臺灣博碩士論文加值系統

本研究利用3種不同類型的雙酚( Bisphenol A, Bisphenol F, CPDP) 單體與6-胺基-1-己醇反應，成功開發出含氧氮苯並并環己烷二醇單體 (BPABBD、BPFBBD、CPDPBBD)並將其當成聚氨酯鏈延長劑，而其中CPDPBBD 為具有cardo結構的二醇單體。此具有cardo結構的雙酚單體，為本實驗室經由簡單的石油烴高溫裂解製五碳烯烴餾分-雙環戊二烯(dicyclopentadiene, DCPD) 為原料，與苯酚進行一系列反應生成有cardo結構之雙酚 (bisphenol) 單體 (CPDP)。含氧氮苯并環聚氨酯之製備，首先選取三種不同類型的聚醇軟鏈段:聚四氫呋喃 (PTMEG)、聚己內酯 (PCL)、聚碳酸酯 (PCPO) 與苯基甲烷二異氰酸酯 (MDI) 製備預聚物。再將上述之BPABBD、BPFBBD、CPDPBBD鏈延長劑，各別加入預聚物中形成聚氧氮苯并環己烷-聚氨酯共聚物。此共聚物最大特色在於，高分子鏈中的氧氮苯并環己烷可經由加溫進行交聯反應，使分子結構變得更緊密。有利於經由改善製程而得微調材料性質。此研究之所有單體經由核磁共振氫譜鑑定，氧氮苯并環己烷-聚氨酯共聚物，此聚氨酯則以傅里葉轉換紅外光譜鑑定。
在氧氮苯并環己烷開環溫度之量測由微示差掃描熱卡分析儀 (DSC) 進行檢測。研究中發現本系列之聚氧氮苯并環己烷-聚氨酯共聚物，除了在220 oC有放熱峰之外，另一個放熱峰出現在160-180 oC左右。本文利用實驗結果與文獻查詢，提出4種可能造成該結果的原因，包括: (1). 殘留的異氰酸 (-NCO)導致開環，(2). 異氰酸遇水產生之一級胺 (-NH2)導致，(3). 單體上之羥基 (-OH)導致，或是(4). 氧氮苯并環己烷鏈段催化聚氨酯造成降解。此結果也造成了聚氧氮苯并環己烷-聚氨酯共聚物，在加溫開環前後各項性質的差異。為了降低高溫反應的干擾，本研究以150 oC, 1小時做為材料開環之條件。此一系列未加溫開環之聚氨脂的各項數據顯示，當MDI-PCPO與CPDPBBD做為鏈延長劑 (PCPO-CPDPBBD45)，所得之機性能為最佳。其拉力值達 9.1 MPa ( elongation 為 141 %)。DMA 的結果顯示其loss modulus 在溫度 150 oC時才顯現出來。證明具有cardo環狀結構與交聯的聚氨酯適合往高溫應用研究的發展。拉力測試中PTMEG-CPDPBBD45之樣品則有最大伸長量1300%，PCL-CPDPBBD45則有較好的楊氏模數。開環後之樣品雖各項物性質變弱，各樣品中仍以(PCPO-CPDPBBD45)有較佳之結果。本研究不同配方所製備之含氧氮苯并環己烷-聚氨酯共聚物，具有做為彈性體及其他高性能材料之潛力。

A series of poly(benzoxazine-co-urethane)s with novel benzoxazine diols as chain extenders were successfully developed in this work. These diol chain extenders were obtained by differents bisphenol (Bisphenol A, Bisphenol F, CPDP) compounds refluxed with 6-amino-1-hexanol and paraformaldehyde. The soft segments of PU were chosed form polytetramethyleneetherglycol (PTMEG), polycaprolactone (PCL), polycarbonate diol (PCPO) and the diisocyanate of the PU was 4,4-methylenediphenyl diisocyanate (MDI). poly(benzoxazine-co-urethane)s were synthesized by a two-step polymerization method, in which the diisocyanate reacted with polyols first and then reacted with the chain extenders. The characterization of benzoxazine diol monomers were performed by 1H-NMR. The PU films were characterized by FTIR.
The curing temperature of poly(benzoxazine-co-urethane)s are detected by DSC scans, the result exhibited two exothermic peaks in a range of 160-250 oC. Four possible mechanisms were used to explain the phenomena of lower curing temperature. They are including: (1). Benzoxazine attacked by residual isocynated group, (2). By residual primary amine, (3). Hydroxyl group on chain extender, and (4). Intrinsic of benzoxazine core attack urethane linkage. For the sake of decomposition issue, the curing temperature was set at 150 oC. In this research of PU formula, PCPO-MDI-CPDPBBD45 uncured and cured samples exhibited the best performance in tensile stress and DMA measurement. They are 9.1 MPa ( elongation is 141 %) in stress-stain plot and DMA exhibited the loss modulus temperature at 150 oC. The TGA test the thermal stabilities of poly(benzoxazine-co-urethane)s and the results showed polyurethanes with higher benzoxazine content and cardo structure show higher char yield at high temperature, which suggested they possessed better thermal stability. In stress-strain curves, with more rigid backbone, the cardo-type polyurethanes possessed better mechanical properties than those polyurethanes based on BPABBD and BPFBBD. The mechanical properties can be modified with different composition of benzoxazine. The trend suggested PU-Bzs possess the potential for the application needed for high mechanical reinforcement.

誌謝 I
摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XIII
壹、緒論 1
貳、文獻回顧 2
2.1五碳在化學工業之應用 2
2.1.1 環戊二烯 (CPD) 3
2.1.2 雙環戊二烯 (DCPD) 5
2.2 Cardo結構介紹及在高分子上之應用 7
2.3 反應中間體製備 14
2.4聚氨酯之簡介 16
2.4.1 聚氨酯之原料及特性 16
2.4.2 聚氨酯彈性體簡介 20
2.5氧代氮代苯并環己烷 (Benzoxazine, Bz)18-22 22
2.6氧代氮代苯并環己烷-聚氨酯共聚物 26
2.7 研究動機 28
參、實驗內容 30
3.1 藥品及溶劑 30
3.2 實驗儀器 34
3.3 實驗流程圖 36
3.4 單體合成步驟 40
3.4.1反應前驅物CPP製備 40
3.4.2 含cardo結構之雙苯酚中間體 (CPDP)製備 41
3.4.3 由CPDP合成含五碳環雙氧氮苯並環己烷二醇單體製備 42
3.4.4 由BPA合成含二甲基雙苯氧氮并環己烷二醇單體製備 43
3.4.5 由BPF合成雙氧氮苯并環己烷二醇製備 44
3.5聚氧氮苯併環己烷聚胺酯薄膜製備 45
3.5.1 以PTMEG2000為軟鏈段結構聚氨酯製備 45
3.5.2 以PCL3000為軟鏈段結構聚氨酯製備 46
3.5.3 以PCPO2000為軟鏈段結構聚氨酯製備 47
肆、結果與討論 48
4.1 單體合成之分析及鑑定 48
4.1.1反應前驅物CPP分析與鑑定 48
4.1.2含cardo結構之雙苯酚中間體 (CPDP)分析與鑑定 52
4.1.3含Cardo雙氧氮苯并環己烷醇單體 (CPDPBBD) 製備 53
4.1.4含二甲基雙氧氮苯并環己烷醇單體(BPAPBBD)製備 54
4.1.5雙氧氮苯并環己烷醇單體(BPFBBD)製備 55
4.1.6 甲基氧氮苯并環己烷雙醇單體開環溫度分析 56
4.2 Poly(benzoxazine-co-urethane) (PU-Bz)合成與鑑定 58
4.2.1 PTME-PUs 之 FT-IR光譜分析 59
4.2.2 PCL-PUBZs 之 FT-IR光譜分析 59
4.2.3 PCPO-PUs 之 FT-IR光譜分析 60
4.3 PU-BZs熱性質分析 62
4.3.1 TGA熱重分析 62
4.3.2 DSC微差掃描熱分析 65
4.4聚氨酯機械性質分析 73
4.4.1機械性質之拉力測試 73
4.4.2 DMA動態機械性質分析 77
伍、結論 81
陸、附錄 82
柒、參考文獻 87

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