Preparation and properties of epoxy/polyurethane composites containing biomass

本研究將柳杉 (Cryptomeria japonica) 木材以酚/雙酚A混合液及聚乙二醇/丙三醇混合液為溶劑進行液化處理得兩種液化木材 (Liquefied wood; LW)。環氧樹脂 (Epoxy resins; ER) 合成時利用雙酚A及酚/雙酚A液化柳杉與環氧氯丙烷反應合成雙酚A型 (ER) 及液化柳杉型 (LWER) 兩種ER樹脂，並探討兩種ER樹脂在不同三乙基四胺 (Triethylenetetramine; TETA) 添加量條件反應性及硬化樹脂性質。聚胺基甲酸酯樹脂 (Polyurethane resins; PU) 合成時以聚乙二醇及聚乙二醇/丙三醇液化柳杉為多元醇原料，異氟爾酮二異氰酸酯 (Isophorone diisocyanate; IPDI) 為異氰酸酯原料，1,4-丁二醇(1,4-BD)及乙二胺(EDA)為鏈延長劑合成不同末端基(-NH, -OH, -NCO)之PU及LWPU樹脂。進一步將不同種類ER樹脂與不同末端基PU樹脂以不同重量比混合製備聚摻合樹脂(ER/PU)，探討不同條件聚摻合樹脂之反應性及硬化樹脂之性質。由試驗結果顯示，ER樹脂添加TETA後之反應性大於LWER樹脂，其中ER樹脂及LWER樹脂分別在環氧基當量/胺當量1/1及1/0.9時有較佳之反應性。不同末端基PU樹脂性質比較，以1,4-丁二醇對PU樹脂分子鏈之延長效果優於乙二胺，其合成樹脂之分子量較大，NH-PU樹脂之分子鏈具備尿素結構，並存在局部架橋構造，LW可提高PU樹脂之熱抵抗性。ER/PU聚摻合樹脂之DSC分析顯示，ER樹脂可與三種末端基PU樹脂發生架橋反應，其中以NCO-PU之反應較為明顯，添加TETA可促進並參與其架橋反應。以ER樹脂為主之硬化ER/PU聚摻合樹脂之性質分析顯示，添加PU樹脂可降低ER樹脂之剛性，提高LWER樹脂之機械強度，添加LWPU可提高ER樹脂之熱抵抗性。而以PU為主之PU/ER聚摻合樹脂之性質分析顯示，於PU樹脂中添加ER樹脂可獲得較佳之拉伸強度，然隨ER樹脂添加量增加，其斷裂伸長率下降。添加ER樹脂可提高OH-PU之Tg溫度，增加NH-PU之熱穩定性。In this study, Cryptomeria japonica(Japanese cedar) were liquefied with polyethylene(PEG)/glycerol and phenol/bisphenol A as the solvent. Two type epoxy resins were synthesized by bisphenol A and phenol/bisphenol A liqueied Cryptomeria japonica which reacted with epichlorohydrin. To explore two kinds of ER resins reaction and properties with added different triethylenetetramine (TETA) ratios. Polyurethane resins(PU) used polyethylene(PEG) and polyethylene(PEG)/glycerol liqueied Cryptomeria japonica as polyol which reactived with isophorone diisocyanate(IPDI),which used 1,4-Butanediol(1,4-BD) and Ethylenediamine(EDA) as chain extender to synthesize PU containing different terminated groups. Further,blended ER resins with differents PU resins had different ratios then investigated reactivity of two resin and properties of ER/PU curing resins.In the result, ER had better reactivity by adding TETA.ER resin and LWER resin had best reactivity when TETA added with epoxy equivalent / amine equivalent ratios was 1/1 and 1/0.9.Compared with PU resins containing different terminated groups,1,4-BD had better chain-extending than EDA,which had higher molecular weight. PU resins used EDA as chain-extender had urea structure and partial bridge structure.Used polyethylene(PEG)/glycerol liqueied Cryptomeria japonica as polyol with raw can improve PU resin's thermal resistance. In ER/PU blended resins, ER can reacted with PU containing three different terminated groups that NCO-PU had obvious reactivity ,and added TETA can improve the crosslinking reaction. In ER/PU curing resins,ER resins added PU resins could reduce the rigidity of ER resin and improved mechanical properties of LWER resin, added LWPU resins can improve ER resins thermal resistance.In PU / ER blended resin,PU resin added ER resin had better tensile strength,when the amount of the increase of ER resin the breaking elongation was decreased.Added ER resins in PU resins could increase the Tg of the OH-PU resins, increase the thermal stability of the NH-PU resins.目錄 摘要……………………………….………………………………..……………………i Summary ……………………………………………….……………………………… ii 目錄……………………………………………………………………………………..iv 表目錄…………………………………………….…………………………………….vi 圖目錄…………………………………………………………………………………...x 第一章 前言…………………………………………………………………………….1 第二章 文獻回顧……………………………………………………………………….3 第三章 環氧樹脂之製備及硬化樹脂之性質……………………………………...15 一、材料與方法…………………...…………………………………………..…15 (一) 試驗材料……………………………………………………………….15 (二) 試驗方法……………………………………………………………….15 二、結果與討論………………………………………………………………...19 (一) 環氧樹脂之基本性質…………………………………………………..19 (二) 環氧樹脂之硬化性……………………………………………………..20 (三) 硬化樹脂之FTIR性質………………………………………………...24 (四) 溶出試驗重量保留率…………………………………………………..26 (五) 硬化樹脂之動態熱機械分析…………………………………………..27 (六) 硬化樹脂之熱重分析…………………………………………………..29 第四章 不同末端基聚胺基甲酸酯樹脂之性質……………………………………...32 一、 材料與方法………………………………………………………………….32 (一)試驗材料………………………………………………………………….32 (二)試驗方法………………………………………………………………….32 二、結果與討論…………………………………………………………………..35 (一) 不同末端基PU樹脂之分子量…………………………………………35 (二) 不同末端基PU樹脂之FTIR分析……………………………………..37 (三) 不同末端基PU樹脂之DSC熱分析……………………………………39 (四) 不同末端基PU樹脂之耐溶劑性………………………………………41 (五) 不同末端基PU樹脂之DMA熱分析…………………………………..41 (六) 不同末端基PU樹脂之TGA熱分析…..………………………………43 第五章 環氧樹脂/聚胺基甲酸酯樹脂聚摻合樹脂之性質…………………………..46 一、 材料與方法………………………………………………………………….46 (一)試驗材料………………………………………………………………….46 (二)試驗方法………………………………………………………………….46 二、 結果與討論………………………………………………………………….49 (一) ER/PU聚摻合樹脂之DSC熱分析…………….……………………….49 (二) ER/PU聚摻合樹脂FTIR圖譜分析…………………………………….52 (三) ER/PU聚摻合樹脂之機械性質分析…………………………………...54 (四) ER/PU聚摻合樹脂之DMA熱分析…………………………………….58 (五) ER/PU聚摻合樹脂之TGA熱分析……………………………………..64 第六章 聚胺基甲酸酯樹脂/環氧樹脂聚摻合樹脂之性質…………………………..70 一、 材料與方法………………………………………………………………….70 (一)試驗材料………………………………………………………………….70 (二)試驗方法………………………………………………………………….70 二、 結果與討論………………………………………………………………….73 (一) PU/ER聚摻合樹脂之DSC熱分析….…………………………………..73 (二) PU/ER聚摻合樹脂之FTIR分析………………………………….…….75 (三) PU/ER聚摻合樹脂之機械性質……………………………….………...77 (四) PU/Epoxy聚摻合樹脂之DMA分析……………………………………78 (五) PU/Epoxy聚摻合樹脂之TGA分析…………………………………….83 第七章 結論……………………………………..…………………………………….87 參考文獻……………………………………..………………………………………...8