臺灣博碩士論文加值系統

本研究以具有不同官能基之一級胺類、甲醛與雙酚芴以及雙胺芴、甲醛與N-(4-羥基苯基)馬來醯亞胺，合成出三種含芴官能基之benzoxazine單體 9,9-bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BPBF; 9,9-bis(3-fur-
furyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BFBF; 9,9-bis(3-maleimideyl-3,4-
dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BMBF ，經由傅利葉轉換紅外線光譜儀(FT-IR)、氫核磁共振光譜儀(1H NMR)與碳核磁共振光譜儀(13C NMR)確認單體之化學結構，證明成功地合成三個單體。
先以雙酚芴、甲醛及苯胺為反應物合成出含有苯胺官能基之benzoxazine單體BPBF，擁有良好的有機溶劑溶解度。Poly(BPBF)具有優異的熱安定性(thermal stability)，高的玻璃轉移溫度(glass transition temperature, Tg) tan δ = 231.1℃。
其次以2-呋喃甲胺(furfurylamine)為起始物，製備了含呋喃官能基之benzoxazine 單體BFBF。Poly(BFBF)具有高的熱裂解溫度(Td = 361.8℃)、高的灰份殘餘率(char yield = 53.8%)、高的玻璃轉移溫度(tan δ = 324.3℃)以及低的熱膨脹係數(coefficient of thermal expansion, CTE = 31.22 ppm/℃)。
進一步以雙胺芴、N-(4-羥基苯基)馬來醯亞胺與甲醛為反應物合成出含馬來醯亞胺官能基之benzoxazine單體BMBF。Poly(BMBF)擁有良好的有機溶劑溶解度，具有兩階段的熱聚合反應，第一階段為馬來醯亞胺之聚合反應，第二階段為benzoxazine的熱開環反應，於開環聚合中形成之網狀結構有效的提升benzoxazine聚合物之交聯密度與熱安定性。Poly(BMBF)具有高的玻璃轉移溫度(Poly(BMBF-I), tan δ = 250.6℃, Poly(BMBF-II), tan δ = 374.4℃)、優異的熱穩定性(Td = 479.6℃)、高的灰份殘餘率(char yield = 64.9%)、高的儲存模數、低的熱膨脹係數(CTE = 30.04 ppm/℃)。
最後以BFBF單體用溶液摻混方式製備BFBF/DGEBA與BFBF/Pa-aptms摻混物；摻混物具有不錯的熱穩定性(Poly(BFBF/DGEBA 30%)，Td = 401.2℃，Poly(BFBF/Pa-aptms 40%)，Td = 407.5℃)，DGEBA比例增加可改善polybenzoxazine易脆的性質增加韌性；摻混Pa-aptms比例提高可增加其硬性，隨後以SEM觀察摻混物之相容性，當DGEBA含量達40% 將產生團聚現象使熱穩定性及尺寸安定性降低。
本研究聚焦在polybenzoxazine性質之改善，以終端需求之概念，利用分子設計觀點將不同功能性的分子基團導入benzoxazine的分子結構中，以提升其加工性、熱安定性、尺寸安定性與材料特性。從研究結果顯示本論文於benzxoazine之物性改善與提升作了相當程度之貢獻：(1)將具有芴的官能基導入benzoxazine，提升其熱穩定性，另可改善polybenzoxazine之尺寸安定性，(2)將呋喃分子基團導入benzoxazine的分子結構中，提升polybenzoxazine的性能，(3)以具有可聚合的馬來醯亞胺導入benzoxazine，提高其交聯密度，大幅提升polybenzoxazine的性質，(4)以DGEBA與Pa-aptms摻混於BFBF單體作共聚合，可有效地改善polybenzoxazine的韌性與硬性。

This study we used different primary amines, formaldehyde, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-aminophenyl)fluorene, formaldehyde, and N-(4-hydroxyphenyl)maleimide as raw materials to synthesize a series of benzoxazine monomer containing fluorene group: 9,9-bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BPBF; 9,9-bis(3-fur- furyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BFBF; 9,9-bis(3-maleimideyl-3, 4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene, BMBF. Chemical structures of the synthesized benzoxazine monomer were confirmed by FT-IR, 1H and 13 C NMR analyses.
First, a benzoxazine monomer, BPBF, with aniline group was synthesized using 9,9-bis(4-hydroxyphenyl)fluorene, formaldehyde, and aniline. The obtained benzoxazine BPBF showed good organic solvent solubility. Poly(BPBF) possessed good thermal stability, and higher glass transition temperature, Tg. The Tg value of poly(BPBF) from the tan δ peak was 231.1℃.
Second, a benzoxazine monomer, BFBF, with furan group was synthesized using furfurylamine. The obtained benzoxazine BFBF revealed that the cured poly(BFBF) possessed good thermal properties with the 5% weight loss temperature of 361.8℃, and char yield at 800℃ of 53.7%. In addition, it showed higher Tg and the Tg from the tan δ peak was 324.3℃. The coefficient of thermal expansion of poly(BFBF) was 31.22 ppm/℃.
Third, a benzoxazine monomer, BMBF, with maleimide group was synthesized using 9,9-bis(4-aminophenyl)fluorene, formaldehyde, and N-(4-hydroxyphenyl)maleimide as raw materials. The cured BMBF exhibited good solvent solubility, and thermal stability. DSC results showed that there are two stages polymerization, the first stage is from the polymerization of maleimide and the second stage is from the ring opening of benzoxazine. Network structures were formed during polymerization, which increases the crosslink density and thermal stability of the poly(BMBF). Thermal analyses results found that the Tg of tan δ was 374.4℃, the 5% weight loss temperature was 479.6℃, the char yield at 800℃ was 64.9%, and the coefficient of thermal expansion of poly(BMBF) was 30.04 ppm/℃.
Finally, BFBF was blended individually with DGEBA and Pa-aptms. The obtained blends showed good thermal stability, for example: the 5% weight loss temperature of BFBF/DGEBA 30% was 401.2℃, and that for BFBF/Pa-aptms 40% was 407.5℃. The toughness of the blend can be improved by the increase of DGEBA content in the blend. On the contrary, the rigid of the blend can be increased by the addition of Pa-aptms in the blend. The SEM micrograph showed that there was phase separation for BFBF/DGEBA 40%, and result in lower thermal properties and dimension stability.
In this study we introduced different function groups into benzoxazine structure, and improved their processing, thermal properties, and dimension stability. We focus on (1) introduced fluorene group into benzoxazine and increased their thermal stability, (2) introduced furan group into benzoxazine and improved polybenzoxazine properties, (3) introduced polymerizable maleimide into benzoxazine and increased crosslink density, (4) blended BFBF individually with DGEBA and Pa-aptms, and improved toughness or rigidity properties of polybenzoxazine.

摘 要 I
ABSTRACT III
誌 謝 V
目 錄 VI
圖 目 錄 VIII
表 目 錄 XI
第一章 緒論 1
1-1 前言 1
第二章 文獻回顧 3
2-1 Polybenzoxazine之簡介 3
2-2 Polybenzoxazine之特性 10
2-3 Polybenzoxazine之改質 10
2-4 含可聚合之官能基 benzoxazine 11
2-5 主鏈含benzoxazine聚合物 15
2-6 Benzoxazine之聚合反應分析 17
2-7 Benzoxazine之難燃性 18
2-8 積分程序分解溫度(Integral procedure decomposition temperature,
IPDT) 20
2-9 Benzoxazine之熱裂解動力學 21
2-10 芴之簡介 22
2-11 含芴結構的中間體 23
2-12 聚醯亞胺 (Polyimide, PI) 24
2-13 呋喃 (Furan) 26
2-14 酚醛樹脂之介紹 26
2-15 環氧樹脂之介紹 26
2-16 研究動機 27
第三章 實驗 29
3-1 實驗流程 29
3-2 實驗藥品 30
3-3 儀器設備 33
3-4 實驗步驟 36
3-4-1 N-(4-Hydroxyphenyl)maleic acid, NHMA之合成 36
3-4-2 N-(4-Hydroxyphenyl)maleimide, HPM之合成 37
3-4-3 9,9-Bis(4-aminophenyl)fluorene, BAPF之合成 37
3-4-4 9,9-bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene,
BPBF之合成 38
3-4-5 9,9-bis(3-furfuryl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene,
BFBF之合成 39
3-4-6 9,9-bis(3-maleimideyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene,
BMBF之合成 40
3-4-7 3,4-dihydro-3-phenyl-2H-1,3-benzoxazine, Pa之合成 41
3-4-8 3,4-dihydro-3-(3-(trimethoxysily)propyl-2H-1,3-benzoxazine,
Pa-aptms之合成 42
3-5 摻混熟化樣品製備 42
第四章 結果與討論 44
4-1 單體鑑定 44
4-1-1 N-(4-Hydroxyphenyl)maleic acid (NHMA)之結構鑑定與分析 44
4-1-2 N-(4-Hydroxyphenyl)maleimide (HPM) 之結構鑑定與分析 45
4-1-3 9,9-Bis(4-aminophenyl)fluorene (BAPF) 之結構鑑定與分析 46
4-1-4 9,9-bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene
(BPBF) 之結構鑑定與分析 49
4-1-5 9,9-bis(3-furfuryl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene
(BFBF) 之結構鑑定與分析 51
4-1-6 9,9-bis(3-maleimideyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)fluorene
(BMBF) 之結構鑑定與分析 53
4-1-7 3,4-dihydro-3-(3-(trimethoxysily)propyl-2H-1,3-benzoxazine
(Pa-aptms) 之結構鑑定與分析 56
4-2 溶解度測試 57
4-3 Polybenzoxazine聚合反應 58
4-4 熱性質分析 68
4-5 熱機械性質分析 72
4-6 以摻混方式製備高分子 76
4-7 摻混物聚合反應 77
4-8 摻混物熱性質分析 82
4-9 摻混物熱機械性質分析 84
4-10 摻混物表面形態 88
第五章 結論 90
第六章 未來展望 92
第七章 參考文獻 93

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