(3.237.234.213) 您好!臺灣時間:2021/03/09 13:11
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果

詳目顯示:::

我願授權國圖
: 
twitterline
研究生:趙婉卉
研究生(外文):ZHAO, WAN-HUI
論文名稱:含酯基團液晶環氧樹脂/含DOPO硬化劑之合成、鑑定及其物理性質之研究
論文名稱(外文):Preparation and Properties of Liquid Crystalline Epoxy Resin Containing Ester Group and Curing Agent Based on DOPO
指導教授:何宗漢何宗漢引用關係鄭錫勳鄭錫勳引用關係
指導教授(外文):HO, TSUNG-HANCHENG, SHI-SHIUN
口試委員:何宗漢鄭錫勳顏福杉謝正悅
口試委員(外文):HO, TSUNG-HANCHENG, SHI-SHIUNYEN, FU-SHASIE, JHENG-YUE
口試日期:2020-06-30
學位類別:碩士
校院名稱:國立高雄科技大學
系所名稱:化學工程與材料工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2020
畢業學年度:108
語文別:中文
論文頁數:131
中文關鍵詞:液晶環氧樹脂酯基團阻燃硬化劑DOPO熱性質阻燃性
外文關鍵詞:liquid crystalline epoxy resinester groupflame retardantDOPOthermal propertiesflame retardancy
相關次數:
  • 被引用被引用:0
  • 點閱點閱:49
  • 評分評分:系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0
本研究分別合成含酯基團之液晶環氧樹脂 (LCE)及含DOPO阻燃硬化劑 (TDCA-DOPO),利用紅外線光譜儀 (FTIR)、核磁共振儀 (1H-NMR、31P-NMR)及質譜儀 (MS)鑑定其結構。透過微分掃描熱卡計 (DSC)及偏振光學顯微鏡 (POM)觀察LCE的液晶相變行為,於DSC結果顯示,出現一個吸熱峰和兩個放熱峰,在降溫過程中,使用POM可觀察到層列型液晶相的扇形焦錐紋理 (fan-shaped focal-conic texture)。
將LCE分別使用不同比例的TDCA-DOPO和DDM當共硬化劑來製備熱固性環氧樹脂 (LCE / TDCA-DOPO / DDM)。利用DSC研究熱固性環氧樹脂玻璃化轉移溫度 (Tg),結果顯示,隨著TDCA- DOPO含量的增加,Tg以些微溫度差異逐漸下降。透過熱重分析儀(TGA)及Hot-Disk研究LCE / TDCA-DOPO / DDM的熱性質,TGA結果顯示,透過增加TDCA-DOPO含量可以提高熱穩定性和焦炭殘餘率;而Hot-Disk結果顯示,導熱係數隨TDCA-DOPO含量增加而下降,但均高於市售環氧樹脂的導熱係數。
利用LOI、UL-94及錐形量熱儀探討熱固性環氧樹脂之難燃性,結果顯示,當磷含量達0.54 wt%時LOI值達到33%且通過UL-94 V-0等級,而熱釋放速率及總煙產生量均降低。
透過SEM、EDS及Raman光譜來探討焦炭殘餘物,結果顯示,添加TDCA-DOPO之焦炭殘餘物較為緻密且膨脹,並含有磷及氮元素,具氮磷共乘效應;Raman光譜結果顯示含有TDCA-DOPO之熱固性環氧樹脂較能產生保護型焦炭。
The liquid crystalline epoxy resin (LCE) containing ester group and curing agent based on DOPO (TDCA-DOPO) were synthesized respectively. The chemical structure of LCE and TDCA-DOPO were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR, 31P-NMR) and mass spectroscopy (MS). The liquid crystalline phase transition behavior of LCE was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). From the DSC result, one endothermal peak and two exothermal peaks were appeared in the DSC curve. The sematic liquid crystalline texture of fan-shaped focal-conic texture was observed during cooling by POM.
The TDCA-DOPO and diaminodiphenylmethane (DDM) were used as co-curing agent and further cured with LCE, and the thermosetting epoxy resin (LCE/TDCA-DOPO/DDM) were prepared by different ratios of TDCA-DOPO/DDM. The glass transition temperature (Tg) was investigated by DSC. The results showed that the Tg was slight differences decreasing gradually by increasing TDCA-DOPO content. The thermal properties of LCE/TDCA-DOPO/DDM were investigated by thermal gravimetric analyzer (TGA) and Hot-Disk. The results of TGA showed that the thermal stability, char yield were increased by increasing TDCA-DOPO content; and Hot-disk results showed that the thermal conductivity was decreasing by increasing TDCA-DOPO content, but all were higher than the commercially available epoxy resins.
The flame retardancy of thermosetting epoxy resin were investigated by LOI, UL-94 and cone calorimeter. The results show that when the phosphorus content was 0.54 wt%, the LOI value of 33% and passes the UL-94 V-0 rating, and the heat release rate and the total smoke production were reducing.
The char residues after cone calorimeter were investigated by SEM, EDS and Raman spectroscopy. The results show that the char residue of added TDCA-DOPO was dense and expanded, and contains phosphorus and nitrogen elements, with nitrogen and phosphorus synergistic effect. Raman results showed that the thermosetting epoxy resin contains TDCA-DOPO was more capable of producing protective char.
摘要 I
Abstract III
致謝 V
總目錄 VI
表目錄 X
圖目錄 XII
SCHEME XVI
第一章 緒論 1
1-1前言 1
1-2歐盟電機電子設備有害物質限用指令 (RoHS) 2
1-3未來材料發展趨勢及要求 5
1-4研究目的 8
第二章 文獻回顧 9
2-1環氧樹脂(Epoxy Resin)9
2-1-1環氧樹脂簡介 9
2-1-2環氧樹脂特性 10
2-2液晶簡介 11
2-2-1液晶起源[15–17] 12
2-2-2液晶分子結構 13
2-2-3液晶分類 14
2-3液晶環氧樹脂簡介 20
2-3-1 Ester液晶環氧樹脂 22
2-4硬化劑簡介 27
2-4-1硬化劑的分類 28
2-4-2共硬化劑 31
2-5高分子燃燒機構 35
2-6難燃原理 37
2-6-1鹵素系難燃原理 39
2-6-2磷系難燃原理 42
2-7含DOPO硬化劑 44
第三章 實驗 49
3-1實驗流程圖 49
3-2材料與藥品 51
3-3實驗裝置圖 53
3-4儀器設備 56
3-5實驗步驟 58
3-5-1 4,4'-dihydroxybiphenyl ester (DHDP)之合成[64] 58
3-5-2 4,4'-di(2,3-epoxypropenyloxy)phenyl benzoate (LCE)之合成 59
3-5-3 1,4-phenylene-bis((6-oxido-6H-dibenz[c,e][1,2]-oxaphosphorinyl)carbinol) (TDCA-DOPO)之合成[65] 61
3-5-4 LCE/TDCA-DOPO/DDM之配製 63
3-5-5硬化試片之製備 65
3-6結構鑑定與物性測試 66
第四張 結果與討論 73
4-1 DHDP與LCE合成及鑑定 73
4-1-1 DHDP與LCE之FT-IR分析 73
4-1-2 DHDP與LCE之1H-NMR分析 75
4-1-3 DHDP與LCE之MS分析 77
4-2 TDCA-DOPO合成及鑑定 79
4-2-1 TDCA-DOPO之FTIR分析 79
4-2-2 TDCA-DOPO之1H-NMR與31P-NMR分析 81
4-2-3 TDCA-DOPO之MS分析 83
4-3 LCE液晶型態之探討 84
4-3-1 DSC分析液晶相範圍 84
4-3-2 POM液晶相觀察 86
4-4熱硬化之探討 88
4-4-1 LCE/TDCA-DOPO/DDM之DSC分析 88
4-5 LCE/TDCA-DOPO/DDM硬化環氧樹脂熱性質探討 89
4-5-1以DSC探討玻璃轉移溫度 89
4-5-2以TGA探討熱穩定性 91
4-5-3以Hot-Disk探討熱傳導係數 93
4-6 LCE/TDCA-DOPO/DDM 硬化環氧樹脂阻燃性探討 95
4-6-1 LOI及UL-94測試 95
4-6-2 Cone calorimeter測試 97
4-7 LCE/TDCA-DOPO/DDM硬化環氧樹脂焦炭分析 99
4-7-1以SEM觀察焦炭形貌 99
4-7-2以EDS檢測焦炭元素 100
4-7-3以Raman光譜測定焦炭石墨化程度 101
第五章 結論 103
第六章 參考文獻 105

[1] 戴學斌、陳耀忠、黃文啟、黃焜銘,"不同EMC封裝材與抗沾黏薄膜之沾黏力研究",工業材料雜誌,212,170-178,2004。
[2] 蔡昆霖、林慶炫,"含磷多官能基環氧樹脂合成及其固化物之探討",國立中興大學化學工程學,碩士論文,2014。
[3] 王春山、謝正悅、林慶炫,"非鹵素難燃電子材料研究",知識創新,5,1-4,2000。
[4] 潘開林、顏毅林、周斌、寧業香,"RoHS符合性自我聲明與測試策略",電子元件與材料,25,68-70,2006。
[5] 汪茜、錢曉耀、洪濤、劉益民、王振華,"RoHS2.0標準實施之探究",中小企業管理與科技,15,296-298,2013。
[6] 鄭志龍,"從2019 Nepcon Nagoya看電子構裝材料發展趨勢(上)",材料世界網,2020。
[7] 詹英楠、黃淑禎、陳凱琪,"半導體晶圓級封裝材料技術發展",工業材料雜誌,366,47-54,2017。
[8] 李宗銘,"新世代半導體構裝技術對封裝",材料世界網,2001。
[9] 詹英楠,陳凱琪,"大面積模封材料技術與發展(下)",工業材料雜誌,393,161-166,2019。
[10] 王春山,"環氧樹脂簡介與最近的發展(一)",化工技術,2 (10),54-57,1994。
[11] 葉仰哲,"全球環氧樹脂市場概況",產業情報網,2015。
[12] 桓內弘,"環氧樹脂應用實務",1986。
[13] 曾效沂、林唯芳,"液晶環氧樹脂的合成與物性研究",國立台灣大學材料科學與工程學,碩士論文,1998。
[14] 王裕堪、劉瑞祥,"側鏈型光學活性液晶高分子之合成及光學特性探討",國立成功大學化學工程系,碩士論文,2007。
[15] V. Nazarenko, M.V. Kurik, G.V. Klimusheva, Z. Y. Gotra, V.M. Sorokin and L.M. Lisetski, "Liquid crystals in Ukraine and Ukrainians in liquid crystals", Journal of Molecular Liquids, 267, 29-33, 2018.
[16] F.Reinitzer, "Contributions to the knowledge of cholesterol", Liquid Crystals, 5, 7, 1989.
[17] G.Friedel, "Lecons de Cristallographie", Bull. Amer. Math. Soc, 18, 364, 1912.
[18] 劉旭唐、何宗漢,"酮基團液晶環氧樹脂之合成及其奈米碳管複合材料之熱性質研究",國立高雄應用科技大學化學工程與材料工程系,碩士論文,2015。
[19] B. Bahadur, "Liquid Crystalline Polymer", World Scientific, 1, 23-25, 1990.
[20] Gray, G.W. and J.W., "Goodby, Smectic liquid crystals: Textures and structures", Philadelphia, 256, 1984.
[21] 陳有志,謝國煌,"懸掛硬桿結構之環氧樹脂與聚胺酯互穿型高分子網狀結構",國立台灣大學化學工程學,碩士論文,2000。
[22] D. Andrienko, "Introduction to liquid crystals", Journal of Molecular Liquids, 267, 520-541, 2018.
[23] S. Upadyaya, P. Bhagavath and D. Sunil, "Azines as liquid crystalline materials: An up-to-date review", Journal of Molecular Liquids, 269, 354-370, 2018.
[24] C. Lou and X. Liu, "Functional dendritic curing agent for epoxy resin : Processing , mechanical performance and curing/toughening mechanism", Composites Part B: Enginnering, 136, 20-27, 2018.
[25] H. Galina and B. Mossety-Leszczak, "Liquid-Crystalline Epoxy Resins", Journal of Applied Polymer Science, 105, 224-228, 2007.
[26] S. Liu, V.S. Chevali, Z. Xu, D. Hui and H. Wang, "A review of extending performance of epoxy resins using carbon nanomaterials",Composites Part B: Engineering, 136, 197-214, 2018.
[27] Y. Li, and M.R. Kessler, "Liquid Crystalline Epoxy Resins, in Liquid Crystalline Polymers: Volume 1–Structure and Chemistry", Springer International Publishing: Cham., 1-17, 2016.
[28] Y. Li, P. Badrinarayanan and M.R. Kessler, "Liquid crystalline epoxy resin based on biphenyl mesogen: Thermal characterization", Polymer, 54(12), 3017-3025, 2013.
[29] S. Cho, E.P. Douglas and J.Y. Lee, "Transition diagrams for a liquid crystalline thermoset containing a rigid-rod epoxy", Polymer Engineering and Science, 46(5), 623-629, 2006.
[30] J.Y. Lee, J. Jang, S.M. Hong, S.S. Hwang and K.U. Kim, "Relationship between the structure of the bridging group and curing ofliquid crystalline epoxy resins", Polymer, 40, 3197-3202, 1999.
[31] J.Y. Lee and J. Jang, "The effect of mesogenic length on the curing behavior and properties of liquid crystalline epoxy resins", Polymer, 47(9), 3036-3042, 2006.
[32] Y.L. Liu, Z.Q. Cai, X. Wen, P. Pi, D. Zheng, J. Cheng and Z. Yang, "Thermal properties and cure kinetics of a liquid crystalline epoxy resin with biphenyl-aromatic ester mesogen", Thermochimica Acta, 513(2), 88-93, 2011.
[33] G. Chen, Q. Zhang, Z. Hu, S. Wang, K. Wu, J. Shi, L. Liang and M. Lu, "Liquid crystalline epoxies bearing biphenyl ether and aromatic ester mesogenic units: Synthesis and thermal properties", Journal of Macromolecular Science, Part A, 56(5), 484–495, 2019.
[34] J.P. Eloundou, J.F. Gerard, D. Harran and J.P. Pascault, "Temperature dependence of the behavior of a reactive epoxy-amine system by means of dynamicrheology", Macromolecules, 29, 6917-6927, 1996.
[35] J. Rocks, L. Rintoul, F. Vohwinkel and G. George, "The kinetics and mechanism of cure of an amino-glycidyl epoxy resin by a co-anhydride as studied by FT-Raman spectroscopy", Polymer, 45(20), 6799-6811, 2004.
[36] G. Lachenal, A. Pierre and N. Poisson, "FT-NIR spectroscopy: trends and application to the kinetic study of epoxy/triamine system", Micron, 27, 329-334, 1996.
[37] K. Horie, H. Hiura, M. Sawada, I. Mita and H. Kambe, "Calorimetric investigation of polymerization reactions. Curing reaction of epoxides with amines", Polymer Chemistry, 8, 1357-1372, 1970.
[38] J. Hu, J. Shan, J. Zhao and Z. Tong, "Water resistance and curing kinetics of epoxy resins with a novel curing agent of biphenyl-containing amine synthesized by one-pot method", Thermochimica Acta, 606, 58-65, 2015.
[39] C. Ma, S. Qiu, B. Yu, J. Wang, C. Wang, W. Zeng and Y. Hu, "Economical and environment-friendly synthesis of a novel hyperbranched poly (aminomethyl phosphine oxide-amine) as co-curing agent for simultaneous improvement of fire safety, glass transition temperature and toughness of epoxy resins", Chemical Engineering Journal, 322, 618–631, 2017.
[40] X. Yang, C. Wang, J. Xia, W. Mao and S. Li, "Study on synthesis of novel phosphorus-containing flame retardant epoxy curing agents from renewable resources and the comprehensive properties of their combined cured products", Progress in Organic Coatings, 110, 195–203, 2017.
[41] 沈永清、張信貞、莊學平、張榮樹,"高分子難然機構及原理",化工資訊,9 (2),15-31,1995。
[42] 歐育湘,"實用阻燃技術",化學工業出版社,2002。
[43] 王家祥、郭炳林,"含磷硬化劑對碳、矽環氧樹脂之反應與難燃性探討",國立成功大學,碩士論文,1998。
[44] 陳柏全、郭炳林,"含磷環氧樹脂硬化劑之合成與難燃性探討",國立成功大學,碩士論文,1999。
[45] 謝宛融、王春山,"新穎非鹵型難燃劑之合成與性質探討",國立成功大學,碩士論文,2004。
[46] S.Y. Lu and I. Hamerton, "Recent developments in the chemistry of halogen-free flame retardant polymers", Progress in Polymer Science, 27(8), 1661-1712, 2002.
[47] L. Costa, P. Goberti, G. Paganetto, G. Camino and P. Sgarzi, "Thermal behaviour of chlorine-antimony fire-retardant systems", Polymer Degradation and Stability, 30(1), 13–28, 1990.
[48] G. Camino, G. Martinasso, L. Costa and R. Gobetto, "Thermal degradation of pentaerythritol diphosphate, model compound for fire retardant intumescent systems: Part II—Intumescence step", Polymer Degradation and Stability, 28(1), 17–38, 1990.
[49] J. Green and M. Dekker, "Thermoplastic Polymer Additives", New York and Basel, 93-203, 1989.
[50] W.A. Rosser, H. Wise, and J. Miller, "Seventh International Symposiumon Combustion", London, Butterworth’s, 175, 1959.
[51] J.W. Hastie, "Mass Spectrometric Studies of Flame Inhi- bition: Analysis of Antimony Trihalides in Flames", Combustion and Flame, 21, 49, 1973.
[52] H.A. Cheema, A. El-Shafei and P.J. Hauser, "Conferring flame retardancy on cotton using novel halogen-free flame retardant bifunctional monomers: synthesis, characterizations and applications", Carbohydrate Polymers, 92, 885-893, 2013.
[53] R.L. Schwarz, W.C. Kuryla and A.J. Dekker, "Flame Retardancy of Polymeric Materials", New York, 2, 104, 1973.
[54] J.W. Lyons, "The Chemistry and Uses of Fire Retardants", Wiley-Interscience, New York, 1, .302-304, 1970.
[55] A. Gentilhomme, M. Cochez, M. Ferriol, N. Oget and J.L. Mieloszynski, "Thermal degradation of methyl methacrylate polymers functionalized by phosphorus-containing molecules. III: Cone calorimeter experiments and investigation of residues" Polymer Degradation and Stability, 88, 92-97, 2005.
[56] A. Granzow, "Flame retardation by phosphorus compounds", Chemical Research, 11, 177, 1978.
[57] J. Zhang, A.R. Horrocks and M.R. Hall, "The Flammability of Polyacrylonitrile and its Copolymers IV. The Flame Retardant Mechanism of Ammo- nium Polyphosphate", Fire and Material, 18, 307-312, 1994.
[58] S. Huo, Z. Liu, C. Li, X. Wang, H. Cai and J. Wang, "Synthesis of a phosphaphenanthrene/benzimidazole-based curing agent and its application in flame-retardant epoxy resin", Polymer Degradation and Stability, 163, 100-109, 2019.
[59] W. Xu, A. Wirasaputra, S. Liu, Y. Yuan and J. Zhao, "Highly effective flame retarded epoxy resin cured by DOPO-based co-curing agent", Polymer Degradation and Stability, 122, 44-51, 2015.
[60] P. Wang and Z. Cai, "Highly efficient flame-retardant epoxy resin with a novel DOPO-based triazole compound: Thermal stability, flame retardancy and mechanism", Polymer Degradation and Stability, 137, 138-150, 2017.
[61] P. Wang, L. Xia, R. Jian, Y. Ai, X. Zheng, G. Chen and J. Wang, "Flame-retarding epoxy resin with an efficient P/N/S-containing flame retardant: Preparation, thermal stability, and flame retardance", Polymer Degradation and Stability, 149, 66-77, 2018.
[62] S. Jin, L. Qian, Y. Qiu, Y. Chen and F. Xin, "High-efficiency flame retardant behavior of bi-DOPO compound with hydroxyl group on epoxy resin", Polymer Degradation and Stability, 166, 344-352, 2019.
[63] P. Wang, L. Chen, H. Xiao and T. Zhan, "Nitrogen/sulfur-containing DOPO based oligomer for highly efficient flame-retardant epoxy resin", Polymer Degradation and Stability, 171, 2020.
[64] 洪明億、何宗漢,"含酯基團液晶型硬化劑之合成、鑑定與熱性質探討及其應用於環氧樹脂之研究",國立高雄應用科技大學化學工程與材料工程系,碩士論文,2016。
[65] X. Wang, Y. Hu, L. Song, H. Yang, W. Xing and H. Lu, "Synthesis and characterization of a DOPO-substitued organophosphorus oligomer and its application in flame retardant epoxy resins", Progress in Organic Coatings, 71, 72–82, 2011.
[66] Y. Cao, X.L. Wang, W.Q. Zhang, X.W. Yin, Y.Q. Shi and Y.Z. Wang, "Bi-DOPO Structure Flame Retardants with or without Reactive Group: Their Effects on Thermal Stability and Flammability of Unsaturated Polyester", Industrial and engineering chemistry research, 56(20), 5913-5924, 2017.
[67] Y.L. Liu, C.S. Wu, K.Y. Hsu and T.C. Chang, "Flame-retardant epoxy resins fromo-cresol novolac epoxy cured with a phosphorus-containing aralkyl novolac", Journal of Polymer Science Part A Polymer Chemistry, 40, 2329–2339, 2002.
[68] Y. Li and M.R. Kessler, "Liquid crystalline epoxy resin based on biphenyl mesogen: Effect of magnetic field orientation during cure", Polymer, 54(21), 5741–5746, 2013.
[69] Q. Zhang, J. Wang, S. Yang, J. Cheng, G. Ding, Y. Hu and S. Huo, "Synthesis of a P/N/S-based flame retardant and its flame retardant effect on epoxy resin", Fire Safety Journal, 113, 2020.
[70] Q. Zhang, S. Yang, J. Wang, J. Cheng, Q. Zhang, G. Ding, Y. Hu and S. Huo, "A DOPO based reactive flame retardant constructed by multiple heteroaromatic groups and its application on epoxy resin: curing behavior, thermal degradation and flame retardancy", Polymer Degradation and Stability, 167, 10-20, 2019.
[71] S.-M. Yuen, C.C. M.-Ma, C.L. Chiang, J.A. Chang, S.W. Huang, S.C. Chen, C.Y. Chuang, C.C. Yang and M.H. Wei, "Silane-modified MWCNT/PMMA composites – Preparation, electrical resistivity, thermal conductivity and thermal stability", Composites Part A: Applied Science and Manufacturing, 38(12), 2527–2535, 2007.
[72] S. Huo, J. Wang, S. Yang, C. Li, X. Wang and H. Cai, "Synthesis of a DOPO-containing imidazole curing agent and its application in reactive flame retarded epoxy resin", Polymer Degradation and Stability, 159, 79-89, 2019.
[73] J. Wang, C. Ma, P. Wang, S. Qiu, W. Cai and Y. Hu, "Ultra-low phosphorus loading to achieve the superior flame retardancy of epoxy resin", Polymer Degradation and Stability, 149, 119-128, 2018.

電子全文 電子全文(網際網路公開日期:20250701)
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top
系統版面圖檔 系統版面圖檔