臺灣博碩士論文加值系統

聚苯醚(PPO)具有高玻璃轉移溫度，及優異的電氣特性如低介電常數及低介電損失係數等性質，常被用於高頻基板以及寬頻的電子通訊元件。然而PPO本身屬於熱塑性材料，因此耐熱性以及尺寸安定性仍不足；除此之外，聚苯醚樹脂具有熔點高，在進行加工時熔融黏度大不易加工，且溶劑的溶解性較低，使預浸材製造過程中樹脂溶液之黏度大，導致在進行多層基板壓製過程時產生缺陷。因此，需要合成低分子量的PPO樹脂(LPPO)，並將其改質成含反應性官能基的熱固性材料，以提高其耐熱性並改善製程上缺陷。
利用氧化偶合聚合法，選用單官能基和雙官能基酚化合物，在銅化合物/胺類化合物等觸媒存在下，可合成得到LPPO，利用FTIR、1H-NMR進行結構鑑定，並利用GPC測定其分子量；再將LPPO與BrCN反應，合成得到含聚苯醚氰酸酯樹脂(LPPOCE)，並利用微分掃描熱卡計(DSC)探討其熱硬化行為，硬化後利用DMA、TMA、DEA、TGA及吸溼性探討其物性。由結果顯示，硬化後的含聚苯醚氰酸酯樹脂(LPPOCE)能保持優異的熱機械性質及高Tg與低介電，且具有低吸濕率的特性。
將不同含量的LPPOCE分別加入環氧樹脂及雙馬來醯亞胺-三氮雜環(BT)樹脂系統中，探討環氧樹脂及BT樹脂的熱硬化行為及其硬化物之物性。由結果顯示，LPPOCE有效地降低環氧樹脂或是BT樹脂硬化物的介電常數及吸濕性，而熱穩定性會隨著LPPOCE添加量增加而提升，但是玻璃轉移溫度會隨著LPPOCE的添加而稍微降低。

Polyphenylene oxide (PPO) are suitable as a material for the printed circuit boards used in the electronic devices that utilize broadband, owing to their high glass transition temperature (Tg ) and favorable high frequency characteristics for example in dielectric constant and dielectric loss. However, PPO resins were not so far sufficiently high in heat resistance and dimensional stability. In addition, these PPO resins carry the disadvantage that they generally have a high melting point, and the use of such a PPO resin for production of prepregs for ordinary multilayer printed circuit boards often resulted in increases in melt viscosity of the prepreg, causing processing defects. Therefore, there is need a low molecular weight PPO (LPPO) and to modify it into a thermosetting resin so as to increase the heat resistance properties and to improve processability.
The LPPO based cyanate Ester (LPPOCE) was successfully prepared from the reaction between BrCN and LPPO, which was synthesized from bifunctional phenol and monofunctional phenol compound through oxidative coupling polymerization route in the presence of copper/amine catalysts. The structure of synthesized LPPOs were confirmed by Fourier transform infrared spectroscopy (FTIR), Gel-Permeation Chromatography (GPC), and nuclear magnetic resonance spectroscopy (NMR). The thermal curing behavior of LPPOCE was studied by differential scanning calorimetry (DSC). The properties of cured LPPOCE were studied by dynamic mechanical analysis (DMA), thermal mechanical analysis (TMA), dielectric analysis (DEA), thermal gravimetric analysis (TGA) and moisture absorption. The results show that cured LPPOCE possess a low dielectric constant, high Tg, low water absorption, and good retention of mechanical properties.
Various contents of LPPOCE were added into epoxy resin and Bismaleimide-Triazine (BT) resin, respectively. The thermal curing behaviors of thermocurable epoxy resin and thermocurable BT resin were investigated, and their cured network’s physical properties were also investigated. The results indicate that LPPOCE effectively reduce the dielectric constant and moisture absorption both of cured epoxy resin and BT resin. The thermal stability properties of cured epoxy resins and BT resin were increased with the increasing of LPPOCE contents, whereas the glass transition temperature slightly decreased.

目 錄
中文摘要 i
英文摘要 ii
誌謝 iv
目錄 v
Scheme viii
表目錄 ix
圖目錄 x
第一章 緒論 1
1-1 前 言 1
1-2 印刷電路板發展趨勢 1
1-3 高頻基板材料的特性 2
1-4 研究之目的 4
第二章 原理與文獻回顧 9
2-1 聚氧化二甲苯（Polyphenylene Oxide; PPO） 9
2-1-1 聚氧化二甲苯的簡介 9
2-1-2 聚氧化二甲苯的結構和特性 9
2-1-2-1 聚氧化二甲苯的結構 9
2-1-2-2 聚氧化二甲苯的特性 9
2-1-3 聚氧化二甲苯的合成及應用 11
2-1-3-1 聚氧化二甲苯的合成 11
2-1-3-2 聚氧化二甲苯的應用 12
2-1-4 聚氧化二甲苯的改質與文獻回顧 13
2-1-4-1 聚氧化二甲苯的改質 13
2-1-4-1-1 物理改質 13
2-1-4-1-2 化學改質 15
2-1-4-2 聚氧化二甲苯的文獻回顧 17
2-2 氰酸酯（Cyanate Ester） 19
2-2-1 氰酸酯簡介與文獻回顧 19
2-2-2 氰酸酯的合成反應原理 22
2-3 雙馬來醯亞胺(BMI) 23
2-4 BT樹脂 25
2-4-1 BT樹脂的簡介 25
2-4-2 BT樹脂的特性和應用 26
2-4-3 BT樹脂的改質與文獻回顧 27
2-5 介電性質概述 29
2-5-1 介電常數 29
2-5-2 介電損失 30
第三章 實驗部份 32
3-1 實驗流程圖 32
3-2 材料與藥品 33
3-3 實驗裝置圖 35
3-4 儀器設備 36
3-5 實驗步驟 37
3-5-1 低分子量PPO（LPPO）之合成 37
3-5-2 LPPO Based Cyanate Ester (LPPOCE) 之合成 38
3-5-3 LPPO Based Cyanate Ester之三環化硬化反應 39
3-5-4 硬化反應動力學之探討 39
3-6 試片之製作 40
3-6-1 含聚苯醚氰酸酯樹脂(LPPOCE)之硬化條件 40
3-6-2 環氧樹脂(CNE)/硬化劑(DDS)/含聚苯醚氰酸酯樹脂(LPPOCE)系統之配方及硬化條件 40
3-6-3 環氧樹脂(CNE)/硬化劑(BADCy)/含聚苯醚氰酸酯樹脂(LPPOCE)系統之配方及硬化條件 40
3-6-4 雙馬來醯亞胺(BMI)/氰酸酯(BADCy)/含聚苯醚氰酸酯樹脂(LPPOCE)系統之配方及硬化條件 41
3-7 結構鑑定與物性測試 41
第四章 含聚苯醚氰酸酯樹脂合成與鑑定及其物性之研究 46
4-1 合成與鑑定 46
4-1-1 LPPO之合成鑑定 46
4-1-2 LPPO Based Cyanate Ester (LPPOCE)之合成鑑定 47
4-2 硬化動力學參數探討 47
4-3 動態機械分析 48
4-4 熱機械分析 49
4-5 熱穩定性分析 50
4-6 吸溼性 50
4-7 介電性質 51
4-8 結論 51
第五章 含聚苯醚氰酸酯樹脂改質環氧樹脂之物性研究 65
5-1 示差掃描熱分析 65
5-2 動態機械分析 65
5-3 熱機械分析 66
5-4 熱穩定性分析 66
5-5 吸溼性 67
5-6 介電性質 67
5-7 結論 68
第六章 含聚苯醚氰酸酯樹脂改質BT樹脂之物性研究 89
6-1示差掃描熱分析 89
6-2 動態機械分析 89
6-3 熱機械分析 89
6-4 熱穩定性分析 90
6-5 吸溼性 90
6-6 介電性質 90
6-7 結論 91
第七章 總結 105
參考文獻 106

【1】邱國展，2002，工業材料，187期，p. 137。
【2】陳孟暉，2001，工業材料，170期，p. 81。
【3】王先毅、黃仕穎、陳姿秀、陳永志，2003，工業材料，189期 p. 136。
【4】N. Kinjo, M. Ogata, K. Nishi and A. Kaneda, 1989, Advances in Polymer Science, 88, Springer-Verlag, Berlin.
【5】C. S. Wang and T. S. Leu, 2000, “Synthesis and characterization of polyimides containing naphthalene pendant group and flexible ether linkages”, polymer, 41(10), p. 3581-3591.
【6】T. S. Leu and C. S. Wang, 2001, “Kinetic Models for Solution Imidization of Polyamic Acid Containing Naphthalene-Pendant Group”, J. Polym. Sci. Part A: Polym. Chem., 39(23), p. 4139-4151.
【7】許再發，黃仁豪，劉文隆，1999，工業材料，151期，p. 100。
【8】C. H. Lin, J. C. Chiang and C. S. Wang, 2003, “Low Dielectric Thermoset. I. Synthesis and Properties of Novel 2,6-Dimethyl Phenol-Dicyclopentadiene Epoxy”, J. Appl. Polym. Sci., 88(11), p. 2607-2613.
【9】C. H. Lin, Z. R. Jiang and C. S. Wang, 2002, “Low Dielectric Thermoset. II. Synthesis and Properties of Novel 2,6-Dimethyl Phenol-Dipentene Epoxy”, J. Polym. Sci. Part A: Polym. Chem., 40(22), p. 4084-4097.
【10】J. P. Pascault, et al., 1994, “Additives and modifiers for cyanate ester resins”, in “Chemistry and Technology of Cyanate Ester Resins”, BLACKIE ACADEMIC & PROFESSIONAL, Chap. 5, p. 128.
【11】H. F. Mark and N. G. Gaylord, 1976, “Encyclopedia of Polymer Science and Technology”, JOHN WILEY, p.92.
【12】朱家駿，2003，電路板會刊，22期，p.56。
【13】I. S. Chung and S. Y. Kim, 2000, “Soluble Polyimides from Unsymmetrical Diamine with Trifluoromethyl Pendent Group”, Macromolecules, 33(9), p. 3190-3193.
【14】S. H. Lin, S. Z. D. Cheng and F. W. Harris, 1998, “Organo- Soluble Polyimides: Synthesis and Polymerization of 2,2’-Bis(trifluoro- methyl)-4,4’,5,5’-Biphenyltetracarboxylic Dianhydride”, Macro- molecules, 31(7), p. 2080-2086.
【15】T. Matsumoto and T. Kurosaki, 1997, “Soluble and Colorless Polyimides from Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3: 5,6-Dianhydrides”, Macromolecules, 30(4), p. 993-1000.
【16】王津，2003，”聚苯醚樹脂改質的發展”，中國西部科技，5期，p. 57-59。
【17】霍剛，2000，”熱固性聚苯醚樹脂在高頻印刷電路板上的應用”，中國塑料，14期，p. 14。
【18】日本特開平 6-17457
【19】日本特公平 8-5818
【20】日本特公平 3-6185
【21】G. Jochen, 2000, “Procede de preparation d’ethers de polyphony- lene fonctionnalises”, US Patent, WO0052074
【22】化工百科全書，2003，化學工業出版社。
【23】吳紹榮，2000，”環氧樹脂/聚氧化二甲苯掺合體反應性、相行為及機械性質之研究”，國立中央大學化學工程系碩士論文。
【24】S. Li, Q. Yuan, G. Ke and L. Wang, 2002, “Modification and Develop-ment of Polyphenylene Oxide”, Hubei Reseach Institute of Chemistry, Wuhan 430074.
【25】Y. Ishii, et al., 2003, “Phase diagram prediction for a blend of Poly (2,6-dimethyl-1,4-phenylene ether)(PPE)/epoxy resin during reac- tion induced phase separation”, Polymer, 44(13), p. 3641-3647.
【26】J. E. Tracy and Warsaw, et al., 1998, ”Curable polyphenylene ether-thermosetting resin composition and process”, US Patent, US5834565
【27】日本特開平 6-206984.
【28】R. A. Pearson and A. F. Yee, 1993, “The preparation and mor- phology of PP0-epoxy blands”, J. Appl. Polym. Sci., 48(6), p. 1051-1060.
【29】因格布雷西特，2000，”生產低分子量聚苯醚樹脂的方法”，CN1334836。
【30】A. J. Braat, et al., 2000, “process for the manufacture of low molecular weight polyphenylene ether resins”, WO0046273.
【31】日本特開 2003-313290，旭化成。
【32】J. V. Crivello, 2003, “Accelerateurs de photopolymerisation cationique”, US Patent, WO03076491，旭化成。
【33】S. Kuberkar and S. K. Gupta, 1996, “Simulation of poly(phenylene oxide) reactors”, Polymer, 37(7), p. 1243-1256.
【34】R. W. Venderbosch, H. E. H. Meijer and P. J. Lemstra, 1994, “Processing of intractable polymers using reactive solvents: 1. Poly(2,6-dimethyl-1,4-phenylene ether)/epoxy resin”, Polymer, 35, p. 4349-4357.
【35】H. Fujiwara, B. S. Kim and T. Inoue, 1996, “Reactive processing of thermoset/thermoplastic blends: A potential for injection molding”, Polym. Eng. and Sci., 36(11), p. 1541-1546.
【36】T. Iijima, T. Nishina, W. Fukuda and M. Tomo, 1996, “Effect of Matrix Compositions on Modification of Bismaleimide Resin by N-Phenylmaleimide-Styrene Copolymers”, J. Appl. Polym. Sci., 60(1), p. 37-45.
【37】T. Fukuhara, Y. Shibasaki, S. Ando and M. Ueda, 2004, “Synthesis of thermosetting poly(phenylene ether) containing allyl groups”, Polymer, 45(3), p. 843-847.
【38】D. A. Shimp, J. R. Christenson and S. J. Ising, 1989, Int. SAMPE. Symp. Exhibit., 34, p. 222.
【39】K. K. Weirauch, P. G. Gemeinhardt and A. L. Baron, 1976, Soc. Plast Eng., Technical, 22, p. 317.
【40】B. G. Richard, 1986, Polymer Preprints, 27, p. 491.
【41】李明峻，1999，”新穎含荼環氧樹脂之合成與性質研究”，成功大學化學工程學系博士論文。
【42】V. A. Pankratov, et al., 1977, Russ. Chem. Rev., vol. 46(3), p. 278.
【43】K. Iwata and J. K. Stille, 1976, “Higher molecular weight phenylated free-radical curing agents: 4,4 -oxybis(triphenyl- methyl hydroperoxide)”, J. Polym. Sci. Polym. Chem. Ed., 14(11), p. 2841-2843.
【44】H. D. Stenzenberger, M. Herzog, W. Romer, R. Scheiblich, S. Pierce and M. Canning, 1985, 30th Int. SAMPE Symp., 30, p. 1568.
【45】R. J. Morgan and E. E. Shin, et al., 1997, “Characterization of the cure reactions of bismaleimide composite matrices”, Polymer, 38(3), p. 639-646.
【46】J. C. Phelan and C. S. P. Sung, 1997, “Cure Characterization in Bis(maleimide)/Diallylbisphenol A Resin by Fluorescence, FT-IR, and UV-Reflection Spectroscopy”, Macromolecules, 30(22), p. 6845-6851.
【47】M. Gaku, et al., 1977, Japanese Patent. 75129700, 1975; JP 77 31279.

【48】F. Iguchi, et al., 1979, Proc. Electr./Electron. Insul. Conf., 14, p. 344.
【49】Z. Tong, 2001, “Bismaleimide-Triazine Resin Used for PCB Lami- nate”, Beijing Insulation Material Work, Beijing 100054.
【50】F. Hickman and B. Forcier, 1996, Printed Circuit Fabrication, 19(8), p. 22.
【51】S. Motoori, et al., 1981, Proc. Electr./Electron. Insul. Conf., 15, p. 168.
【52】M. D. Soucek, R. H. Pater and S. L. Ritenour, 1993, Polym. Prep., 27, p. 408.
【53】A. Chaplin, et al., 2000, “Studying water uptake effects in resins based on cyanate ester/bismaleimide blends”, Polymer, 41(11), p. 3945-3956.
【54】X. P. Zhnag, R. S. Liu and J. M. Liu, 2007, “BT Resins and Research Progress of Its Modification”, Hubei Research Institute of Chemistry, Wuhan 430074.
【55】R. G. Pitler, et al., 1998, Engineering Plastics, ASM International, P. 240.
【56】H. J. Hwang, et al., 2006, “Dielectric and Thermal Properties of Dicyanatadiene Containing Bismaleimide and Cyanate Ester. Part IV”, Polymer, 47(4), p. 1291-1299.
【57】K. Dinakaran, et al., 2003, “Preparation and Characterization of Bismaleimide/1,3-Dicyanatobenzene Modified Epoxy Intercross- linked Matrices”, Eur. Polymer J., 39(11), p. 2225-2233.
【58】A. Gu, 2006, “High performance bismaleimide/cyanate ester hybrid polymer networks with excellent dielectric properties”, Composites Science and Technology, 66(11), p. 1749-1755.
【59】張龍慶，2003，”高性能BT樹脂基覆銅板的研制”，電子元件與材料，9期，p. 27-29。
【60】J. M. Barton, et al., 1999, “A new synthetic route for the prepara- tion of alkenyl functionalized aryl cyanate ester monomers”, Polymer, 40(19), p. 5421-5427.
【61】李雅明，1997，”固態電子學”，全華科技。
【62】A. J. Moulson and J. M. Herbert, 1993, Electroceramics, Mat. Pro. Appl., 310, p. 165.
【63】吳泰伯，1996，”強介電薄膜在半導體記憶體上之應用與發展”，中國材料學會1996年度年會論文集，p. 155。
【64】吳朗，1994，”電子陶瓷-介電”，全欣圖書。
【65】G. Hougham, G. Tesoro and J. Shaw, 1994, “Synthesis and Properties of Highly Fluorinated Polyimides”, Macromolecules, 27(13), p. 3642-3649.
【66】G. Hougham, G. Tesoro and A. Viehbeck, 1996, “Influence of free volume change on the relative permittivity and refractive index in fluoropolyimides”, Macromolecules, 29(10), p. 3453-3456.
【67】G. Hougham, G. Tesoro, A. Viehbeck and J. D. Chapple-Sokol, 1994, “Polarization effects of fluorine on the relative permittivity in polyimides”, Macromolecules, 27(21), p. 5964-5971.
【68】T. J. Lee, et al., 2007, “Synthesis, structures and thermal properties of new class epoxide-terminated telechelic poly(2,6-dimethyl-1,4- phenylene oxide)s”, Polymer, 48(3), p. 734-742.
【69】S. G. Hong and C. S. Yeh, 2007, “Catalytic Effects of Copper Oxides on the Curingand Degradation Reactions of Cyanate Ester Resin”, J. Appl. Polym. Sci., 104(1), p. 442-448.
【70】T. Ozawa, 1970, J. Therm. Anal., 2, p. 301.
【71】H. E. Kissinger, 1957, Anal. Chem., 29, p. 1072.
【72】A. C. Grillent, J. Galy, J. F. Gerard and J. P. Pascault, 1991, “Mechanical and Viscoelastic Properties of Epoxy Networks Cured with Aromatic Diamines”, Polymer, 32(10), p. 1885-1891.
【73】黃建霖，2002，”經互穿網狀（IPN）途徑對聚醯亞胺與環氧樹脂二高分子材料低介電化”，國立成功大學化學工程學系碩士論文。
【74】L. H. SPERLING, 2001, “Introduction to Physical Polymer Science”, Third Edition, Wiley-Interscience.
【75】H. Kimura, S. Ohizumi, T. Nishioka and M. Nakao, 1992, “New Analytical Study for Popcorn Phenomenon”, IEEE, p. 1035-1041.
【76】G. Houglam, G. Tesoro and J. Shaw, 1994, “Synthesis and Properties of Highly Fluorinated Polyimides”, Macrmolecules, 27(13), p. 3642-3649.
【77】D. Martin, 1964, Cyansäurephenylester, Angew. Chem., 76, p. 303.
【78】J. Fan, et al., 2003, “Static and Dynamic Mechanical Properties of Modified Bismaleimide and Cyanate Ester Interpenetrating Polymer Networks”, J. Appl. Polym. Sci., 88(8), p. 2000-2006.