臺灣博碩士論文加值系統

本實驗是藉由低成本的DOPO、Acetone、Resorcinol(及Catechol)利用兩步反應合成兩種低成本、更高含磷量的雙酚單體。再將單體中的羥基結構以甲基丙烯酸酐進行改質，與市售環氧樹酯HP-7200進行固化，在固化的同時甲基丙烯酸基團也會進行自身交聯固化，使其有更高的交聯密度，更高的熱性質。測試其固化物的玻璃轉移溫、熱裂解溫度、介電性質等等。Resorcinol系統經MMA改質後Tg約237 oC ;氮氣環境下Td5%約407 oC ; Dk和Df分別為2.91及0.008。Catechol系統經MMA改質後Tg約208 oC ; 氮氣環境下Td5%約416 oC ; Dk和Df分別為2.87及0.008。此固化物之熱性質和介電性質，Resorcinol系統優於商品DMP進行甲基壓克力改質後之性質 (Tg約220 oC ; 氮氣環境下Td5%約403 oC ; Dk和Df分別為3.07及0.007)。
第二部分是利用本研究合成之單體DPAC-mma和DPAR-mma作為商品SA9000/HP7200固化物之阻燃添加劑，成功將UL-94難燃測試V-1等級之SA9000/HP7200固化物提升至V-0等級。
於實驗過程我們由H-NMR發現兩個現象 (1)DOPO和Acetone反應後的單體，當Temperature >140 oC時會脫去Acetone還原成DOPO (2) 兩個羥基會因為立體障礙的不同，而有不同的反應性。

In this experiment, two low-cost, higher phosphorus-containing bisphenol monomers were synthesized by a two-step reaction using low-cost DOPO, acetone, and resorcinol (or catechol). The hydroxyl structure in the monomer was modified with methacrylic anhydride and cured with commercially available epoxy resin, HP7200. At the same time of curing, the methacrylic group will also undergo self-crosslinking and solidification to achieve its higher crosslinking density, which gives the corresponding polymer the enhanced thermal properties. The cured polymers were tested for glass transition temperature, thermal cracking temperature and dielectric properties. In resorcinol system, the Tg is about 237 oC and Td5% is about 407 oC under the nitrogen atmosphere; Dk and Df values are 2.91 and 0.008, respectively. The catechol system has a Tg of about 208 oC; in a nitrogen atmosphere, Td5% is about 416 oC; Dk and Df values are 2.87 and 0.008, respectively. The thermal and dielectric properties of resorcinol system containing cured polymers are superior to the DMP-mma (Tg = 220 oC, Td5% under nitrogen is 403 oC, and Dk, Df values are 3.07 and 0.007, respectively).
In second part of this thesis, we used two monomers DPAC-mma, and DPAR-mma, which were cured by using commercial SA9000/HP7200 curing agents. The cured product has enhanced properties under UL-94 flame retardant test from V-1 grade to V-0 grade.
The experimental investigation revels, that the monomer DPA will undergo reverse reaction when temperature is greater than 140 oC, and the two hydroxyl groups will be different in reactivity due to the influence of steric hindrance.

目錄
摘要 i
Abstract ii
目錄 iv
Scheme 目錄 viii
Figure 目錄 ix
Table目錄 xi
第一章 緒論 1
第二章 文獻回顧 3
2.1 環氧樹脂簡介 3
2.2 難燃劑介紹8-12 4
2.3 含磷難燃劑阻燃原理15 6
2.4磷系阻燃單體穩定度 8
1. 1st generation 8
2. 2nd generation 8
3. 3rd generation 9
4. 4th generation 10
2.5 DOPO-AP衍生物及穩定性探討 12
2.6活性酯類硬化劑 13
2.7 研究動機 21
第三章 實驗 23
3.1 藥品及溶劑 23
3.2儀器設備 25
3.3化合物合成 27
3.3.1 單體DPA合成 29
3.3.2 單體DPAP合成 30
3.3.3 單體DPAC合成 31
3.3.4 單體DPAR合成 32
3.3.5 單體DPAC-mma合成 33
3.3.6 單體DPAR-mma合成 34
3.3.7 單體DPA-NH合成 35
3.3.8 單體o-DPA-NH合成 36
3.4厚膜製備 37
3.4.1 DPAC、DPAR、DMP與環氧樹脂固化物 37
3.4.2 DPAC-mma、DPAR-mma與環氧樹脂固化物 38
3.4.3 DPAC-mma、DPAR-mma與SA9000和HP7200固化物 40
第四章 結構鑑定與分析 41
4.1 DPA光譜鑑定與分析 41
4.1.1 1H NMR鑑定 41
4.1.2 31P NMR鑑定 42
4.1.3 高解析質譜儀鑑定 43
4.2 DPAP光譜鑑定與分析 44
4.2.1 1H NMR鑑定 44
4.2.2 31P NMR鑑定 45
4.3 DPAC光譜鑑定與分析 46
4.3.1 1H NMR鑑定 46
4.3.2 13C NMR鑑定 48
4.3.3 31P NMR鑑定 50
4.3.4 高解析質譜儀鑑定 51
4.3.5 DSC熔點及純度鑑定 52
4.4 DPAR光譜鑑定與分析 53
4.4.1 1H NMR鑑定 53
4.4.2 13C NMR鑑定 55
4.4.3 31P NMR鑑定 57
4.4.4 高解析質譜儀鑑定 58
4.4.5 DSC熔點及純度鑑定 59
4.5 DPAC-mma光譜鑑定與分析 60
4.5.1 1H NMR鑑定 60
4.5.2 13C NMR鑑定 62
4.5.3 31P NMR鑑定 64
4.5.4 傅立葉轉換紅外線光譜(FTIR)鑑定 65
4.6 DPAR-mma光譜鑑定與分析 66
4.6.1 1H NMR鑑定 66
4.6.2 13C NMR鑑定 68
4.6.3 31P NMR鑑定 70
4.6.4 高解析質譜儀鑑定 71
4.6.5 傅立葉轉換紅外線光譜(FTIR)鑑定 72
4.7 DPA-NH光譜鑑定與分析 73
4.7.1 1H NMR鑑定 73
4.7.2 13C NMR鑑定 75
4.7.3 31P NMR鑑定 77
4.7.4 傅立葉轉換紅外線光譜(FTIR)鑑定 78
4.8 o-DPA-NH光譜鑑定與分析 79
4.8.1 1H NMR鑑定 79
4.8.2 31P NMR鑑定 80
4.8.3傅立葉轉換紅外線光譜(FTIR)鑑定 81
第五章 固化物性質分析與討論 82
5.1 單體溶解度測試 82
5.2 化合物的合成與固化探討 83
5.2.1 DPAR反應觸媒和溫度最佳化 83
5.2.2 DPAR反應時間和產率最佳化 85
5.2.3 雙酚單體衍伸物合成探討 86
5.2.4 DPAC-mma、DPAR-mma與SA9000和HP7200固化物 92
5.3 硬化劑之熱性質與介電性質分析 95
5.3.1 DMA分析 95
5.3.2 TMA分析 97
5.3.3 TGA分析 98
5.3.4 介電性質 102
5.4 阻燃添加劑之熱性質與介電性質分析 103
5.4.1 DMA分析 103
5.4.2 TMA分析 105
5.4.3 TGA分析 107
5.4.4 介電性質 110
5.4.5 UL-94難燃測試 111
5.5 DPA-NH與o-DPA-NH合成探討 112
第六章 結論 116
參考文獻 117

1.Garg, A. C.; Mai, Y.-W. Failure mechanisms in toughened epoxy resins—A review. Composites Science and Technology 1988, 31 (3), 179-223.
2.Morgan, R., Structure-property relations of epoxies used as composite matrices. In Epoxy Resins and Composites I, Springer: 1985; pp 1-43.
3.T., S. Cyclic organophosphorus compounds. 1972.
4.著, 桓.; 譯, 賴., 環氧樹脂應用實務. 復漢出版社: 1993.
5.May, C., Epoxy resins: chemistry and technology. Routledge: 2018.
6.Spurr, A. R. A low-viscosity epoxy resin embedding medium for electron microscopy. Journal of ultrastructure research 1969, 26 (1-2), 31-43.
7.Luft, J. H. Improvements in epoxy resin embedding methods. The Journal of Cell Biology 1961, 9 (2), 409-414.
8.Lu, S.-Y.; Hamerton, I. Recent developments in the chemistry of halogen-free flame retardant polymers. Progress in polymer science 2002, 27 (8), 1661-1712.
9.Irvine, D.; McCluskey, J.; Robinson, I. Fire hazards and some common polymers. Polymer Degradation and Stability 2000, 67 (3), 383-396.
10.Lomakin, S. M.; Zaikov, G. E., Ecological aspects of polymer flame retardancy. Vsp: 1999; Vol. 10.
11.Lewin, M. Flame retardancy of polymeric materials. CHIMICA OGGI-CHEMISTRY TODAY 1997, 15 (6-7), 41-41.
12.Sorathia, U., Flame retardant materials for maritime and naval applications. In Advances in fire retardant materials, Elsevier: 2008; pp 527-572.
13.Innes, J. In Flame retardants and their market applications, Flame retardants, 1996; 1996; pp 61-69.
14.Rakotomalala, M.; Wagner, S.; Döring, M. Recent developments in halogen free flame retardants for epoxy resins for electrical and electronic applications. Materials 2010, 3 (8), 4300-4327.
15.謝正悅; 林慶炫; 王春山. 非鹵素難燃電子材料－含磷環氧樹脂. 科學發展月刊 2000, 第28卷第11期.
16.Lin, Y.; Jiang, S.; Gui, Z.; Li, G.; Shi, X.; Chen, G.; Peng, X. Synthesis of a novel highly effective flame retardant containing multivalent phosphorus and its application in unsaturated polyester resins. RSC Advances 2016, 6 (89), 86632-86639.
17.Lin, C. H.; Lin, C. H. Synthesis and properties of polyimides derived from 1, 4‐bis (4‐aminophenoxy)‐2‐(6‐oxido‐6H‐dibenz [c, e][1, 2] oxaphosphorin‐6‐yl) phenylene. Journal of Polymer Science Part A: Polymer Chemistry 2007, 45 (14), 2897-2912.
18.Chen, C.-H.; Shiao, W.-F.; Ariraman, M.; Lin, C.-H.; Juang, T.-Y. High-performance thermosets derived from acetovanillone-based reactive polyethers. Polymer 2018.
19.Lin, C. H.; Chang, S. L.; Wei, T. P. High‐Tg Transparent Poly (ether sulfone) s Based on Phosphinated Bisphenols. Macromolecular Chemistry and Physics 2011, 212 (5), 455-464.
20.Lin, C. H.; Lin, H. T.; Tian, Y. W.; Dai, S. A.; Su, W. C. Preparation of phosphinated bisphenol from acid‐fragmentation of 1, 1, 1‐tris (4‐hydroxyphenyl) ethane and its application in high‐performance cyanate esters. Journal of Polymer Science Part A: Polymer Chemistry 2011, 49 (22), 4851-4860.
21.Hougham, G.; Tesoro, G.; Shaw, J. Synthesis and properties of highly fluorinated polyimides. Macromolecules 1994, 27 (13), 3642-3649.
22.Nakamura, S.; Arima, M. Characterization of the network structure o epoxy resins cured with active esters. International Journal of Polymer Analysis and Characterization 1995, 1 (1), 75-86.
23.Takeuchi, K.; Suzuki, E.; Morinaga, K.; Arita, K., Active ester resin, method for producing the same, thermosetting resin composition, cured product of the thermosetting resin composition, semiconductor encapsulating material, pre-preg, circuit board, and build-up film. Google Patents: 2014.
24.Arita, K.; Suzuki, E., Thermosetting resin composition, cured product thereof, active ester resin, semiconductor encapsulating material, prepreg, circuit board, and build-up film. Google Patents: 2014.
25.Dershem, S. M., Hydrolytically resistant thermoset monomers. Google Patents: 2013.
26.Yeager, G. W.; Colborn, R. E., Poly (phenylene ether)—polyvinyl thermosetting resin. Google Patents: 2003.
27.Chen, C.-H.; Liu, C.-H.; Ariraman, M.; Lin, C.-H.; Juang, T.-Y. Phosphinated Poly (aryl ether) s with Acetic/Phenyl Methacrylic/Vinylbenzyl Ether Moieties for High-T g and Low-Dielectric Thermosets. ACS Omega 2018, 3 (6), 6031-6038.
28.Chen, C. H.; Tsai, Y. L.; Jeng, R. J.; Lin, C. H. Identification of the reaction mechanism between phenyl methacrylate and epoxy and its application in preparing low-dielectric epoxy thermosets with flexibility. Polymer 2018, 140, 225-232.
29.Yeager, G. W.; Colborn, R. E. US Patent 6352782 BS 2002.
30.Zúñiga, C.; Larrechi, M. S.; Lligadas, G.; Ronda, J. C.; Galià, M.; Cádiz, V. Phosphorus flame retardant polybenzoxazine foams based on renewable diphenolic acid. Polymer degradation and stability 2013, 98 (12), 2617-2626.