臺灣博碩士論文加值系統

聚異戊二烯 (Polyisoprene, PI) 為天然橡膠的主要成分，是一種重要的彈性體材料，具有良好的抗疲勞性、生物相容性和經濟效益。為了防止材料在長時間使用後磨損或裂紋所造成之安全問題，在過去幾年中，許多研究致力於新型軟材料的自愈化學。針對目前自修復天然橡膠的論文中，離子鍵的引入是實現橡膠自愈行為的常用方法之一。然而，這些研究往往需要較為複雜的改性方法或者改質過程中含有金屬離子。因此，在本文中，我們展示了一種簡單且環保的合成方法，可通過一步驟反應合成自修復橡膠。藉由 L-半胱氨酸 (L-cysteine, LC) 結構中之胺基與羧基，透過-NH2基團、C=O基團與-OH基團產生氫鍵作用力，以達到自修復目的。此外，LC可由動物的毛髮或蹄進一步提取而得，為環境友善之原物料。LC單體藉由小的空間立體與PI形成強氫鍵相互作用力，並達到動態交聯，並藉由PI固有的可拉伸性，形成彈性體。在此我們藉由LC之-SH基團與PI之雙鍵結構 進行硫醇-烯反應，通過不同 LC 重量與聚合物中雙鍵數量的比率，從而合成了 PI-LC-X（X = 10、30 和 50），並研究其聚合物結構、熱性能和機械性能，同時探討氫鍵對於該材料之熱物性質影響。其中PI-LC-30具有較強之應力以及好的聚合物鏈流動性，有助於材料在室溫下之自修復行為。

Polyisoprene (PI), a primary ingredient of natural rubber, is a critical class of elastomer materials with good fatigue resistance, biocompatibility, and economic benefits. However, to prevent the material from wearing out or cracking after a long time of use, a tremendous effort has been made to self-healing chemistry in the last few years for novel soft materials. In the current papers on self-healing natural rubber, the introduction of ionic bonds is one of the common methods to achieve the self-healing behavior of rubber. However, there are usually difficult modification methodologies or containing metal ions. In this study, we demonstrate a simple and eco-friendly synthetic method to synthesize self-healing rubber through a one-step reaction. Through the amine group and carboxyl group in the L-cysteine (LC) structure, the hydrogen bonding force is generated by the -NH2 group, C=O group and -OH group to achieve self-healing. In addition, LC can be further extracted from animal hair or hooves and is an environmentally friendly raw material. The LC monomer forms a strong hydrogen bond interaction force with PI through a small three-dimensional structure, realizes dynamic cross-linking, and forms an elastomer through the inherent stretchability of PI. In this study, we conduct a thiol-ene reaction through the -SH group of LC and the double bond structure of PI, through the ratio of different LC weights to the number of double bonds in the polymer, PI-LC-X (X = 10, 30, and 50), were thus synthesized. We investigate the structural, thermal, and mechanical properties of the PI-LC, and discuss the effect of hydrogen bonding on material properties. In particular, PI-LC-30 film has strong stress and retains the fluidity of the polymer chain, which helps the material to self-healing at room temperature.

中文摘要 I
Abstract II
Table Captions V
Figure Captions VI
Chapter 1 Introduction 10
Chapter 2 Basic Theory and Literature Review 15
2.1 Properties and Applications of Polyisoprene 15
2.1.1 Elastic properties 15
2.1.2 Applications of Polyisoprene 15
2.1.3 Application of isoprene oligomers 17
2.2 Self-healing behavior 19
2.2.1 Overview of Self-Healing chemisty 20
2.2.2 Example of Self-healing Polyisoprene 22
2.2.2.1 Self-healing using disulfide/polysulfide bonds 22
2.2.2.2 Self-healing by epoxy natural rubber blended ionomer 24
2.2.2.3 Self-healing behavior by hydrogen bonding or ionic bonding 24
2.2.2.4 Self-healing behavior by hydrogen bonding 27
2.3 Thiol-ene Reaction 28
2.4 Hydrogen bonding option 30
2.4.1 Introduction of hydrogen bonding in supramolecular chemistry 31
2.4.2 Self-healing moiety selection 32
Chapter 3 Experimental Section 35
3.1 Experimental Materials 35
3.2 Instrument 36
3.3 Experimental Method 36
3.3.1 Synthesis Flow Chart of PI-LC elastomer 36
3.3.2 Synthesis of the PI-LC 37
3.3.3 Preparation of PF-LC thin films 37
3.4 Analyze Experimental Methods 38
3.4.1 Structural Identification 38
3.4.2 Material Analysis 38
3.4.3 Self-Healing Property Analysis 39
3.4.4 Rheological Measurements 39
Chapter 4 Results and Discussion 40
4.1 Synthesis and Identification of PI-LC 40
4.2 Material Mechanical Property and Rheology Analysis 45
4.3 Thermal Properties Analysis and hydrogen bond characteristics 47
4.4 Self-healing Studies and Analysis of Self-Healing Surface Morphology 55
4.5 Material Tear-resistant Test and Cyclic tensile tests 59
Chapter 5 Conclusion 63
Chapter 6 Future Work 64
6.1 Synthesis Strategy 64
6.1.1 Synthesis of sugar-based thiols 64
6.1.2 Synthesis and material characterization of sugar-based polyisoprene 66
Chapter 7 Reference 67

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