篇名 | 含丁二炔基-聚氨基甲酸酯合成與衰解特性 |
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卷期 | 28:3 |
並列篇名 | Synthesis and Characteristics of Degradation of Diacetylene Group-Containing Polyurethane |
作者 | 莊富盛 、 許耀基 、 曾雯卿 |
頁次 | 119-134 |
關鍵字 | 聚氨基甲酸酯 、 丁二炔基團 、 衰解 、 熱重分析 、 Polyurethane 、 Diacetylene group 、 Degradation 、 Thermogravimetry analysis 、 TGA |
出刊日期 | 200609 |
本研究主要目的為以預聚合體法合成含丁二炔基之聚氨基甲酸酯(PU-DA)共聚合體, 並探討其衰解特性。研究中,採用2,4-丁二炔-1,6 己二醇(2,4-DA)、聚丁醚二醇(PTMG)與4,4’-二苯甲基二異氰酸酯(MDI)反應,以形成不同組成的PU-DA 共聚合體。在熱重分析上, PU-DA 共聚合體出現兩個明顯的衰解階段,雖然與一般的聚氨基甲酸酯(PU)相似,然而由TG-DTG 結合TG-IR 與TG-DSC 的結果, 分析衰解過程吸放熱與裂解產生CO2 出現的溫度範圍, 可發現由於PU-DA 共聚合體其硬鏈節具有局部交叉聚合反應的網絡,因此第一衰解階段的穩定性高於PU。此外,由於PU-DA 之硬鏈節的局部交叉聚合, 故延緩裂第二衰解階段。隨後PU-DA 於高溫下產生裂解自由基交聯與再裂解, 故PU-DA第二衰解階段出現高於PU 之最大失重速率溫度與失重量,以及低於PU 的最大失重速率。此外,PU-DA 的熱重曲線隨2,4-DA 含量往高溫移動, 也說明硬鏈節產生了局部交叉聚合反應在熱衰解上穩定化的效應。這些PU-DA 共聚合體之兩階段的衰解特性及特性衰解溫度的裂解機構,藉由TG-IR與TG-DSC 分析提出於文中。
Aim of this study is to synthesize the diacetylene group-containing polyurethane(PU-DA) copolymers, which consist of 2,4-Hexamethylene- 1,6-diol(2,4-DA), 4,4’diphenylmethane diisocyanate(MDI) and polytetramethylene glycol(PTMG), by a pre-polymerization method and investigate the characteristics of degradation of the copolymers. The thermogravimetry analysis (TGA) of various PU-DA copolymers clearly exhibited two stages of degradation that agree with typical polyurethane(PU) but the stability of the first stage of degradation for the PU-DA copolymers exceed PU due to the hard segmented network resulting from topochemical solid-state polymerization. The facts were coming from those data of endotherm, exdotherm and carbon dioxide resulting from the analysis of TG-DTG that combine with the analysis of TG-IR and TG-DSC in the process of degradation. Because the degradation of hard segment of PU-DA occurred the cross-polymerization in the first stage of degradation, the second stage of degradation is postponed. Subsequently, the radical segments of decompostion yield the crosslinkage and re-decomposition. The second stage of degradation for PU-DA copolymers has higher the maximum temperature and weight loss than PU, and has a lower rate of weight loss. Furthermore, as the 2,4-DA content increase, the TG curves of PU-DA copolymers are shifted to higher the temperature regions. The event is also illustrating the fact of thermal ability of degradation for the effect of topochemical solid-state polymerization. The characteristics of degradation and mechanisms of degradation on the first and second stage of degradation were demonstrated by the analysis of TG-IR and TG-DSC.