含丁二炔基－聚氨基甲酸酯合成與衰解特性

Synthesis and Characteristics of Degradation of Diacetylene Group-Containing Polyurethane

莊富盛(F. S. Chuang) ； 許耀基(Y. C. Shu) ； 曾雯卿(W. C. Tsen)

《界面科學會誌》 28卷3期 (2006/09) Pp. 119-134

https://doi.org/10.30020/JCCIS.200609.0001

摘要

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。

關鍵字

聚氨基甲酸酯 ； 丁二炔基團 ； 衰解 ； 熱重分析

並列摘要

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.

並列關鍵字

polyurethane ； diacetylene group ； degradation ； thermogravimetry analysis (TGA)