臺灣博碩士論文加值系統

利用dopotriol分別與cyanogens bromide（BrCN）及epichlorohydrin合成新穎三官能氰酸酯（dopotcy）及新穎三官能環氧樹脂（dopotep），並利用NMR、IR、EA及MS來鑑定其結構。
第一部份是將dopotcy與商業用氰酸酯（badcy）或商業用epoxy（dgeba）進行共聚合。硬化後的氰酸酯分別利用微差掃描熱分析（DSC） 、熱重分析儀（TGA）量測其裂解溫度（Td）、介電分析（DEA）及吸水性等測量。在dopotcy-badcy和dopotcy-dgeba共聚物，硬化後玻璃轉移溫度範圍分別為245～275oC和206～262oC會隨三官能氰酸酯（dopotcy）含量增加而上升。而導入三官能氰酸酯對介電性質影響不大。
第二部份， dopotep與dgeba及硬化劑（ddm）進行硬化反應。dopotep / dgeba / ddm systems的玻璃轉移溫度也會隨三官能epoxy（dopotep）含量增加而上升，其範圍為159～223oC。在導入三官能epoxy（dopotep）對介電常數有稍微下降。

A novel tri-functional cyanate ester (dopotcy) and a novel novel tri-functional epoxy (dopotep) were synthesized from a tri-functional novolac (dopotriol) with cyanogens bromide and epichlorohydrin, respectively. Their structures were successfully confirmed by FTIR, NMR spectra, mass spectra and elemental analysis.
In the first part, dopotcy was copolymerized with a commercial cyanate ester (badcy) or with a commercial epoxy resin (dgeba). Properties of cured cyanate ester copolymers were evaluated by differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA). The glass-transition temperatures of cured dopotcy-badcy and dopotcy-dgeba copolymers are in the range of 245-275oC and 206-262oC, respectively, both increasing with the content of dopotcy. Dielectric analyses indicate that introducing dopotcy into badcy will not sacrifice the low-dielectric characteristic of badcy.
In the second part, dopotep was cured with dgeba and ddm. The glass-transition temperatures of dopotep/dgeba/ddm system are in the range of 159-223oC, increasing with dopotep. Experimental results indicate that introducing dopotep lower the dielectric properties.

目 錄
中文摘要 I
Abstract II
致 謝 III
表 目 錄 VI
圖 目 錄 VII



第一章 緒論 1

第二章 原理與文獻回顧 3
2- 1 氰酸脂簡介與發展概況及應用 3
2-1- 1 cyanate ester 的合成反應原理 5
2-1- 2 氰酸酯與環氧樹脂的硬化反應機構 6
2- 2 環氧樹脂 8
2- 3 epoxy的合成原理 10
2- 4 高分子難燃原理 12
2-3- 1 高分子燃燒機構 12
2-3- 2 高分子燃燒的因素 15
2-3- 3 高分子難燃化之原理 17
2- 5 難燃劑之原理與種類 18
2-5- 1 填充型難燃劑 19
2-5- 2 鹵系和磷系難燃劑 21
2-5- 3 膨脹型難燃劑 23
2-5- 4 共乘作用 24
2-5- 5 難燃劑之選擇 26
2- 6 含磷環氧樹脂之開發與應用 28

第三章 實 驗 30
3- 1 藥品與儀器 30
3-1- 1 反應單體 30
3-1- 3 儀器 31
3- 2 氰酸酯(cyanate ester)之合成 32
3- 3 合成dopotep 33
3- 4 試片硬化條件 34
3- 5 性質測試與分析 36
第四章 三官能的氰酸酯共聚酯之合成與性質分析 42
4- 1 單體之合成與分析 42
4-1- 1 dopotcy的合成分析 42
4- 2 氰酸脂共聚酯硬化反應 44
4-2- 1 cocyanate ester systems 44
4-2- 2 微差掃描熱分析 45
4-2- 3 紅外線光譜分析 46
4-2- 4 微差掃描熱分析 48
4-2- 5 熱安定性分析 49
4-2- 6 介電性質 49
4-2- 7 吸水性質 50
4- 3 環氧樹脂與氰酸脂硬化反應 51
4-3- 1 dgeba / dopotcy systems 51
4-3- 2 微差掃描熱分析 51
4-3- 3 紅外線光譜分析 52
4-3- 4 熱安定性分析 57
4-3- 5 介電性質 58
4-3- 6 吸水性質 59
4- 4 結論 60

第五章 三官能的環氧樹脂之硬化與性質分析 63
5- 1 單體之鑑定與分析 63
5-1- 1 dopotep的合成分析 63
5- 2 環氧樹脂之硬化反應 65
5-2- 1 dgeba / dopotep/ ddm systems 65
5-2- 2 微差掃描熱分析 65
5-2- 3 熱安定性分析 66
5-2- 4 介電性質 66
5- 3 結論 67

第六章 總 結 68

參考資料………………………………………………………………………….....70

表 目 錄
Table 3- 1 equivalent ratio of dopotcy and badcy ………………………...…..34
Table 3- 2 equivalent ratio of dgeba and dopotcy 35
Table 3- 3 equivalent ratio of dgeba and dopotep 35
Table 4- 1 DSC analysis with a heating rate 10oC/min of various cyanate esters ……………………………...…………………………………..46
Table 4- 2 FTIR Spectral Assignments 47
Table 4- 3 Sample designations and thermal properties of cured dcxtcy 48
Table 4- 4 Sample designations and thermal properties of cured dg1tcy 52
Table 4- 5 FTIR Spectral Assignments 55
Table 4- 6 TGA analysis data for various equivalent ratio of dopotcy and dgeba………………………………………………………………....57
Table 5- 1 Sample designations and thermal properties of cured dgxtgy ….64

圖 目 錄
Figure 2- 1 Pathways proposed for the reaction of cyanate ester with epoxy …………………………………………………………………………7
Figure 2- 2 Reaction of cyanate ester with epoxy 7
Figure 2- 3 Bisphenol A 環氧樹脂的化學構造與物性的關係 9
Figure 2- 4 燃燒循環示意圖 13
Figure 2- 5 耐燃劑之分類 19
Figure 4- 1 Infrared spectrum of dopotcy 71
Figure 4- 2 Infrared spectrum of dopotcy 71
Figure 4- 3 1H-NMR spectrum of dopotcy 72
Figure 4- 4 13C-NMR spectrum of dopotcy 72
Figure 4- 5 31P-NMR spectrum of dopotcy 73
Figure 4- 6 1H-1H COSY NMR spectrum of dopotcy 73
Figure 4- 7 1H-13C HSQC NMR spectrum of dopotcy 74
Figure 4- 8 DSC scan of dopotcy 75
Figure 4- 9 Mass spectrum of dopotcy 75
Figure 4- 10 DSC scans of uncured dcxtcy at room temperature 76
Figure 4- 11 DSC scans of badcy after incremental stepwise curing at each temperature 77
Figure 4- 12 DSC scans of dc1tc0.17 after incremental stepwise curing at each temperature 78
Figure 4- 13 DSC scans of dc1tc0.28 after incremental stepwise curing at each temperature 79
Figure 4- 14 DSC scans of dc1tc0.43 after incremental stepwise curing at each temperature 80
Figure 4- 15 DSC scans of dc1tc0.63 after incremental stepwise curing at each temperature 81
Figure 4- 16 DSC scans of dopotcy after incremental stepwise curing at each temperature 82
Figure 4- 17 Infrared spectrum of badcy after incremental stepwise curing at each temperature, 20oC per increment for 2hr 83
Figure 4- 18 Infrared spectrum of dc1tc0.17 after incremental stepwise curing at each temperature, 20oC per increment for 2hr 83
Figure 4- 19 Infrared spectrum of dc1tc0.28 after incremental stepwise curing at each temperature, 20oC per increment for 2hr 84
Figure 4- 20 Infrared spectrum of dc1tc0.43 after incremental stepwise curing at each temperature, 20oC per increment for 2hr 84
Figure 4- 21 Infrared spectrum of dc1tc0.63 after incremental stepwise curing at each temperature, 20oC per increment for 2hr 85
Figure 4- 22 Infrared spectrum of dopotcy after incremental stepwise curing at each temperature, 20oC per increment for 2hr 85
Figure 4- 23 DSC analysis of dcxtcy 86
Figure 4- 24 TGA analysis of dcxtcy 86
Figure 4- 25 Moisture absorptions of dcxtcy 87
Figure 4- 26 DSC scans of uncured dg1tcy at room temperature 88
Figure 4- 27 Infrared spectrum of dg1tc0.4 after incremental stepwise curing at each temperature, 20oC per increment for 20min 89
Figure 4- 28 Infrared spectrum of dg1tc0.6 after incremental stepwise curing at each temperature, 20oC per increment for 20min 89
Figure 4- 29 Infrared spectrum of dg1tc0.8 after incremental stepwise curing at each temperature, 20oC per increment for 20min 90
Figure 4- 30 Infrared spectrum of dg1tc1 after incremental stepwise curing at each temperature, 20oC per increment for 20min 90
Figure 4- 31 Infrared spectrum of dg1tc1.2 after incremental stepwise curing at each temperature, 20oC per increment for 20min 91
Figure 4- 32 DSC analysis of dg1tcy 92
Figure 4- 33 TGA analysis of dg1tcy 92
Figure 4- 34 Moisture absorptions of dg1tcy 93
Figure 5- 1 Infrared spectrum of dopotep…………………………...…………94
Figure 5- 2 Infrared spectrum of dopotep 94
Figure 5- 3 1H-NMR spectrum of dopotep 95
Figure 5- 4 13C-NMR spectrum of dopotep 95
Figure 5- 5 31P-NMR spectrum of dopotep 96
Figure 5- 6 1H-1H COSY NMR spectrum of dopotep (2.4-4.4ppm) 96
Figure 5- 7 1H-1H COSY NMR spectrum of dopotep (6.6-8.2ppm) 97
Figure 5- 8 1H-13C HSQC NMR spectrum of dopotep (2.1-4.8ppm) 98
Figure 5- 9 1H-13C HSQC NMR spectrum of dopotep (6.5-8.2ppm) 99
Figure 5- 10 Mass spectrum of dopotep 100
Figure 5- 11 DSC analysis of dgxtgy 100
Figure 5- 12 TGA analysis of dgxtgy 101

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