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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 童世煌 | zh_TW |
dc.contributor.advisor | Shih-Huang Tung | en |
dc.contributor.author | 鍾旻潔 | zh_TW |
dc.contributor.author | Min-Chieh Chung | en |
dc.date.accessioned | 2024-03-04T16:15:27Z | - |
dc.date.available | 2024-03-05 | - |
dc.date.copyright | 2024-03-04 | - |
dc.date.issued | 2024 | - |
dc.date.submitted | 2024-02-05 | - |
dc.identifier.citation | 1.林哲增. 熱塑性聚酯彈性體綠色製程及應用. 2019. https://www.materialsnet.com.tw/DocView.aspx?id=42431.
2.Research, G. V. 熱塑性聚酯彈性體 (TPEE) 市場規模、佔有率、趨勢分析報告:按類型、最終用途、按地區、細分市場預測,2023-2030 年. 2023. https://www.gii.tw/report/grvi1376227-thermoplastic-polyester-elastomer-market-size.html. 3.Nagai, Y.; Ogawa, T.; Zhen, L. Y.; Nishimoto, Y.; Ohishi, F. Analysis of weathering of thermoplastic polyester elastomers .1. Polyether-polyester elastomers. Polym. Degrad. Stabil. 1997, 56 (1), 115-121. 4.Jiang, R.; Yao, S.; Chen, Y. C.; Liu, T.; Xu, Z. M.; Park, C. B.; Zhao, L. Effect of chain topological structure on the crystallization, rheological behavior and foamability of TPEE using supercritical CO2 as a blowing agent. J. Supercrit. Fluids 2019, 147, 48-58. 5.Jiang, R.; Chen, Y. C.; Yao, S.; Liu, T.; Xu, Z. M.; Park, C. B.; Zhao, L. Preparation and characterization of high melt strength thermoplastic polyester elastomer with different topological structure using a two-step functional group reaction. Polymer 2019, 179, 13. 6.Gabriëlse, W.; Soliman, M.; Dijkstra, K. Microstructure and phase behavior of block copoly(ether ester) thermoplastic elastomers. Macromolecules 2001, 34 (6), 1685-1693. 7.Yang, W.; Ma, L.; Song, L.; Hu, Y. Fabrication of thermoplastic polyester elastomer/layered zinc hydroxide nitrate nanocomposites with enhanced thermal, mechanical and combustion properties. Mater. Chem. Phys. 2013, 141 (1), 582-588. 8.Lee, T. Y.; Lee, C. H.; Cho, S.; Lee, D. H.; Yoon, K. B. Enhancement of physical properties of thermoplastic polyether-ester elastomer by reactive extrusion with chain extender. Polym. Bull. 2011, 66 (7), 979-990. 9.Zhou, W. D.; Zhang, Y. J.; Xu, Y.; Wang, P. L.; Gao, L.; Zhang, W.; Ji, J. H. Synthesis and characterization of bio-based poly(butylene furandicarboxylate)-b-poly(tetramethylene glycol) copolymers. Polym. Degrad. Stabil. 2014, 109, 21-26. 10.Buckley, C. P.; Prisacariu, C.; Martin, C. Elasticity and inelasticity of thermoplastic polyurethane elastomers: Sensitivity to chemical and physical structure. Polymer 2010, 51 (14), 3213-3224. 11.Kang, S. H.; Ku, D. C.; Lim, J. H.; Yang, Y. K.; Kwalk, N. S.; Hwang, T. S. Characterization for pyrolysis of thermoplastic polyurethane by thermal analyses. Macromol. Res. 2005, 13 (3), 212-217. 12.Ojha, U.; Kulkarni, P.; Faust, R. Syntheses and characterization of novel biostable polyisobutylene based thermoplastic polyurethanes. Polymer 2009, 50 (15), 3448-3457. 13.Fasce, L. A.; Pettarin, V.; Marano, C.; Rink, M.; Frontini, P. M. Biaxial yielding of polypropylene/elastomeric polyolefin blends: Effect of elastomer content and thermal annealing. Polym. Eng. Sci. 2008, 48 (7), 1414-1423. 14.Lee, H. y.; Kim, D. H.; Son, Y. Effect of octene content in poly (ethylene‐co‐1‐octene) on the properties of poly (propylene)/poly (ethylene‐co‐1‐octene) blends. J. Appl. Polym. Sci. 2007, 103 (2), 1133-1139. 15.Mohite, A. S.; Rajpurkar, Y. D.; More, A. P. Bridging the gap between rubbers and plastics: a review on thermoplastic polyolefin elastomers. Polym. Bull. 2022, 1-35. 16.Bhattacharya, A. B.; Chatterjee, T.; Naskar, K. Automotive applications of thermoplastic vulcanizates. J. Appl. Polym. Sci. 2020, 137 (27), 19. 17.Ghahramani, N.; Iyer, K. A.; Doufas, A. K.; Hatzikiriakos, S. G. Rheology of thermoplastic vulcanizates (TPVs). J. Rheol. 2020, 64 (6), 1325-1341. 18.Maji, P.; Naskar, K. Styrenic block copolymer-based thermoplastic elastomers in smart applications: Advances in synthesis, microstructure, and structure-property relationships-A review. J. Appl. Polym. Sci. 2022, 139 (39), 21. 19.Yang, J. P.; Germack, D. S.; Spontak, R. J. Characterization of controlled-distribution hydrogenated styrenic block copolymers by nuclear magnetic resonance spectroscopy. ACS Appl. Polym. Mater. 2023, 5 (8), 6003-6011. 20.Gong, S.; Zhao, S.; Chen, X.; Liu, H.; Deng, J.; Li, S.; Feng, X.; Li, Y.; Wu, X.; Pan, K. Thermoplastic polyamide elastomers: Synthesis, structures/properties, and applications. Macromol. Mater. Eng. 2021, 306 (12), 2100568. 21.Fu, X. B.; Zhang, T.; Yang, J. C.; Zhang, G.; Zhang, M. L.; Wang, X. J.; Yang, J. Structures and properties of newly synthesized semi-aromatic polyamide thermoplastic elastomers. Polym. Chem. 2022, 13 (34), 4980-4991. 22.Deleens, G.; Foy, P.; Maréchal, E. Synthese et caracterisation de copolycondensats sequences poly (amide-seq-ether)—I. Synthese et etude de divers oligomeres ω, ω'difonctionnels du poly (amide-11). Eur. Polym. J. 1977, 13 (5), 337-342. 23.Wang, Y. Q.; Wang, X. D.; Du, Z. J.; Mi, J. G.; Zhang, C. Evolution of cell morphology from sub-macroscale to nanoscale in modified thermoplastic polyether ester elastomer via supercritical CO2 foaming. J. Supercrit. Fluids 2021, 171, 11. 24.Coleman, D. Block Copolymers - Copolymerization of ethylene terephthalate and polyoxyethylene glycols. J. Polym. Sci. 1954, 14 (73), 15-28. 25.Mao, H. I.; Chen, C. W.; Rwei, S. P. Synthesis and nonisothermal crystallization kinetics of poly(butylene terephthalate-co-tetramethylene ether glycol) copolyesters. Polymers 2020, 12 (9), 20. 26.塑膠薄膜材料網-寰宇尖端薄膜有限公司. 3分鐘了解什麼是熱塑性彈性體(TPE). 2023. http://www.film-top1.com/product-info.asp?id=662. 27.Lu, J. W.; Zhang, H.; Chen, Y. M.; Ge, Y. K.; Liu, T. Mechanical and rheological properties and CO2-foaming behavior of reactively modified TPEE with controlled chain entanglement. J. CO2 Util. 2022, 62, 11. 28.Härth, M.; Kaschta, J.; Schubert, D. W. Shear and elongational flow properties of long-chain branched poly(ethylene terephthalates) and correlations to their molecular structure. Macromolecules 2014, 47 (13), 4471-4478. 29.Chen, J. X.; Lv, Q. L.; Wu, D. F.; Yao, X.; Wang, J.; Li, Z. S. Nucleation of a thermoplastic polyester elastomer controlled by silica nanoparticles. Ind. Eng. Chem. Res. 2016, 55 (18), 5279-5286. 30.Huang, J.; Qiu, Y. X.; Wu, D. F.; Wang, J. New way to tailor thermal stability and mechanical properties of thermoplastic polyester elastomer: relations between interfacial structure and surface treatment of spodumene slag. Ind. Eng. Chem. Res. 2017, 56 (21), 6239-6246. 31.Qiu, Y. X.; Wu, D. F.; Xie, W. Y.; Wang, Z. F.; Peng, S. Thermoplastic polyester elastomer composites containing two types of filler particles with different dimensions: Structure design and mechanical property control. Compos. Struct. 2018, 197, 21-27. 32.Lee, I. J.; Choi, S. W.; Kim, H. T.; Kim, J. H.; Baik, D. H. Preparation and characterization of high molecular weight thermoplastic polyetherester elastomers using chain extender. Fiber. Polym. 2021, 22 (11), 2947-2953. 33.Yu, L. L.; Yu, Z.; Yang, L. J.; Wen, S. B.; Zhang, Z. X. Development of thermoplastic polyether ester elastomer microcellular foam with high resilience: Effect of chain extension on foaming behavior and mechanical properties. J. Appl. Polym. Sci. 2023, 140 (22), 9. 34.Zhi‐Lian, T.; Gao, Q.; Nan‐Xun, H.; Sironi, C. Solid‐state polycondensation of poly (ethylene terephthalate): Kinetics and mechanism. J. Appl. Polym. Sci. 1995, 57 (4), 473-485. 35.Cruz, S. A.; Zanin, M. PET recycling: Evaluation of the solid state polymerization process. J. Appl. Polym. Sci. 2006, 99 (5), 2117-2123. 36.Kim, T. Y.; Lofgren, E. A.; Jabarin, S. A. Solid-state polymerization of poly(ethylene terephthalate). I. Experimental study of the reaction kinetics and properties. J. Appl. Polym. Sci. 2003, 89 (1), 197-212. 37.Ma, Y.; Agarwal, U. S.; Sikkema, D. J.; Lemstra, P. J. Solid-state polymerization of PET: influence of nitrogen sweep and high vacuum. Polymer 2003, 44 (15), 4085-4096. 38.Yan, H.; Yuan, H.; Gao, F.; Zhao, L.; Liu, T. Modification of poly (ethylene terephthalate) by combination of reactive extrusion and followed solid‐state polycondensation for melt foaming. J. Appl. Polym. Sci. 2015, 132 (44). 39.童世煌. 高分子固態物理課堂講義. 2022. 40.Jeon, S. H.; Jeong, J. E.; Kim, S.; Jeon, S.; Choung, J. W.; Kim, I. Hardness modulated thermoplastic poly(ether ester) elastomers for the automobile weather-strip application. Polymers 2021, 13 (4), 14. 41.Kwiatkowska, M.; Kowalczyk, I.; Rozwadowski, Z.; Piesowicz, E.; Szymczyk, A. Hytrel-like copolymers based on furan polyester: The effect of poly (butylene furanoate) segment on microstructure and mechanical/elastic performance. Molecules 2023, 28 (7), 2962. 42.Parra, D. F.; Marchini, L. G.; Komatsu, L. G. H.; de Oliveira, C. B.; Oliani, W. L.; Rangari, V. K. AgNPs@ ZnO hybride nanoparticles infused thermoplastic polyester elastomer and their biocide effect. SN Appl. Sci. 2021, 3, 1-13. 43.Bourg, V.; Valette, R.; Le Moigne, N.; Ienny, P.; Guillard, V.; Bergeret, A. Shear and extensional rheology of linear and branched polybutylene succinate blends. Polymers 2021, 13 (4), 18. 44.Stange, J.; Uhl, C.; Münstedt, H. Rheological behavior of blends from a linear and a long-chain branched polypropylene. J. Rheol. 2005, 49 (5), 1059-1079. 45.Ge, Y. K.; Yao, S.; Xu, M. L.; Gao, L.; Fang, Z. Y.; Zhao, L.; Liu, T. Improvement of poly(ethylene terephthalate) melt-foamability by long-chain branching with the combination of pyromellitic dianhydride and triglycidyl isocyanurate. Ind. Eng. Chem. Res. 2019, 58 (9), 3666-3678. 46.Khabaz, F.; Khare, R. Effect of chain architecture on the size, shape, and intrinsic viscosity of chains in polymer solutions: A molecular simulation study. J. Chem. Phys. 2014, 141 (21), 10. 47.Nébouy, M.; de Almeida, A.; Brottet, S. n.; Baeza, G. P. Process-oriented structure tuning of PBT/PTHF thermoplastic elastomers. Macromolecules 2018, 51 (16), 6291-6302. | - |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/92044 | - |
dc.description.abstract | 熱塑性聚酯彈性體(Thermoplastic Polyester Elastomer, TPEE)是由聚酯硬鏈段與聚醚軟鏈段連接成的嵌段共聚物,結合了熱固性橡膠的彈性特質及熱塑性高分子在高溫下易加工的特性。然而,商用TPEE因為其分子量較低的線性結構及較窄的分子量分佈,造成熔融強度低或彈性不足的問題,不利於紡絲、吹塑、發泡製程。
本研究中以混煉法混摻異氰尿酸三縮水甘油酯(Tris(2,3-epoxypropyl) isocyanurate, TGIC)、Joncryl®ADR擴鏈劑(ADR)或均苯四甲酸二酐(pyromellitic dianhydride, PMDA),以提高TPEE的分子量及支化程度,藉此提升TPEE的流變性質,為了避免高溫下長時間改質發生副反應或熱降解,後續將固態聚合法作為混煉的附加製程,讓尚具有反應活性的末端基與添加劑能夠在相對低溫與真空的環境下繼續反應。 實驗數據顯示,添加ADR 1 phr為提高TPEE流變性質的最佳改質條件,熔融態流變分析表明,改質後的TPEE流變儲存模數及剪切黏度分別較原料提高1.1倍及1.8倍,並發現有支化結構的剪切致稀現象,經過固態聚合後,流變儲存模數及剪切黏度更是提高至母粒的2.4倍及49.4倍,也有更加明顯的剪切致稀現象。此外,較寬的分子量分佈及較低的本質黏度可以證實添加ADR擴鏈劑能形成一些分子量較高的支化結構,再透過固態聚合讓樣品進一步發生反應使分支結構含量上升,因而提高流變性質。後續進行了TPEE經過改質後的結晶性質、微結構與機械性質分析,同時探討了二次加工可行性。 | zh_TW |
dc.description.abstract | Thermoplastic Polyester Elastomer (TPEE) is a copolymer comprised of polyester as hard segments and polyether as soft segments. TPEEs combine the elastic characteristics of thermosetting rubber with the processability of thermoplastic polymers at elevated temperatures. However, commercial TPEE faces challenges such as low melt strength and insufficient elasticity due to its linear structure with low molecular weight and relatively narrow molecular weight distribution, which hinders its suitability for processes like spinning, blow molding, or foaming.
In this study, compounding was employed to blend TPEE with chain extender, namely Tris(2,3-epoxypropyl) isocyanurate (TGIC), Joncryl® ADR (ADR), and pyromellitic dianhydride (PMDA). The aim was to enhance the molecular weight and branching structure of TPEE, thereby improving its rheology properties. To avoid the possibility of side reactions or thermal degradation during high-temperature reactions, subsequent solid-state polymerization (SSP) was utilized as an additional processing step. SSP enables reactive end groups and additives to continue reacting under relatively low-temperature and vacuum conditions. The experimental results revealed that the addition of 1 phr ADR was the optimal modification condition for enhancing the rheology properties of TPEE. Rheological analysis in the melt state indicated that the modified TPEE exhibited a 1.1 times increase in rheological storage modulus and a 1.8 times increase in shear viscosity compared to the pristine material. Moreover, shear-thinning indicative of a branching structure was observed. After solid-state polymerization, the rheological storage modulus and shear viscosity further increased to 2.4 times and 49.4 times that of the pristine material, respectively, accompanied by more pronounced shear-thinning behavior. Besides, the higher value of polydispersity index (PDI) and the lower intrinsic viscosity also prove that the addition of ADR chain extender facilitates the formation of higher molecular weight branched structures. Furthermore, through solid-state polymerization, the sample undergoes additional reactions leading to an increased content of branched structures, thereby enhancing its rheological properties.Subsequent analyses included the crystalline properties, microstructure, mechanical properties of modified TPEE, and its feasibility for secondary processing were also investgated. | en |
dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2024-03-04T16:15:27Z No. of bitstreams: 0 | en |
dc.description.provenance | Made available in DSpace on 2024-03-04T16:15:27Z (GMT). No. of bitstreams: 0 | en |
dc.description.tableofcontents | 口試委員會審定書 i
誌謝 ii 摘要 iii Abstract iv 目錄 vi 圖目錄 ix 表目錄 xiv 第一章 前言及研究動機 1 第二章 文獻回顧 3 2.1熱塑性彈性體 (Thermoplastic elastomer, TPE) 3 1.熱塑性聚氨酯(Thermo Polyurethane, TPU): 4 2.聚烯系彈性體(Thermoplastic Olefin, TPO): 5 3.動態加硫聚烯彈性體(Thermoplastic Vulcanizate, TPV): 5 4.聚苯乙烯系彈性體(Thermoplastic Styrenic Elastomer, TPS/TPR): 6 5.聚醯胺系彈性體(Thermoplastic Polyamide Elastomer, TPAE): 6 6.熱塑性聚酯彈性體(Thermoplastic Polyester Elastomer, TPEE): 7 2.2加入添加劑增加TPEE熔體強度 12 2.2.1 無機填充材 12 i.奈米二氧化矽(nanosilica) 12 ii.礦渣(Slag) 13 2.2.2 添加鏈延長劑 14 i.二異氰酸二苯甲烷(Methylene diphenyl diisocyanate, MDI) 14 ii.2,2'-雙(2-噁唑啉)(2,2'-bis(2-oxazoline), 2,2'-BOZ) 15 2.2.3 添加鏈分支劑 15 i.異氰尿酸三縮水甘油酯 (Tris(2,3-epoxypropyl) isocyanurate, TGIC) 15 ii.擴鏈劑(Joncryl® ADR) 17 2.3固態聚合(Solid-state polymerization, SSP) 18 2.3.1 固態聚合機制 18 2.3.2 影響固態聚合反應動力學的因素 19 2.3.3 利用固態聚合法提高分子量及流變性質 21 第三章 實驗方法與器材 22 3.1實驗藥品 22 1. 熱塑性聚酯彈性體 (Thermoplastic polyester elastomer, TPEE) 22 2. 異氰尿酸三縮水甘油酯 (Tris(2,3-epoxypropyl) isocyanurate, TGIC) 22 3. 擴鏈劑 (Epoxy ) 23 4. 均苯四甲酸二酐(pyromellitic dianhydride, PMDA) 23 5. 六氟異丙醇(hexafluoro-2-propanol, HFIP) 23 6. 苯酚(phenol) 24 7. 1,1,2,2-四氯乙烷(1,1,2,2-Tetrachloroethane) 24 3.2實驗樣品製備流程 25 3.2.1 混煉法樣品製備(Micro-compounding, MC) 25 3.2.2 固態聚合(Solid-state polymerization, SSP) 26 3.2.3 樣品命名規則 26 3.3實驗儀器與參數設定 26 3.3.1 熱重分析儀 (Thermogravimetric analysis, TGA) 26 3.3.2 示差掃描熱量分析儀 (Differential scanning calorimetry, DSC) 27 3.3.3 熱壓成型機 (Hot-pressing) 27 3.3.4 微量雙螺桿混煉機 (Micro twin screw compounder) 28 3.3.5 流變儀 (Rheometer) 29 3.3.6 動態機械分析儀 (Dynamic mechanical analysis, DMA) 31 3.3.7 小角及廣角X光散射 (Small/Wide angle X-ray scattering, SAXS/WAXS) 33 3.3.8 尺寸排除色譜法(Size-exclusion chromatography, SEC) 34 3.3.9 奧士瓦黏度計(Ostwald Viscometer) 35 3.3.10 全反射式衰減紅外光譜儀 (Attenuated total reflection infared spectroscopy, ATR-IR) 38 3.3.11 偏光顯微鏡 (Polarized optical microscope, POM) 38 第四章 結果與討論 39 4.1全反射式衰減紅外光譜儀 (ATR-IR)結構與組成分析 39 4.1.1 TPEE組成分析 39 4.1.2 反應機制與結構圖 40 4.1.3 TPEE/ADR樣品分析 41 4.1.4 TPEE/TGIC樣品分析 41 4.1.5 TPEE/PMDA樣品分析 41 4.2熔融態流變性質分析 45 4.2.1 TPEE振幅掃描 45 4.2.2 TPEE/ADR 頻率掃描測試 46 4.2.3 TPEE/ADR穩態黏度測試 49 4.2.4 TPEE/TGIC頻率掃描測試 51 4.2.5 TPEE/TGIC穩態黏度測試 55 4.2.6 TPEE/PMDA頻率掃描測試 57 4.2.7 TPEE/PMDA穩態黏度測試 60 4.3毛細管黏度計本質黏度與SEC分子量分析 62 4.3.1 TPEE本質黏度及分子量分析 62 4.3.2 TPEE/ADR本質黏度及分子量分析 64 4.3.3 TPEE/TGIC本質黏度及分子量分析 67 4.4DMA動態溫度掃描對Tg的分析 70 4.4.1 TPEE/ADR動態溫度掃描分析 70 4.4.2 TPEE/TGIC動態溫度掃描分析 71 4.5熱性質分析 72 4.5.1 TPEE熱重損失分析 72 4.5.2 TPEE混煉前後的DSC分析 72 4.5.3 TPEE/ADR的DSC分析 72 4.5.4 TPEE/TGIC的DSC分析 74 4.6偏光顯微鏡 (POM) 76 4.6.1 TPEE的POM圖形 76 4.6.2 TPEE/ADR的POM圖形 76 4.6.3 TPEE/TGIC的POM圖形 78 4.7SAXS/WAXS分析 79 4.7.1 TPEE/ADR的SAXS結構分析 80 4.7.2 TPEE/ADR的WAXS結晶分析 82 4.7.3 TPEE/TGIC的SAXS結構分析 83 4.7.4 TPEE/TGIC的WAXS結晶分析 84 4.8改質TPEE機械性質分析 86 4.8.1 TPEE/ADR蠕變回復分析 86 4.8.2 TPEE/TGIC蠕變回復分析 88 4.9二次加工後熔融流變性質分析 90 第五章 結論 92 第六章 參考資料 94 附錄 100 一、FTIR 100 二、熔融態流變暫態黏度測試 101 三、DSC 104 四、SAXS/WAXS 108 五、DMA 113 | - |
dc.language.iso | zh_TW | - |
dc.title | 利用擴鏈劑及固態聚合法改質對熱塑性聚酯彈性體分子量與流變性質的影響 | zh_TW |
dc.title | Effects of Chain Extenders and Solid-State Polymerization on the Molecular Weight and Rheological Properties of Thermoplastic Polyester Elastomer | en |
dc.type | Thesis | - |
dc.date.schoolyear | 112-1 | - |
dc.description.degree | 碩士 | - |
dc.contributor.oralexamcommittee | 邱文英;鄭如忠;陳錦文 | zh_TW |
dc.contributor.oralexamcommittee | Wen-Yen Chiu;Ru-Jong Jeng;Chin-Wen Chen | en |
dc.subject.keyword | 熱塑性聚酯彈性體(TPEE),擴鏈劑,混煉,固態聚合,流變, | zh_TW |
dc.subject.keyword | Thermoplastic Polyester Elastomer (TPEE),Chain extender,Compouding,Solid-state polymerization (SSP),Rheology, | en |
dc.relation.page | 117 | - |
dc.identifier.doi | 10.6342/NTU202400301 | - |
dc.rights.note | 同意授權(全球公開) | - |
dc.date.accepted | 2024-02-06 | - |
dc.contributor.author-college | 工學院 | - |
dc.contributor.author-dept | 高分子科學與工程學研究所 | - |
顯示於系所單位: | 高分子科學與工程學研究所 |
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