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研究生:尤昭云
研究生(外文):Chao-Yun Yu
論文名稱:液化木質材料製造聚胺基甲酸酯樹脂及其醇解回收再利用
論文名稱(外文):Polyurethane Resins Made from Liquefied Woody Materials and Its Recovery Utilization with Glycolysis
指導教授:李文昭李文昭引用關係
指導教授(外文):Wen-Jau Lee
學位類別:碩士
校院名稱:國立中興大學
系所名稱:森林學系所
學門:農業科學學門
學類:林業學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:88
中文關鍵詞:醇解反應液化木質材料聚胺基甲酸酯PU發泡體
外文關鍵詞:GlycolysisLiquefied woody materialPolyurethanePU foams
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  • 被引用被引用:4
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本研究將柳杉(Cryptomeria japonica; Japanese cedar)、麻竹(Dendrocalamus latiflorus; Ma bamboo)及桂竹(Phyllostachys makinoi; Makino bamboo)等木質材料以聚乙二醇及丙三醇之混合液為溶劑,H2SO4及HCl為催化劑進行液化處理,並將其液化木質材料與4,4’-二苯甲烷二異氰酸酯(PMDI)反應製造聚胺基甲酸酯發泡體,探討PU樹脂調配條件對PU發泡體性質之影響。另利用二乙二醇、乙二醇及丙二醇為溶劑,二乙醇胺為催化劑,對此PU發泡體進行醇解反應,並進一步利用此醇解產物做為回收多元醇原料,探討其與PMDI及1,6-六亞甲基-二異氰酸酯(Hexamethylene diisocyanate; HDI)之三聚合體(Desmodur N)兩種異氰酸酯反應再製造發泡體之可行性。由試驗結果得知,以PEG-400/glycerol為液化藥劑,H2SO4為催化劑對柳杉、麻竹及桂竹均有良好之液化效果;液化木質材料所製造PU發泡體之性質受各成分調配比例所影響,其中異氰酸酯比例較高者,其PU樹脂中液化木質材料之架橋反應較完全,發泡體機械性能及耐溶劑性較高,吸水性較低。以液化生質物為基質之PU發泡體利用二醇類為溶劑,二乙醇胺為催化劑,在150~190℃加熱溫度下可快速進行醇解反應。FTIR光譜分析顯示經醇解處理後,其胺基甲酸酯鍵結及尿素鍵結產生降解;GPC分子量分析顯示,醇解產物的平均分子量隨反應時間延長而下降。醇解產物再應用於PU發泡體製造時,宜採用重量比75/25之原生多元醇/醇解產物為多元醇原料,其所得再製發泡體機械強度高,載重之形變量較小,耐溶劑之重量保存率高。TGA熱重分析顯示,添加醇解產物可使PU發泡體之耐熱性提高。以聚乙二醇為多元醇原料之發泡體,增加醇解產物之添加量,可提高發泡體在高溫熱裂解後之重量殘留率。
In this study, Japanese cedar (Cryptomeria Japonica), Ma bamboo (Dendrocalamus latiflorus) and Makino bamboo (Phyllostachys makinoi) were liquefied in polyethylene glycol/glycerol co-solvent with H2SO4 or HCl as catalyst. The liquefied woody materials were blended with PMDI (4,4’-Diphenylmethane diisocyanate;MDI) to prepare the PU foams. The effects of preparation conditions of PU resin on the properties of PU foams were investigated. In addition, diethylene glycol, ethylene glycol and propylene glycol as solvent and diethanolamine as the catalyst was used in the glycolysis of PU foams. The glycolysis products were blended with PMDI and Desmodur N to prepare the PU foams. The feasibility of PU foams made from the glycolysis products and their properties were investigated, too. The results showed that Japanese cedar, Ma bamboo and Makino bamboo all had a good liquefaction efficiency as liquefied in polyethylene glycol/glycerol co-solvent with H2SO4 as a catalyst. The properties of PU foams made from liquefied woody material were influenced by the formulas of PU resins. Wherein, the PU foams made with a higher ratio of isocyanate would had a more complete crosslinking structure, a better mechanical properties and solvent resistance, and a lower water adsorption. The results showed that dihydric alcohol as the solvent with diethanolamine as the catalyst under 150~190℃ was useful in the glycolysis of the liquefied woody material-based PU foams. FTIR analysis showed that the urethane bond and urea bond in PU forms were degraded after glycolysis. GPC analysis showed that the average molecular weight of the glycolysis product would decrease as the reaction time was prolonged. When the glycolysis products were used to re-manufacture the PU foams, using the mixture of raw polyol/glycolysis products with a weight ratio of 75/25 as the polyol would be the most suitable. Those PU foams had a high mechanical strength, low loading deformation and a high percent of weight retention for solvent resistance TGA analysis showed that the heat-resistance of the PU foams could be increased by blending with glycolysis products. When PU foams were prepared with PEG as the raw materials, increasing the amount of glycolysis product added could increase the char content after thermal degradation at high temperature.
摘要........................................................i
Summary....................................................ii
目錄.......................................................iv
圖目次.....................................................vi
表目次.....................................................xi
第一章 前言.............................................1
第二章 文獻回顧….......................................3
第三章 液化木質材料製造聚胺基甲酸酯發泡體之性質........15
壹、材料與方法.............................................15
一、試驗材料...............................................15
二、試驗方法...............................................16
貳、結果與討論.............................................20
一、液化木質材料之性質.....................................20
二、液化木質材料之FTIR分析.................................21
三、PU樹脂之DSC等溫硬化性..................................26
四、液化木質材料製備PU發泡體之壓縮特性.....................32
五.、液化木質材料製備PU發泡體之耐溶劑性....................36
六、液化木質材料製備PU發泡體之吸水特性.....................37
七、PU發泡體耐熱性之DSC熱分析..............................38
第四章 聚胺基甲酸酯發泡體之醇解處理及其醇解產物之性質..40
壹、材料與方法.............................................41
一、試驗材料...............................................41
二、試驗方法...............................................42
貳、結果與討論.............................................43
一、醇解產物之性質.........................................43
二、醇解產物之FTIR分析.....................................48
三、醇解產物之分子量分析...................................52
第五章 醇解產物再製造PU發泡體及其性質..................59
壹、材料與方法.............................................59
一、試驗材料...............................................59
二、試驗方法...............................................60
貳、結果與討論.............................................61
一、PU發泡體之性質及外觀形態...............................62
二、醇解產物製備PU發泡體之壓縮特性.........................71
三、醇解產物製備PU發泡體之耐溶劑性及吸水特性...............72
四、PU發泡體之DSC熱分析....................................74
五、TGA分析................................................77
第六章 結論............................................83
參考文獻...................................................85
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