臺灣博碩士論文加值系統

本研究將柳杉（Cryptomeria japonica; Japanese cedar）木材以酚或酚/雙酚 A 為溶劑，H2SO4 為催化劑進行液化處理，並將液化柳杉及酚分別與福馬林反應合成 Novolac 型酚醛樹脂（Phenol-formaldehyde resin; PF），另以雙酚 A 與環氧氯丙烷 反 應 合 成 環 氧 樹 脂 ； 並 將 Novolac 樹 脂 與 環 氧 樹 脂 混 合 製 備 摻 合 樹 脂 （Polyblending resin），或與環氧氯丙烷反應製備環氧化 PF 樹脂（Epoxidized Novolac-type PF resin），探討各不同條件複合系樹脂（Alloy resin）在不同硬化劑 存在下之硬化行為，及所製作成型板之性質。由結果顯示以液化木材或酚為原料 所 製 備 之 Novolac 型 PF 樹 脂 具 備 熱 熔 融 性 ， 添 加 六 亞 甲 基 四 胺 （Hexamethylenetetramine; Hexamine）為硬化劑後則可加熱硬化；環氧樹脂混合三 乙基四胺（Triethylene tetramine; TETA）、Hexamine 或順丁烯二酸酐（Maleic anhydride; MA）在 DSC 熱掃描過程均出現架橋反應放熱峰；Novolac/環氧樹脂之 摻合樹脂添加三苯基磷（Triphenylphosphine）為催化劑可加熱硬化，另添加 Hexamine 則可促進其熱硬化性，進一步添加 TETA 則可於常溫下即發生架橋反 應；硬化之摻合樹脂具有良好之尺寸安定性及熱抵抗性，其中混合液化木材為基 質之 PF 樹脂者有較佳之高溫熱抵抗性，添加 Hexamine 可提高摻合樹脂成型板溶 出試驗之重量保留率，並降低其熱活動性；環氧化 Novolac 型 PF 樹脂採用 TETA/Hexamine 混合硬化劑有較佳之溶出試驗重量保留率，環氧化可提高 Novolac 樹脂在高溫側之熱抵抗性，硬化樹脂含有木質成分可進一步提升熱抵抗性；環氧 化 PF 樹脂混合填料木粉、Hexamine、TETA 及硬酯酸鋅可熱壓製作成型板，其板 材之溶出試驗重量保留率大於未環氧化 PF 樹脂所製作者。

In this study, Cryptomeria japonica (Japanese fir) was liquefied in phenol or phenol/bisphenol A with H2SO4 as catalyst. Novolac-type phenol-formaldehyde resins (PF) were synthesized by reacting liquefied wood or phenol with formalin. Epoxy resin was prepared by reacting bisphenol A with epichlorohydrin. The polyblending resins were prepared by mixing PF with epoxy, and the epoxidized novolac-type PF resins were prepared by reacted with epichlorohydrin. The curing behavior and the properties of moldings for alloy resins with various cross-linking agents were investigated. The results show that novolac-type PF resins had the behavior of hot-melting and could be hot-thermosetting when mixing with hexamethylenetetramine (hexamine). DSC analysis showed an exothermic peak due to crosslinking reaction for epoxy resin that mixed with triethylene tetramine (TETA), hexamineand maleic anhydride (MA). Novolac/epoxy polyblending resins could be hot-setted when triphenylphosphine was added as a catalyst. Additional adding of hexamine could promote the reactivity of thermosetting, and further adding of TETA could lead the curing reaction occured at room temperature. The cured polyblending resins had good dimensional stability after dissolution test and had higher heat resistance. It had better high temperature resistance for that blended with liquefied wood-based novolac-type resin. Moldings made with polyblending resins by adding hexamine had better weight retention and lower heat activities. Epoxidized PF resins that cured with TETA/hexamine mixture as the hardener had better weight retention. The heat resistance of novolac-type resin could be improved after epoxidized, and it could advance be increased by the components of lignocelluse. Molding could be made with the mixture of epoxidized PF resins, wood powder, hexamine, TETA and
zinc stearate under hot-pressing. They had higher weight retention after acetone dissolution test than that made with unepoxidized novolac-type resins.

摘要.........i
Summary .........ii
目錄.........iv
表目次.........vi
圖目次.........x
第一章 前言.........1
第二章 文獻回顧.........3
一、生質物之液化作用及其應用.........3
二、酚樹脂之反應特性及改質處理.........9
三、環氧樹脂之合成及其應用.........15
四、熱分析儀在樹脂性質探討之應用.........20
第三章
Novolac/Epoxy 聚摻合樹脂之硬化性 .........24
一、材料與方法.........24
二、結果與討論.........30
（一）液化柳杉之性質.........30
（二）Novolac 型 PF 樹脂之性質.........34
（三）環氧樹脂之性質.........40
（四）Novolac/Epoxy 聚摻合樹脂之 DSC 熱硬化性.........43
（五）環氧樹脂及 Novolac 型 PF 樹脂之反應動力學 .........51
第四章
Novolac/Epoxy 聚摻合樹脂成型板之性質 .........54
一、材料與方法.........54
二、結果與討論.........57
（一）Novolac/Epoxy 聚摻合樹脂成型物之物理機械性質.........57
（二）Novolac/Epoxy 聚摻合樹脂成型物之熱動態機械性質 ......60
（三）Novolac/Epoxy 聚摻合樹脂成型物之熱重分析 .........66
第五章
環氧化 Novolac 型 PF 樹脂.........72
一、材料與方法.........72
二、結果與討論.........75
（一）環氧化 Novolac 型 PF 樹脂之性質.........75
（二）環氧化 Novolac 型 PF 樹脂之 DSC 硬化性分析.........78
（三）硬化樹脂之性質分析.........84
（四）環氧化 Novolac 型 PF 樹脂成型板之性質.........91
第六章
結論.........94
參考文獻.........96

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