環氧樹脂與含液化木材聚胺基甲酸酯樹脂之反應性及其硬化摻合樹脂之性質

The reactivity of epoxy resin with liquefied wood contained polyurethane resin and properties of their cured blended resins

本研究以重量混合比65/35之聚乙二醇／液化木材（Liquefied wood; LW）為多元醇原料，異氟爾酮二異氰酸酯為異氰酸酯原料，乙二胺／1,4-丁二醇為鏈延長劑合成具備NCO、NH及OH末端基之含液化木材聚胺基甲酸酯（LW contained polyurethane resins; LWPU）；另以雙酚A與環氧氯丙烷反應合成雙酚A型環氧樹脂（Epoxy resin; ER），並將ER樹脂與LWPU以重量比10/1混合調配ER/NCOLWPU、ER/NH-LWPU及ER/OH-LWPU三種摻合樹脂，探討ER/LWPU摻合樹脂之反應性及其硬化樹脂之機械性質、熱性質。由結果得知，ER樹脂可與LWPU發生架橋反應，其中以ER/NCO-LWPU 有較高反應性。而添加三乙基四胺（TETA）為架橋劑時，ER/LWPU摻合樹脂之高分子化主要透過ER 之環氧基與架橋劑之胺基進行開環聚合。三種ER/LWPU硬化摻合樹脂之機械強度比較，ER/NCOLWPU有較大之彎曲強度，較低之彈性模數。DMA熱分析結果顯示，ER/NH-LWPU及ER/OH-LWPU 硬化摻合樹脂內部存在兩相結構，而ER/NCO-LWPU則為同質結構，且其阻尼值波峰出現在較高溫側。TGA熱分析結果顯示ER/LWPU硬化摻合樹脂之熱裂解包含四個溫度階段，起始熱裂解溫度發生在264~272℃，其中ER/NH-LWPU之熱抵抗性優於其他兩種摻合樹脂。 In this study, polyethylene glycol/liquefied wood (LW) with a weight ratio of 65/35, isophorone diisocyanate and ethylenediamine/1,4-butanediol were used as the polyol, isocyanate and chain extender, respectively, to synthesize LW contained polyurethane resins (LWPU) with NCO, NH and OH end group. On the other hand, epoxy resin (ER) was synthesized by reacting bisphenol A with epichlorohydrin. The blended resins, named ER/NCO-LWPU, ER/NH-LWPU and ER/OH-LWPU were prepared by mixing ER and LWPU with a weight ratio of 10/1. The reactivity of the ER/LWPU blended resins and the mechanical and thermal properties of their cured resins were investigated. The results show that the crosslinking reaction can occur between ER and LWPU. Among which, ER/NCO-LWPU has the highest reactivity. When the triethylenetetramine (TETA) is added as a crosslinking agent, the polymerization of ER/LWPU blended resins is mainly through the ring-opening polymerization between epoxide groups of the ER and amine groups of the crosslinking reagent. Comparison of the mechanical strength of different ER/ LWPU blended resins, ER/NCO-LWPU has greater bending strength and lower elastic modulus than others. The result of DMA shows that a two-phase structure existed in ER/NH-LWPU and ER/OH-LWPU cured resins, while ER/NCO-LWPU has a homogeneous structure with the damping peak appearing at the higher temperature side. The result of TGA shows that the thermal degradation of ER/LWPU cured blended resins consists of four temperature stages. The initial thermal degradation occurred at temperature between 264℃ and 272℃. The thermal resistance of ER/NH-LWPU is better than that of the other two blended resins.