Development of asymmetrical phosphine and fluorine containing polyimides for flexible LCD display and dicyclopentadiene-benzoxazine/cyanate ester for low dielectric copper clad laminate materials
Part I：
利用含有單官能的酚基與胺基的不對稱單體(1)分別與3-三氟甲基-4-氯硝基苯和2-三氟甲基-4-氯硝基苯由SNAr與高壓還原，製備出不對稱二胺單體(3)及單體(6)。由X光單晶繞射圖顯示單體(3)與單體(6)有著差異極大的分子構型。並與市售的五種雙酸酐製備出(4a-4e)與(7a-7e)兩系列的PI，並探討三氟甲基位置對於PI性質的影響。其中(7)系列有著比較好的Tg、尺寸安定性、穿透率及疏水性，(4)系列則有比較好的有機溶解性、較低的折射率介電常數。
Part II：
以DCPD-novolac、苯胺及甲醛製作DCPD-phenol型的benzoxazine。並以氰酸酯BADCY為基質製備共聚物。並進行DCPD-BZ與BADCY反應型共聚物，相容性、微結構、熱性質及介電性質的研究。首先以DSC及IR光譜監測共聚物反應性，並在固化反應中觀察到第一個反應為氰酸酯的三環化形成triazine，第二是triazine與Benzoxazine之間的共反應形成alkyl isocyanurate 和 diphenyl ether連結，第三為Benzoxazine的自身開環交聯，第四則為isocyanurate與phenol之間的共反應形成carbamate連結。並由DMA的單一tanδ顯示共聚物為勻相高分子而且保有不錯玻璃轉移溫度以及尺寸安定性。並且吸水性測試與介電儀中數據顯示其吸水性與介電常數分析中都有優異的疏水性與低的介電常數。Part I：
Two unsymmetric diamines, 1-(4-(2-frifluoromethyl-4-aminophenoxy)phenyl)-1-(4-aminophenyl)- 1-(6-oxido-6H -dibenz oxaphosphorin-6-yl)ethane (3) and 1-(4-(3-frifluoromethyl-4-aminophenoxy)phenyl)-1-(4-aminophenyl)- 1-(6-oxido-6H -dibenz oxaphosphorin-6-yl)ethane (6), were prepared from the nucleophilic substitution of 1-(4-hydroxyphenyl)-1-(4-aminophenyl)-1- (6-oxido-6H –3-dibenz oxaphosphorin-6-yl)ethane (1) with 3-trifluoromethyl-4-chloronitrobenzene and 2-trifluoromethl-4-chloronitrobenzene,respectively, followed by catalytic hydrogenation. Single crystal diffractogram shows diamine (6) is more rigid than diamine (3). Polyimides (4a-4e) and (7a-7e) were prepared from five commercially dianhydride (a-e) with (3) and (4), respectively. The effect of the position of trifluoromethyl (ortho or meta to amine) on properties of the resulting polyimides was discussed. Among the two series polyimides, Polyimides (7) exhibit higher Tg, dimensional stability, transmittance, and hydrophbility, while polyimides (4) display better organo-solubility, lower refractive index and dielectric constant.
Part II：
Dicyclopentadiene(DCPD) phenol-based benzoxazine (DCPD-Bz) was prepared from the Manich condensation of DCPD-phenol, formaldehyde, and aniline. Copolymers based on DCPD-Bz and dicyanate ester of bisphenol A (BADCY) were prepared. The miscibility, microstructure, and the thermal and dielectric properties of the reactive blends of DCPD-Bz and BADCY were studied. DSC and IR were applied to monitor the curing reactions of the reactive blends. Four reactions were observed in the curing reactions: the first is the cyclotrimerization of cyanate ester, producing the triazine structure; the second is the coreaction between the triazine structure and benzoxazine, forming alkyl isocyanurate and diphenyl ether linkages; the third is the ring-opening of benzoxazine; and the fourth is the coreaction between isocyanurate and phenol, forming carbamate linkage. The coreaction decomposes the polycyanurate structures and brings parts of the polycyanurate structures into the polybenzoxazine matrix. Thus, a miscible blend can be achieved, as judged by the single composition-dependent Tg in the dynamic mechanical and thermal mechanical analyses. The experimental data also show that the dimensional stability, moisture absorption and dielectric properties are enhanced via the reactive blends.摘要 II
ABSTRACT III
第一部分: 1
第一章:緒論與研究動機 2
1.1緒論: 2
1.2研究動機: 3
第二章:文獻回顧與實驗設計 4
2.1.分子設計1-27: 4
2.2芳香族親核性取代反應28-34: 11
2.3本實驗室先前研究35-37: 15
2.4取代基團位置38-43: 16
第三章:單體合成與分析鑑定 19
3.1實驗藥品與溶劑 19
3.2儀器設備: 20
3.3單體合成與鑑定 21
3.3.1單體(2)合成與鑑定 21
3.3.2單體(3)之合成與鑑定 29
3.3.4 聚合物(4)系列之合成、薄膜製備與鑑定 37
3.3.5單體(5)之合成與鑑定 40
3.3.6單體(6)之合成與鑑定 48
3.3.7 聚合物(7)系列之合成、薄膜製備與鑑定 56
第四章 性質分析與結果討論 59
4.1硝基單體(2)、(5)合成 59
4.2二胺單體(3)、(6)合成 60
4.3高分子(4)、(7)合成 61
4.4熱性質分析 62
4.5機械強度測試 70
4.6光學性質及介電常數 72
4.7接觸角與吸水率 79
4.8有機溶解度測試 83
第五章:結論與未來展望 88
結論: 88
未來展望: 88
第二部分: 90
第六章:緒論與研究動機 91
6.1緒論: 91
6.2研究動機: 92
第七章:文獻回顧 93
7.1 DCPD簡介48-49: 93
7.2 Benzoxazine樹酯簡介50-53: 94
7.3 DCPD-Phenol54-55: 95
7.4氰酸酯簡介56-61: 96
7.5氰酸酯共聚物62-76: 97
7.6氰酸酯與Benzoxazine樹酯73-76: 101
第八章:預聚物合成與分析鑑定 107
8.1實驗藥品與溶劑 107
8.2儀器設備: 107
8.3單體合成與鑑定 108
8.3.1 DCPD-novolac (1)合成與鑑定 108
8.3.2 DCPD-BZ (2)合成與鑑定 111
第九章: 性質分析與結果討論 115
9.1 DCPD-novolac (1)合成 115
9.2 DCPD-BZ(2)合成 116
9.3 DSC放熱峰探討 119
9.5 FT-IR共聚反應機制探討 121
9.6共聚熱性質 131
9.7共聚吸水性與接觸角分析 135
9.8共聚介電性質 139
第十章: 結論 141
結論: 141
參考文獻 142
附錄 146
Monomer (2) SCXRD Data 146
Monomer (3) SCXRD Data 158
Monomer (5) SCXRD Data 170
Monomer (6) SCXRD Data 18
