臺灣博碩士論文加值系統

本研究以聚乙二醇-丙三醇混合液為液化藥劑，鹽酸及硫酸為催化劑，對未處理及經乙醇萃取之柳杉木材及樹皮進行液化處理，並以液化產物之殘渣率、黏度、不揮發分、酸價、羥價做為液化效果之評估指標；進一步將液化產物與聚二苯甲烷二異氰酸酯(PMDI)混合，並添加水為發泡劑、有機矽氧烷為界面活性劑、二月桂酸二丁基錫為催化劑製造硬質聚胺基甲酸酯發泡體 (Polyurethane foams；PU foams)；另將液化柳杉與Desmodur N混合，並加入界面活性劑、催化劑及1,4-丁二醇為鏈延長劑製造回彈性PU發泡體及PU彈性體。由試驗結果得知，柳杉木材有較高之全纖維素含量，樹皮則有較多之木質素及抽出成分含量；心、邊材之化學主成分無明顯差異，抽出成分含量則以心材大於邊材；經乙醇萃取處理對柳杉之化學主成分無影響，醇苯抽出物含量則明顯降低。液化處理時，各部位柳杉木材及經乙醇萃取材均有良好之液化效果，在液比2.5/1，經150℃加熱90 min後，其中液化木材之殘渣率在2.06%以下。樹皮則較不易進行液化處理，其液比須3/1以上，且所得液化樹皮之殘渣率及黏度均較高。各不同條件液化柳杉均可與PMDI反應製造硬質PU發泡體，所得發泡體之密度介於0.027~0.059 g/cm3，其外觀型態及物理機械性質受液化產物之特性所影響，以液化柳杉木材所製作者有較高之壓縮強度，以液化邊材及樹皮所製備者吸水能力較佳。將液化柳杉與Desmodur N反應可製造軟質PU發泡體及PU彈性體，其軟質PU發泡體具有回彈特性及壓縮回復性，吸水能力較PMDI製造者低，密度介於0.15-0.19 g/cm3。各種液化柳杉應用於PU彈性體製造時，以液化木材為原料所製造者，其彈性係數、拉伸強度及破壞伸長率較高。DSC熱分析顯示常溫硬化之PU發泡體及彈性體在高溫加熱過程中會出現後硬化放熱現象，但約在300℃產生熱裂解現象。

In this study, both the untreated and ethanol extracted wood and bark of Cryptomeria japonica were liquefied in polyethylene glycol-glycerol co-solvent with HCl and H2SO4 as catalyst. The residue content, viscosity, nonvolatile, acid number and hydroxyl number of the liquefied materials were used as the index to evaluate the efficiency of liquefaction. The liquefied materials were blended with PMDI (poly-4,4’-diphenylmethane diisocyanate), and adding water as a blowing agent, organosiloxane as a surfactant and dibutyl tin dilaurate as a catalyst to prepare the rigid polyurethane (PU) foams. Besides, the liquefied materials were blended with the Desmodur N (trimer of hexamethylene diisocyanate), and adding the surfactant, catalyst and 1,4-butanediol to prepare the flexible PU foams and PU elastomers. From the results, the wood of C. japonica had higher content of holocellulose than the bark, but less content of lignin and extractive than the bark. It was unobvious difference between the heartwood and sapwood in the content of main chemical component. Heartwood had more extractive than sapwood. The ethanol extraction would not influence the main chemical component of C. japonica, but would decrease the extractive content. Both the untreated and ethanol extracted wood had good liquefaction effect. As liquefied with the weight ratio of solvent to wood at 2.5/1 and heating at 150℃ for 90 minutes, the un-liquefied residue in the liquefied wood was lower than 2.06%. However, the bark was more difficult to be liquefied, the weight ratio of solvent/wood used should be over 3.0/1, but the liquefied bark still had more residue content and higher viscosity. All of the C. japonica those liquefied with various liquefaction conditions could react with PMDI to manufacture the rigid PU foams. The density of these PU foams was between 0.027 and 0.059 g/cm3. However, the appearance and physical mechanical properties of PU foams were affected by characteristic of liquefied materials. The PU forms made from liquefied wood had higher compressive strength. But those made from liquefied sapwood or liquefied bark had better water adsorption properties. The liquefied Cryptomeria japonica could react with Desmodus N to make the flexible PU foams and elastomers. The density of flexible PU foams from liquefied wood and bark were between 0.15 and 0.19 g/cm3, and had the flexible and compression reversional properties. But their water adsorption property was worse than rigid PU foams made from PMDI. While the liquefied C. japonica was applying to make the PU elastomers, using the liquefied wood as raw materials had higher elastic module, tensile strength and broken elongation than others. The DSC thermal analysis showed that the PU foams and elastomers cured at room temperature would appear a post-curing exothermic phenomenon under the heating process. The thermal degradation of PU products would occur at the temperature about 300℃.

目錄………………………………………………………………i
圖目次……………………………………………………………iii
表目次……………………………………………………………viii
摘要………………………………………………………………xii
Summary …………………………………………………………xiii
第一章 前言……………………………………………………1
第二章 文獻回顧………………………………………………3
ㄧ、生物質液化…………………………………………………3
二、PU材料之製造及反應原理…………………………………5
三、液化生物質應用於PU材料製造……………………………13
第三章 柳杉材之液化效果及液化產物之性質………………17
ㄧ、材料與方法…………………………………………………17
(一)試驗材料……………………………………………………17
(二)試驗方法……………………………………………………18
二、結果與討論…………………………………………………23
(一)柳杉木材及樹皮之化學組成分 …………………………23
(二)液化木質材料之基本性質…………………………………24
(三)液化木質材料之FT-IR分析 ………………………………31
(四)液化木質材料之分子量及分子量分佈……………………37
第四章 硬質PU發泡體之製造及其性質………………………40
ㄧ、材料與方法…………………………………………………40
(一)試驗材料……………………………………………………40
(二)試驗方法……………………………………………………41
二、結果與討論…………………………………………………45
(一)硬質PU發泡體之外觀型態…………………………………45
(二)硬質PU發泡體之FT-IR分析 ………………………………47
(三)硬質PU發泡體之機械特性…………………………………51
(四)硬質PU發泡體之吸水特性及耐溶劑性……………………54
(五)硬質PU發泡體之熱分析……………………………………56
第五章 軟質PU發泡體之製造及其性質………………………61
ㄧ、材料與方法…………………………………………………61
(一)試驗材料……………………………………………………61
(二)試驗方法……………………………………………………63
二、結果與討論…………………………………………………66
(一)不同組成條件對軟質PU發泡體成型及外觀特徵之影響…66
(二)軟質PU發泡體之機械特性…………………………………74
(三)吸水特性及耐溶劑性. ……………………………………81
(四)熱性質………………………………………………………83
第六章 PU彈性體之製造及其性質……………………………87
ㄧ、材料與方法…………………………………………………87
(一)試驗材料……………………………………………………87
(二)試驗方法……………………………………………………88
二、結果與討論…………………………………………………90
(一) PU彈性體之拉伸性質 ……………………………………90
(二) PU彈性體之FT-IR分析……………………………………94
(三)PU彈性體之熱分析…………………………………………98
第七章 結論……………………………………………………103
參考文獻…………………………………………………………105

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