Agent. ", U.S.Patent 3,823,103,1974.26. S. R. Fahrenholtz and T. K. Kwei, "Compatibility of Polymer Mixtures Containing Novolac Resin " Macromolecules, Vol 14, No. 4. pp 1076-1079,1981.27. J. L. Hedrick, I. Yilgor, G. L. Wilkes, and J.E.McGrath, "Chemical Modification of Matrix Resin Networks with Engineering Thermoplastics. I. Phenolic Hydroxyl Terminated Poly(Aryl Ether Sulfone)-Epoxy System " Polymer Bulletin, Vol.13, 201~208, 1985.28. M. M. Colemon, C. J. Serman, and P. C. Painter, "Effect of Cross-Linking on the Degree of Molecular Level Mixing in a Polymer Blend " Macromolecules, 20, 266~232, 1987.29. G. R. Hatfield, and G. E. Maciel, "Solid-State NMR Study of the Hexamethylenetetramine Curing of Phenolic Resins " Macromolecules, Vol.20, 608~615, 1987.30. H. I. Kim, E. M. Pearce, and T. K. Kewi, "Miscibility Control by Hydrogen Bonding in Polymer Blends and Interpenetrating Networks " Macromolecules, Vol.22, 3374~3380, 1989.31. A. Matsumoto, K. Hasegwa, A. Fukuda, and K. Otsuki, "Study on Modified Phenolic Resin.I.Modification with Homopolymer Prepared from p-Hydroxyphenylmaleimide ", Journal of Applied Polymer Science, Vol. 43, 365~372,1991.32. A. Matsumoto, K. Hasegwa, A. Fukuda, and K. Otsuki, "Study on Modified Phenolic Resin. II. Modification with P-Hydroxy-phenylmaleimide / Styrene Copolymer " Journal of Applied Polymer Science, Vol. 44, 205~212, 1992.33. A. Matsumoto, K. Hasegwa, A. Fukuda, and K. Otsuki, "Study on Modified Phenolic Resin. II.Modification with p-Hydroxyphenyl-maleimide/ Acrylic Ester Copolymer " Journal of Applied Polymer Science, Vol. 44, 1547~1556,1992.34. A. Matsumoto, K. Hasegwa, and A. Fukuda, "Studies on Modified Phenolic Resin. IV. : Properties of Phenolic Resin Modified with 4-Hydroxyphenylmaleimide/ n-Butylacrylate Copolymer ",Polymer Inter-national, Vol. 30, No.30, 65~72, 1992.35. Xiuxun ,Wang; Hiromu Saito and Takashi , Inoue, "Mechanical Property-Structure Relationship in Binary Mixtures of Poly (oxymethylene) and Novolac Resin " Kobunshi Ronbunshu / Japanese Journal of Polymer Science And Technology, Vol.49, No.7, 555-560,199236. Ishii Toshake, "Modification of Epoxy Resins by Resol Type Phenolic Resin ", Japanese Journal of Polymer Science and Technology, Vol.49, No.8, 671~676,199237. Huai-Chim Chang , "Study of the Synthesis and the Compatibility of Phenolic/Poly(N-butyl Acrylate) IPNS "Polymeric Materials Science and Engineering,Vol.9,No.2.33~37,199338. X. Zhang, and D. H. Solomon, "Phase Structures of Hexamine Cross-Linked Novolac Blends. I. Blend with poly(methyl methacrylate) " Macromolecules, Vol. 27, No. 18, 4919 ,1994.39. Toshifumi Okuno,Miyaji , "Phenolic Resin Molding Compounds and The Articles Thereof ", U. S. Patent No. 5,336,724. 1994.40. Rosy ,Antony and C.K.S. Pillai, "Synthesis and Thermal Characteristic of Chemically Modified Phenolic Resins " Journal of Applied Polymer Science, Vol.54, No.4, 429~438, 1994.41. X. Ning, and H.Ishida, "Phenolic Materials via Ring-Opening Polymerization of Benzoxazines : Effect of Molecular Structure on Mechanical and Dynamic Mechanical Properties " Journal of Polymer Science : Part B :Polymer Physics, Vol.32, 921~927, 1994.42. X. Ning, and H.Ishida, "Phenolic Materials via Ring-Opening Polymerization : Synthesis and Characterization of Bisphenol-A Based Benzoxazines and Their Polymers " Journal of Polymer Science : Part A : Polymer Chemistry, Vol.32, 1121~1129, 1994.43. Chengguo Wang, Qifeng Peng , Junhai Liu, Xitai Sun, Jing Zhu and Qigong Cai, "Tensile-Shear Strength and Breaking Morphology for Vibration Damping Laminated Steel Sheet " Acta Metallurgica Sinica,Series A：Physical Metallurgy＆Materials Science, Vol.7, No.2, 114~118, 1994.44. M.Mueller; K.M.Beinborn and K.J.Huettinger, "Significance of the Fibre Coating in the Production of Carbon Fibre-Reinforced Carbons from HT Carbon Fibre and Phenolic Resin as Matrix Precursor II.Phenolic Resin Coatings " Carbon, Vol.33, No.8, 1043~1046, 1995.45. L. K. Aggarwal, K. K. Asthana and Rajni Lakhani, "Epoxy-Phenolic IPN Coating for Concrete and Reinforcing Steel. " Indian Concrete Journal, Vol.69, No.5, 269~273, 1995.46. Masaki Hasegawa,Tadashi Kobayashi,Pushpalal G. K. Dinilprem, "New Class of High Strength,Water and Heat Resistant Polymer-Cement Composite Solidified by an Essentially Anhydrous Phenol Resin Precursor. " Cement and Concrete Research, Vol.25, No.6, 1191~1198, 1995.47. Lianzhen Lin ; Yoshioka,Mariko; Yaoguang ,Yao and Nobuo ,Shiraishi, "Preparation and Properties of Phenolated Wood / Phenol / For-maldehyde Cocondensed Resin. " Journal of Applied Polymer Science, Vol.58, No.8, 1297~1304, 1995.48. J. Jang, and S. Shin, "Cure Studues of a Benzoxazine-Based Phenolic Resin by Isothermal Experiment " Polymer Journal, Vol.27, No.6, 601~606, 1995.49. Carey, Paul; Lott, Michelle, "Sand Binder Systems Part VIII-Ester-Cured Alkaline Phenolic Resins " Foundry Management＆ Technology, Vol.123,No.10, 21~26,199550. Gang , Yu, "Study on Phenolic Resin Modified with Tung Oil-Curing Behavior and Kinetic Analysis " Gaofenzi Cailiao Kexue Yu Gong-cheng / Polymeric Materials Science And Engineering, Vol.11, No.2,121~ 126,199551. Nafaa Mekhilef and Pavlos Hadjiandreou, "Miscibility Behaviour of Ethylene Vinyl Acetate / Novolac Blends " Polymer, Vol.36, No.4 , 2165~2171,199552. Hew-Der Wu; Ming-Shiu Li; Chen-Chi M. Ma; Yio-Don Wu, "toughened phenolic resin for pultruded composites." Annual Technical Conference - ANTEC, Conference Proceedings Proceedings of the 53rd Annual Technical Conference. Part 2 (of 3) May 7-11 1995 v2 1995.53. Hew-Der Wu; Ming-Shiu Lee; Yiu-Don Wu; Yi-Feng Su; Chen-Chi M. Ma, "fiber-reinforced polyurethane-toughened phenolic resin. II. Mechanical properties, thermal properties, and flame resistance." Journal of Applied Polymer Science v62 n1 Oct 3 1996.54. Hatsuo Ishida.; Douglous I Allen.,"Physical and Mechanical Characterization of Non-Zero Shrinkage Polybenzoxazines. " Journal of Polymer Science,Part B：Polymer Physics, Vol.34, No.6 , 1019~1030,1996.55. Andrew J Foden.; P.Balaguru.;,Richard E. Lyon ,"Mechanical Properties and Fire Response of GEOPOLYMER Structural Composites." International SAMPE Symposium and Exhibition (Proceedings), Vol.41, No.1 , 748~758,1996.56. Roderick A. McDonald,; Shahid P. Qureshi, "Feasibility Study for Non-Volatile Cure of Novolak-Epoxy Composites. " International SAMPE Symposium and Exhibition(Proceedings), Vol.41, No.2 , 1573~1586,1996.57. A. A. Shariatmadari, T. V. Parry, G. M.Parton, "Fracture Strength and Tougjness of Some Phenolic Concretes " Journal of Materials Science, Vol.31,No.2,413~422,199658. Wen-Yen ,Chiang and Dong-Meau ,Chang, "Mechanical and Dynamic Properties of Graft Polyurethane/Allyl Novolac Resin Simultaneous Interpenetrating Network " Polymer International, Vol.39,No.1,55~ 60,199659. A. Y. Uyarel and I. Pektas, "Thermal Analysis Investigation of New Insulator Compositions Based on EPDM and Phenolic Resin " Journal of Thermal Analysis，Vol.46,No.1,163~176,199660. Aijuan Gu; Guozheng Liang and Liwen Lan, "Modification of Polyaralkyl-Phenolic Resin and Its Copolymer with Bis-malemide " Journal of Applied Polymer Science, Vol. 59, No.6, 975~979, 199661. Zhikai Zhong and Qipeng Guo, "The Misicibility and Morphology of Hexamine Cross-Linked Novolac / Poly( -caprolactone) Blends. " Polymer, Vol.38, No.2, 729,1997.62. Her-Der Wu;Chen-Chi M. Ma;andChar-Ming Lin, "Processability and Properities of Phenoxy Resin Toughened Phenolic Resin Composites"of Applied Polymer Science,,Vol.63,911,199763. Chen-Chi M. Ma; Hew-Der Wu; Yi-Feng Su; Ming-Shiu Lee; Yiu-Don Wu, "fiber reinforced novolac type phenolic composite processability, mechanical properties and flame resistance." Composites: Part A: Applied Science and Manufacturing v 28 n 9-10 1997.64. Chen-Chi M. Ma; Hew-Der Wu; Peter P. Chu; Han-Thing Tseng, "of thermodynamic properties of Novolak-type phenolic resin and aliphatic polyester blends: Painter-Coleman association model study of compositional homogeneity." Macromolecules v 30 n 18 Sep 8 1997.65. Chen-Chi M. Ma; Shien-Fu Meng; Long Y. Chiang; Lee Y. Wang; Chu, P. Peter; Wu, "and characterization of fullerene-derived polymer blended with Novolac type phenolic resin." Fullerene Science and Technology v 5 n 5 Aug 1997.66. Chen-Chi M. Ma; Chih-Tsung Lee; Hew-Der Wu, "fiber reinforced poly(ethylene oxide) toughened novolac type phenolic resin: Mechanical properties, thermal stability, and flame retardance." International SAMPE Technical Conference Composites for Real World Proceedings of the 1997 29th International SAMPE Technical Conference Oct 28-Nov 1 1997 v 29 1997.67. Chen-Chi M. Ma; Chih-Tsung Lee; Hew-Der Wu, "properties, thermal stability, and flame retardance of pultruded fiber-reinforced poly(ethylene oxide)-toughened Novolak-type phenolic resin." Journal of Applied Polymer Science v 69 n 6 Aug 8 1998.68. Chen-Chi M. Ma; Han-Thing Tseng; Hew-Der Wu, "diisocyanate polyester-toughened Novolak-type phenolic resin: Synthesis, characterization, and properties of composites." Journal of Applied Polymer Science v 69 n 6 Aug 8 1998.69. Chen-Chi M. Ma; Hew-Der Wu; Chih-Tsung Lee, "of hydrogen bonding in the novolak-type phenolic resin blends." Journal of Polymer Science, Part B: Polymer Physics v 36 n 10 Jul 30 1998.70. Peter P. Chu; Hew-Der Wu; Chih-Tsung Lee, "properties of novolac-type phenolic resin blended with poly(ethylene oxide)." Journal of Polymer Science, Part B: Polymer Physics v 36 n 10 Jul 30 1998.71. Hew-Der Wu; Peter P. Chu; Chen-Chi M. Ma, "properties of the novolac type phenolic resin blended with poly(hydroxyl ether of bisphenol A)." Polymer v 39 n 3 Feb 1998.72. Feng-Yih Wang, "on The Polyamide Resins Thoughened Novolac Type Phenolic Resin."國立清華大學化學工程研究 所碩士論文, 1998.73. 李育德，蔡明福， "高溫酚醛絕熱材料改質研究" 國立清華大學自強科學研究中心委託合作研究計畫總結研 究報告，1998。74. General Electric Co.: US-PS 2 258 218 (1941)75. Dow Corning Corp.: DE-PS 937 555 (1956)76. Stenbeck, G.: DE-OS 1 694 97477. Westinghouse Electric Corp.: US-PS 2 836 740 (1958)78. Dow Corning Corp.: US-PS 2 842 522 (1958)79. M. A. Kiselev, A. I. Kuzayev, "Preperation and Properties of Silicone Modified Phenol-Formaldehyde Resin." U.S. Patent 2,658,054 (1963).80. Kyonobu, Oonishi; Shuji, Hayase; Rumiko, Horiguchi; Gokochi, Tooru, "containing ultraviolet photoresists" Jpn. Kokai Tokkyo Koho JP 01159638 [89159638] (IPC G03C-001/71), 22 Jun 1989, Appl. 87/317857, 16 Dec 1987, 10 pp.81. Yukio, Abe; Toshi, Iizuka; Juji, Myashita; Yutaka Arai, , "of Silicone-Modified Phenolic Resin Fibers Resisting Heat, Chemicals and Moisture" Jpn. Kokai Tokkyo Koho JP 01 68516 [89 68516] (IPC D01F-006/76), Mar. 14 (1989), Appl. 87/123554, 20 May 1987, 5 pp.82. Jean-Paul Pillot, Jacques Dunogues, Jacqeline Gerval, Ninh Dao The and Mai Van Thanh, "Hydro-Silylation of Cardanol by Methyldichloro-Silance Application to the Synthesis of New Silicone Grafted Phenolic Resin." Eur. Polym, J. Vol.22, 3374~3380, 1989.83. Kenichi, Yanagisawa; Masaru, Ota, "Modified Phenolic Resins for Semiconductor sealants" Jpn Kokai Tokkyo Koho JP 02173025 [90173025] (IPC C08G-008/28), 4 Jul 1990, Appl. 88/326040, 26 Dec 1988, 6 pp.84. Hisashi Sugiyama, Takashi Inoue, and Kazuo Nate, "Study on Organosilicon Positive Resist. I. Syntheses and Characterization of Silsesquioxane, Siloxane, and Silmethylene Polymers with Phenolic Hydroxy Groups." J. of App. polym. Sci., Vol. 44, 1573-1582 1992.85. C. P. Reghunadhan, Nair ; R. L. Bindu and V. C. Joseph, "Cyanate Esters Based on Cardanol Modified-Phenol-Formaldehyde Resins：Syntheses and Thermal Characteristics " Journal of Polymer Science,Part A：Polymer Chemistry, Vol.33, No.4, 621~627, 1995.86. Lightbody, Alan William; Jones, John Edward, "of hybrid phenolic/polysiloxane resins." PCT Int. Appl. WO 9719977 A1 5 Jun 1997, 18 pp.87. Wang, Chao; Zhang, Bin; Guan, Chang Shen, "on polysiloxane-modified phenolic resin-butadiene-acrylonitrile rubber adhesive." Zhongguo Jiaonianji, 6(1), 14-17 (Chinese) 1997 Zhongguo Jiaonianji Bianjibu..88. Haraguchi, Kazutoshi; Usami, Yusho, "organic-inorganic hybrid materials composed of phenolic resin and silica." DIC Tech. Rev., 3, 42-46 (English) 199789. Mandal, Humayun; Hay, Allan S. "and characterization by MALDI-TOF MS of polycyclic siloxanes derived from p-substituted Novolac resins by MALDI-TOF MS." Journal of Polymer Science, Part A: Polymer Chemistry, vol. 36, No. 14, 2429-2437, 1998.90. Limiting Oxygen Index Chamber Operation Manual.ATLAS equipment Corp 199091. 薛敬和編譯,"實驗法"高立圖書有限公司(1986)92. A. C. Fernandes, J. W. Barlow, and D. R. Paul, "Containing Tetramethyl Bisphenol-A Polycarbonates. 1. Styrenic Polymers." Polymer, 27, 1778, 1986.93. 宋享金，「以熱塑性樹脂及碳60製預聚合物改質酚醛樹脂及試製高性能複合材料之研究」，清華大學化學工程 研究所碩士論文1998.