改質EPDM/Silica奈米複合材料的製備及特性研究

Preparation and Properties of Modified EPDM/Silica Nanocomposites

王學平(Shyue-pyng Wang)

指導教授 ： 石燕鳳

朝陽科技大學/理工學院/應用化學系/碩士(2009年)

摘要

本研究是一種新型的方法將溶膠凝膠(Sol-Gel)法導入有機高分子主體以形成有機─無機高分子複合材料。實驗首先利用馬來酸酐接枝在乙烯丙烯双烯橡膠(EPDM)上進行改質及探討馬來酸酐(MAH)的接枝率，並利用ethanolamine 、3-aminopropyltriethoxysilane 試劑進行合成聚亞醯胺(polyimide)，另外，在已具馬來酸酐接枝的EPDM 上加入丙三醇(Glycerine)行改質並做比較。再將這些已改質的EPDM 在酸催化下，將四乙基矽氧烷(TEOS)導入高分子主體上以形成奈米網狀結構的有機─無機高分子複合材料，並探討導入後之物理化學性質、微結構及熱性質變化。實驗結果由DSC 檢測分析可以得知使用過氧化二苯甲醯(benzyl peroxide,BPO)在EPDM接枝馬來酸酐時的反應溫度及時間控制在恆溫100℃反應達到1 小時後反應即完成。由FT-IR 檢測得知，在1784cm-1 有明顯接枝在主鏈上馬來酸酐的C=O 吸收峰，且其接枝率約為2.9%，另外本研究也探討改變馬來酸酐的接枝含量 5.9 及7.7%的接枝率之影響。而TEOS 導入後所形成的有機─無機高分子複合材料經FT-IR 檢測得知在1000~1100cm-1 有Si-O-Si 網狀結構的吸收峰。而由掃瞄式電子顯微鏡(SEM)觀察結果顯示無機氧化物均勻分散在有機高分子中，形成勻稱性的有機─無機混成材料。熱重分析(TGA)檢測顯示具無機氧化物網狀結構的高分子混成材料比有機高分子在10%的熱重量損失上均有較高的熱重損失溫度。利用固態NMR 鑑定無機在基材中形成網狀結構T2、T3 以及Q2、Q3、Q4 結構，另外利用計算積分面積來了解形成網狀結構各型態之比例。機械性質測試發現經導入無機材料時可以提高抗張強度，當添加比例達到5.7%時有最佳的抗張強度以及伸長率。

關鍵字

乙烯丙烯双醯橡膠 ； 馬來酸酐 ； 溶膠凝膠法 ； 聚亞醯胺

並列摘要

In this study, a novel approach to form the organic-inorganic polymeric materials has been prepared through the sol-gel process. First of all, ethylene propylene diene monomer (EPDM) was modified by grafting maleic anhydride (MAH) to the polymer backbone. Subsequently, ethanolamine or 3-aminopropyltriethoxysilane were added to form the imidized structure. Then the Tetraethylsiloxane (TEOS) was incorporated into these polymers to form
the organic-inorganic polymeric materials. And the physical properties, microstructure and thermal nature of these materials were investigated. The DSC analysis reveals that the EPDM-graft-MAH reaction using BPO as initiator is completed under 100℃ and 1 hour. The results of FT-IR show the degree of grafting of MAH can be detected by the C=O absorption peak of MAH at 1784 cm-1. Moreover, after incorporation of TEOS and forming the organic-inorganic polymer composite materials, the absorption peaks at 1000 ~ 1100 cm-1 (Si-O-Si network structure) have been found. Scanning electron microscopy (SEM) observation showed that inorganic oxide was well dispersed in the polymer matrix. Thermogravimetric analysis (TGA) showed that the 10% weight loss temperature of polymer composite materials was larger than that of pristine organic polymer. And solid-state NMR was utilized to identify the organic network structures are T2, T3, Q2, Q3 or Q4 forms. Moreover, the ratio of different form was calculated by the integral area. It is found that the tensile strength can be improved by incorporation of the inorganic materials, and when the MAH-grafting ratio was 5.7%, the best tensile strength and elongation were obtained.

並列關鍵字

EPDM ； Maleation ； Sol-Gel ； Polyimide

參考文獻

1. M. V. Duin, H. Dikland, Polym Deg and Stab, 92, 2287–2293 (2007).

2. N. Sombatsompop, C. Kumnuantip, J of Appl Polym Sci, Vol. 87,1723–1731 (2003).

6. V. A. Matonis, N. C. Small, Polym Eng Sci, 9, 100 (1969).

7. V. A. Matonis, N. C. Small, Polym Eng Sci, 9, 99 (1969).

10. X. F. Zhang, Y. Zhang, Z.L. Peng, J. Appl. Polym. Sci., 77, 2641 (2000).