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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 鄭如忠(Ru-Jong Jeng) | |
| dc.contributor.author | Yu-Ching Chen | en |
| dc.contributor.author | 陳昱清 | zh_TW |
| dc.date.accessioned | 2021-06-16T05:11:33Z | - |
| dc.date.available | 2017-08-25 | |
| dc.date.copyright | 2014-08-25 | |
| dc.date.issued | 2014 | |
| dc.date.submitted | 2014-08-18 | |
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C.; Garnier, L.; Kraft, A., Shape-memory properties of segmented polymers containing aramid hard segments and polycaprolactone soft segments. Polymers 2010, 2 (2), 71-85. 54. Kim, B. K.; Lee, S. Y.; Xu, M., Polyurethanes having shape memory effects. Polymer 1996, 37 (26), 5781-5793. 55. Lee, B. S.; Chun, B. C.; Chung, Y.-C.; Sul, K. I.; Cho, J. W., Structure and thermomechanical properties of polyurethane block copolymers with shape memory effect. Macromolecules 2001, 34 (18), 6431-6437. 56. Gu, S.; Jana, S., Effects of Polybenzoxazine on Shape Memory Properties of Polyurethanes with Amorphous and Crystalline Soft Segments. Polymers 2014, 6 (4), 1008-1025. 57. Saralegi, A.; Foster, E. J.; Weder, C.; Eceiza, A.; Corcuera, M. A., Thermoplastic shape-memory polyurethanes based on natural oils. Smart Materials and Structures 2014, 23 (2), 025033. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/55953 | - |
| dc.description.abstract | 本論文使用精準控制的poly(urea/malonamide)側鏈，探討其應用在形狀記憶聚氨酯的效果。可精準控制分子量及鏈長的poly(urea/malonamide)樹枝狀(DG 系列)與直線型(LG 系列)氫鍵側鏈提供聚胺酯的物理交聯；聚氨酯主鏈SPU使用同一鍋以確保聚氨酯主鏈的分子量及其分佈相同。
聚胺酯利用MDI及CAPA®2303 (Mn=3000)為主體，導入反應性的小分子雙醇，製備具有可後修飾官能基azetidine-2,4-dione之聚胺酯Side-chain polyurethane (SPU)主鏈。反應性官能基azetidine-2,4-dione作為交聯點，使用不同側鏈接枝率導入精準合成的不同代數或鏈長之poly(urea/malonamide)側鏈及來調控聚氨酯的氫鍵物理交聯密度。製備出側鏈精準合成的氫鍵物理交聯聚氨酯系統，並比較樹枝狀和直線型側鏈對聚胺酯性質的影響。 由NMR、IR、EA、Mass及GPC分析，確認製備出精準控制分子量或鍊長的poly(urea/malonamide)聚合物，並由DSC分析的結果可知，樹枝狀及直線型poly(urea/malonamide)側鏈，隨著代數提升、氫鍵數量增加可觀察到玻璃轉移溫度的上升。 DMA觀察聚胺酯的機械性質及相轉移tanδ溫度，都因物理交聯密度的增加而提高。其中SPU-DG系列因樹枝狀側鏈本身氫鍵密度高，比直線型側鏈更有效提升了低溫的儲存模數；而SPU-LG系列的直線型側鏈在物理交聯補強聚胺酯機械性質的同時，還能保有明顯的相轉移峰。有別於SPU-DG系列，SPU-LG系列的儲存模數在相轉移區域之後有rubbery plateau region，提升了橡膠態的儲存模數。 利用Thermal mechanical test進行形狀記憶測試，發現SPU-DG系列聚氨酯具有良好的形狀固定率，但形狀回復效果普遍較差。而高代數側鏈的SPU-LG系列聚氨酯具備有良好的形狀固定率及形狀維持率。本研究的形狀記憶效果以S45-DG2.5-50、S45-DG2.5-25、S35-LG2.5-50、S45-LG2.5-50、S45-LG2.5-25和S45-LG3.5-50聚胺酯的效果最佳，形狀回復率和形狀固定率都維持在90%以上。 | zh_TW |
| dc.description.abstract | With precise synthetic control of hydrogen bond-rich side chains, shape memory polyurethanes (PUs) were prepared. These PUs comprising dendritic (DG series) or linear (LG series) polyurea/malonamide hydrogen bond-rich side chains with uniform chain lengths, providing physical crosslinking interactions to PUs. With the reactive functional group, azetidine-2,4-dione as the side chain of SPU to be a crosslinking site, different grafting ratios with various chain lengths of poly(urea/malonamides) were incorporated onto SPU. Consequently the physical crosslinking density could be adjusted.
Via NMR, IR, EA, Mass and GPC analysis, we were able to confirm that the precise control of the poly (urea/malonamide) chain lengths were obtained. Differential scanning calorimeter (DSC) showed that, with the increasing chain length of the dendritic or linear poly (urea/malonamide), the glass transition temperature rose as a result of increasing hydrogen bonding interactions. Cyclic thermal-mechanical tests were conducted for evaluating shape memory properties. A higher E'low value would make the movement of the polymer chains limited at low temperatures. Consequently the shape retention was enhanced. Moreover, a significant phase transition peak (tanδmax) and a broad rubbery plateau region would also help to improve shape recovery. Because of this, SPU-DG series exhibited excellent shape retention, but relatively poor shape recovery. On the other hand, the SPU-LG series with higher generation side chains exhibited excellent shape and shape retention. S45-DG2.5-50, S45-DG2.5-25, S35-LG2.5-50, S45-LG2.5-50, S45-LG2.5-25 and S45-LG3.5-50 exhibited excellent shape memory effect, with both shape recovery and shape retention higher than 90%. It is concluded that these well-defined PUs with excellent shape-memory effect have been successfully developed in this work. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T05:11:33Z (GMT). No. of bitstreams: 1 ntu-103-R01549016-1.pdf: 7809643 bytes, checksum: a3ce69b0b9234ebf811ca9ded7c98d65 (MD5) Previous issue date: 2014 | en |
| dc.description.tableofcontents | 摘要 I
Abstract II 目錄 III 圖目錄 VII 表目錄 XI 壹、緒論 1 貳、文獻回顧 2 2.1形狀記憶材料之簡介 2 2.1.1形狀記憶材料的原理14 3 2.1.2 高分子形狀記憶之來源12b 3 2.1.3熱感應型(thermo-responsive)形狀記憶高分子 4 2.2聚氨酯樹脂之簡介 7 2.2.1聚胺酯之原料及特性21 8 2.3規則樹枝狀分子(dendrimer)簡介 11 2.3.1 Dendrimer合成路徑 13 2.3.2規則樹枝狀衍生物 15 2.4超分子聚合物43 16 2.4.1氫鍵作用力誘導相分離 16 2.4.2熱可逆聚氨酯超分子 17 2.5形狀記憶高分子之應用 18 2.6研究動機 20 参、實驗內容 23 3.1藥品及溶劑 23 3.2實驗儀器 26 3.3實驗流程圖 27 3.4合成步驟 29 3.4.1 IDD之製備 29 3.4.2 反應型單體之合成 30 3.4.3 規則樹枝狀poly(urea/malonamide)聚合物之合成 31 3.4.4 直線型poly(urea/malonamide)聚合物之合成 35 3.4.5 含脂肪族一級胺官能基側鏈之合成 37 3.4.6 含反應官能基之聚胺酯材料 (SPU)之製備 38 3.4.7 側鏈物理交聯之聚胺酯材料之製備 39 3.4.8 側鏈物理交聯聚胺酯材料之接枝率 40 肆、結果與討論 41 4.1合成具反應選擇性單體IDD 41 4.2 DEA-diol之合成與鑑定 44 4.3 樹枝狀poly(urea/malonamide)聚合物之合成 (DG 系列) 46 4.3.1 [DG-0.5]-C18之合成與結構鑑定 46 4.3.2 [DG1]-C18之合成與結構鑑定 48 4.3.3 [DG1.5]-C18之合成與結構鑑定 50 4.3.4 [DG2]-C18之合成與結構鑑定 52 4.3.5 [DG-2.5]-C18之合成與結構鑑定 55 4.4 直線型poly(urea/malonamide)聚合物之合成 (LG 系列) 58 4.4.1 [LG1]-C18之合成與結構鑑定 58 4.4.2 [LG1.5]-C18之合成與結構鑑定 60 4.4.3 [LG2]-C18之合成與結構鑑定 62 4.4.4 [LG2.5]-C18之合成與結構鑑定 64 4.4.5 [LG3]-C18之合成與結構鑑定 66 4.4.6 [LG3.5]-C18之合成與結構鑑定 68 4.5 含脂肪族一級胺官能基側鏈之合成 70 4.5.1 A-[DG-0.5]-C18之合成與結構鑑定 70 4.5.2 A-[DG-1.5]-C18之合成與結構鑑定 72 4.5.3 A-[DG-2.5]-C18之合成與結構鑑定 73 4.5.4 A-[LG-1.5]-C18之合成與結構鑑定 74 4.5.5 A-[LG-2.5]-C18之合成與結構鑑定 76 4.5.6 A-[LG-3.5]-C18之合成與結構鑑定 77 4.6 樹枝狀與直線型poly(urea/malonamide) 聚合物之熱性質分析 79 4.6.1 樹枝狀與直線型poly(urea/malonamide)聚合物之TGA熱重分析 79 4.6.2 樹枝狀與直線型poly(urea/malonamide)聚合物之DSC微差掃描熱分析 80 4.7 側鏈物理性交聯之形狀記憶聚胺酯材料之製備 81 4.7.1 具側鏈反應型官能基聚氨酯主鏈之合成 (SPU) 81 4.7.2 側鏈樹枝狀物理交聯之形狀記憶聚氨酯合成 (SPU-DG系列) 82 4.7.3 側鏈直線型物理交聯之形狀記憶聚氨酯合成 (SPU-LG系列) 82 4.8聚胺酯之側鏈接枝率與FT-IR光譜之比較 85 4.8.1 聚胺酯之側鏈接枝率 85 4.8.2 聚胺酯FT-IR光譜之比較 86 4.9 側鏈物理性交聯聚氨酯之熱性質分析 89 4.9.1 TGA熱重分析 89 4.9.2 DSC微差掃描熱分析 90 4.10 側鏈物理性交聯聚氨酯之機械性質分析 95 4.11 側鏈物理性交聯聚氨酯之動態機械性質分析 (DMA) 99 4.11.1樹枝狀氫鍵物理交聯側鏈SPU-DG系列聚氨酯之儲存模數(E’) 99 4.11.2直線型氫鍵物理交聯側鏈SPU-LG系列聚氨酯之儲存模數(E’) 101 4.11.3樹枝狀氫鍵物理交聯側鏈SPU-DG系列聚氨酯之tanδ 102 4.11.4直線型氫鍵物理交聯側鏈SPU-LG系列聚氨酯之tanδ 103 4.11.5氫鍵物理交聯側鏈聚氨酯SPU-DG與SPU-LG系列之DMA分析結果之比較 105 4.12 側鏈物理性交聯聚氨酯形狀記憶測試 107 4.12.1 SPU-DG系列聚氨酯之形狀記憶測試 108 4.12.2 SPU-LG系列聚氨酯之形狀記憶測試 110 伍、結論 112 陸、參考文獻 114 附錄………………………………………………………………………………….119 | |
| dc.language.iso | zh-TW | |
| dc.title | 精準合成物理交聯型poly(urea/malonamide)側鏈之形狀記憶聚氨酯 | zh_TW |
| dc.title | Side-chain physically reinforced SMPUs via precise architectures control of poly(urea/malonamide) | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 102-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 蘇文?,林慶炫,李榮和,劉英麟 | |
| dc.subject.keyword | 物理交聯,形狀記憶,聚胺酯, | zh_TW |
| dc.subject.keyword | Physical crosslink,Shape memory,Polyurethane, | en |
| dc.relation.page | 121 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2014-08-19 | |
| 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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