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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭如忠(Ru-Jong Jeng) | |
dc.contributor.author | Yun-Cheng Chung | en |
dc.contributor.author | 鍾昀澄 | zh_TW |
dc.date.accessioned | 2021-06-17T07:09:10Z | - |
dc.date.available | 2021-07-24 | |
dc.date.copyright | 2019-07-24 | |
dc.date.issued | 2019 | |
dc.date.submitted | 2019-07-22 | |
dc.identifier.citation | 1.Vathke‐Ernst, H.; Hoffmann, H., Cycloadditions of Allyl Cations, 261) Norbornene Derivatives from Cyclopentadiene and 2, 4‐Dimethyl‐3‐penten‐2‐ol in an Acidic Two Phase System. A Stepwise Diels‐Alder‐like Cyclization. Chemische Berichte 1981, 114 (4), 1464-1475.
2.Dinda, M.; Chakraborty, S.; Si, M. K.; Samanta, S.; Ganguly, B.; Maiti, S.; Ghosh, P. K., Solar driven uphill conversion of dicyclopentadiene to cyclopentadiene: an important synthon for energy systems and fine chemicals. RSC Advances 2014, 4 (97), 54558-54564. 3.Hsiao, S. H.; Li, C. T., Synthesis and characterization of new adamantane‐based cardo polyamides. Journal of Polymer Science Part A: Polymer Chemistry 1999, 37 (10), 1435-1442. 4.Korshak, V. V.; Vinogradova, S. V.; Vygodskii, Y. S., Cardo polymers. 1974. 5.Wang, X.; Liu, F.; Lai, J.; Fu, Z.; You, X., Comparative investigations on the effects of pendent trifluoromethyl group to the properties of the polyimides containing diphenyl-substituted cyclopentyl Cardo-structure. Journal of Fluorine Chemistry 2014, 164, 27-37. 6.Hu, Z.; Li, S.; Zhang, C., Synthesis and properties of polyamide–imides containing fluorenyl cardo structure. Journal of applied polymer science 2007, 106 (4), 2494-2501. 7.Guo, D.-D.; Sheng, S.-R.; Mao, X.-C.; Liu, X.-L.; Jiang, J.-W., New poly (ether benzoxazole) s containing xanthene cardo groups. High Performance Polymers 2016, 28 (3), 309-314. 8.Papava, G. S.; Maisuradze, N.; Zarkua, Z.; Dokhturishvili, N.; Sarishvili, Z.; Razmadze, G.; Vinogradova, S.; Korshak, V., Synthesis and study of diols containing bisphenol fragments and of polymers produced on their basis. Acta polymerica 1988, 39 (8), 445-448. 9.Yang, C. P.; Chen, R. S.; Yu, C. W., Preparation and characterization of organosoluble polyimides based on 1, 1‐bis [4‐(3, 4‐aminophenoxy) phenyl] cyclohexane and commercial aromatic dianhydrides. Journal of applied polymer science 2001, 82 (11), 2750-2759. 10.Dai, S.; Lin, C.; Rao, D.; Stuber, F.; Carleton, P.; Ulrich, H., Selective indirect oxidation of phenol to hydroquinone and catechol. The Journal of Organic Chemistry 1985, 50 (10), 1722-1725. 11.S Patil, L.; S Suryawanshi, V.; B Pawar, O.; D Shinde, N., An Improved, Highly Efficient Method for the Synthesis of Bisphenols. Journal of Chemistry 2011, 8 (4), 2016-2019. 12.Engels, H. W.; Pirkl, H. G.; Albers, R.; Albach, R. W.; Krause, J.; Hoffmann, A.; Casselmann, H.; Dormish, J., Polyurethanes: versatile materials and sustainable problem solvers for today’s challenges. Angewandte Chemie International Edition 2013, 52 (36), 9422-9441. 13.Szycher, M., Szycher's handbook of polyurethanes. CRC press: 1999. 14.刘晓燕; 顾林玲; 李娟, 聚碳酸酯二元醇及其在聚氨酯材料中的应用. 聚氨酯工业 2004, 19 (1), 6-8. 15.Lelah, M. O.; Cooper, S. L., Polyurethanes in Medicine. CRC Press: 1986. 16.Stokes, K.; McVenes, R.; Anderson, J. M., Polyurethane elastomer biostability. Journal of biomaterials applications 1995, 9 (4), 321-354. 17.Boretos, J. W.; Pierce, W. S., Segmented polyurethane: a new elastomer for biomedical applications. Science 1967, 158 (3807), 1481-1482. 18.Ni, P.; Li, J.; Suo, J.; Li, S., Novel polyether polyurethane/clay nanocomposites synthesized with organic‐modified montmorillonite as chain extenders. Journal of applied polymer science 2004, 94 (2), 534-541. 19.Wan, L.; Han, D.; Liu, Q.; Xu, Z.; Huang, F., Polyether‐based main‐chain‐type polytriazole elastomer with benzoxazine via a 1, 3‐dipolar cycloaddition reaction. Journal of Applied Polymer Science 2016, 133 (1). 20.Zhang, K.; Zhuang, Q.; Liu, X.; Cai, R.; Yang, G.; Han, Z., Synthesis and copolymerization of benzoxazines with low-dielectric constants and high thermal stability. Rsc Advances 2013, 3 (15), 5261-5270. 21. Ghosh, N.; Kiskan, B.; Yagci, Y., Polybenzoxazines—new high performance thermosetting resins: synthesis and properties. Progress in polymer Science 2007, 32 (11), 1344-1391. 22.Kirschbaum, S.; Landfester, K.; Taden, A., Synthesis and thermal curing of benzoxazine functionalized polyurethanes. Macromolecules 2015, 48 (12), 3811-3816. 23.Chernykh, A.; Agag, T.; Ishida, H., Effect of polymerizing diacetylene groups on the lowering of polymerization temperature of benzoxazine groups in the highly thermally stable, main-chain-type polybenzoxazines. Macromolecules 2009, 42 (14), 5121-5127. 24.Wang, C.-F.; Wang, Y.-T.; Tung, P.-H.; Kuo, S.-W.; Lin, C.-H.; Sheen, Y.-C.; Chang, F.-C., Stable superhydrophobic polybenzoxazine surfaces over a wide pH range. Langmuir 2006, 22 (20), 8289-8292. 25.Ishida, H.; Allen, D. J., Physical and mechanical characterization of near‐zero shrinkage polybenzoxazines. Journal of polymer science Part B: Polymer physics 1996, 34 (6), 1019-1030. 26.Kocaarslan, A.; Kiskan, B.; Yagci, Y., Ammonium salt catalyzed ring-opening polymerization of 1, 3-benzoxazines. Polymer 2017, 122, 340-346. 27.Uchida, S.; Kawauchi, T.; Furukawa, N.; Takeichi, T., Polymer alloys of high-molecular-weight benzoxazine and epoxy resin. High Performance Polymers 2014, 26 (7), 846-855. 28.Takeichi, T.; Guo, Y.; Agag, T., Synthesis and characterization of poly (urethane‐benzoxazine) films as novel type of polyurethane/phenolic resin composites. Journal of Polymer Science Part A: Polymer Chemistry 2000, 38 (22), 4165-4176. 29.Baqar, M.; Agag, T.; Ishida, H.; Qutubuddin, S., Poly (benzoxazine-co-urethane) s: A new concept for phenolic/urethane copolymers via one-pot method. Polymer 2011, 52 (2), 307-317. 30.Weber, E.; Helbig, C.; Seichter, W.; Czugler, M., A new functional cyclophane host. Synthesis, complex formation and crystal structures of three inclusion compounds. Journal of inclusion phenomena and macrocyclic chemistry 2002, 43 (3-4), 239-246. 31.Parsania, P.; Shah, P.; Patel, K.; Patel, R., Synthesis and characterization of the poly-(2-methoxycyanurate) of 1, 1′-bis-(4-hydroxyphenyl)-cyclohexane. Journal of Macromolecular Science—Chemistry 1985, 22 (11), 1495-1508. 32.Wu, C.-H.; Lin, Y.-R.; Yeh, S.-C.; Huang, Y.-C.; Sun, K.-H.; Shih, Y.-F.; Su, W.-C.; Dai, C.-A.; Dai, S. A.; Jeng, R.-J., A Facile Synthetic Route to Ether Diols Derived from 1, 1-Cyclopentylenylbisphenol for Robust Cardo-Type Polyurethanes. Macromolecules 2019. 33.Yeganeh, H.; Jangi, A., Thermally curable polyurethanes containing naphthoxazine groups in the main chain. Polymer International 2010, 59 (10), 1375-1383. 34. Kiskan, B.; Yagci, Y.; Ishida, H., Synthesis, characterization, and properties of new thermally curable polyetheresters containing benzoxazine moieties in the main chain. Journal of Polymer Science Part A: Polymer Chemistry 2008, 46 (2), 414-420. 35.Tuzun, A.; Kiskan, B.; Alemdar, N.; Erciyes, A. T.; Yagci, Y., Benzoxazine containing polyester thermosets with improved adhesion and flexibility. Journal of Polymer Science Part A: Polymer Chemistry 2010, 48 (19), 4279-4284. 36.Gilbert, E.; Morales, G.; Spontón, M.; Estenoz, D., Design of thermosetting polymeric systems based on benzoxazines modified with maleic anhydride. Journal of Applied Polymer Science 2018, 135 (17), 46183. 37.Kudoh, R.; Sudo, A.; Endo, T., A highly reactive benzoxazine monomer, 1-(2-hydroxyethyl)-1, 3-benzoxazine: activation of benzoxazine by neighboring group participation of hydroxyl group. Macromolecules 2010, 43 (3), 1185-1187. 38.Han, L.; Zhang, K.; Ishida, H.; Froimowicz, P., Study of the Effects of Intramolecular and Intermolecular Hydrogen‐Bonding Systems on the Polymerization of Amide‐Containing Benzoxazines. Macromolecular Chemistry and Physics 2017, 218 (18), 1600562. 39.Zhang, K.; Han, L.; Nie, Y.; Szigeti, M. L.; Ishida, H., Examining the effect of hydroxyl groups on the thermal properties of polybenzoxazines: using molecular design and Monte Carlo simulation. RSC advances 2018, 8 (32), 18038-18050. 40.Kiskan, B.; Koz, B.; Yagci, Y., Synthesis and characterization of fluid 1, 3‐benzoxazine monomers and their thermally activated curing. Journal of Polymer Science Part A: Polymer Chemistry 2009, 47 (24), 6955-6961. 41.Wang, J.; Wu, M.-q.; Liu, W.-b.; Yang, S.-w.; Bai, J.-w.; Ding, Q.-q.; Li, Y., Synthesis, curing behavior and thermal properties of fluorene containing benzoxazines. European Polymer Journal 2010, 46 (5), 1024-1031. 42.Feng, T.; Wang, J.; Wang, H.; Ramdani, N.; Zu, L.; Liu, W.; Xu, X., Copolymerization of fluorene‐based main‐chain benzoxazine and their high performance thermosets. Polymers for Advanced Technologies 2015, 26 (6), 581-588. 43.Dunkers, J.; Ishida, H., Reaction of benzoxazine‐based phenolic resins with strong and weak carboxylic acids and phenols as catalysts. Journal of Polymer Science Part A: Polymer Chemistry 1999, 37 (13), 1913-1921. 44.Bernardini, J.; Licursi, D.; Anguillesi, I.; Cinelli, P.; Coltelli, M.-B.; Antonetti, C.; Galletti, A. M. R.; Lazzeri, A., Exploitation of Arundo Donax L. hydrolysis residue for the green synthesis of flexible polyurethane foams. BioResources 2017, 12 (2), 3630-3655. 45.Sun, J.; Wei, W.; Xu, Y.; Qu, J.; Liu, X.; Endo, T., A curing system of benzoxazine with amine: reactivity, reaction mechanism and material properties. RSC Advances 2015, 5 (25), 19048-19057. 46.Sudo, A.; Mori, A.; Endo, T., Promoting effects of urethane derivatives of phenols on the ring‐opening polymerization of 1, 3‐benzoxazines. Journal of Polymer Science Part A: Polymer Chemistry 2011, 49 (10), 2183-2190. 47.Yeganeh, H.; Shamekhi, M. A., Poly (urethane-imide-imide), a new generation of thermoplastic polyurethane elastomers with enhanced thermal stability. Polymer 2004, 45 (2), 359-365. 48.Takeichi, T.; Ujiie, K.; Inoue, K., High performance poly (urethane-imide) prepared by introducing imide blocks into the polyurethane backbone. Polymer 2005, 46 (25), 11225-11231. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/72884 | - |
dc.description.abstract | 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。 | zh_TW |
dc.description.abstract | 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. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T07:09:10Z (GMT). No. of bitstreams: 1 ntu-108-R06549016-1.pdf: 5991224 bytes, checksum: 92cbb1d33b9099742d32dd657c9e1656 (MD5) Previous issue date: 2019 | en |
dc.description.tableofcontents | 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 | |
dc.language.iso | zh-TW | |
dc.title | 以氧氮苯并環己烷雙醇作為鏈延長劑製備聚氨酯之合成與鑑定 | zh_TW |
dc.title | Novel benzoxazine-based diols as chain extender for polyurethanes: synthesis and characterization | en |
dc.type | Thesis | |
dc.date.schoolyear | 107-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 葉世傑,戴憲弘,蘇文炯,汪孟緯 | |
dc.subject.keyword | 雙環戊二烯,cardo結構,聚氧氮苯並環己烷聚氨酯, | zh_TW |
dc.subject.keyword | dicyclopentadiene,cardo-type structure,poly(benzoxazine-co-urethane)s, | en |
dc.relation.page | 90 | |
dc.identifier.doi | 10.6342/NTU201901733 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2019-07-23 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
顯示於系所單位: | 高分子科學與工程學研究所 |
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