本研究以苯磺酸及對甲苯磺酸為催化劑進行孟宗竹之酚液化處理，探討其最適當之液化條件，及液化產物用於製備resol型酚甲醛樹脂（phenol formaldehyde；PF）與間苯二酚-酚-甲醛樹脂（resorcinol phenol formaldehyde；RPF）之最適當合成條件，及其樹脂應用於合板與木材之膠合性能。結果顯示，酚液化孟宗竹材之最適當液化條件為酚/竹粉重量比3.0/1.0，苯磺酸催化劑用量，以對酚添加量為5-15 %，反應溫度130 ℃，反應60 min。酚液化竹材以製備水溶性Resol型酚樹脂條件時，以甲醛/酚化竹材產物（phenolated bamboo；Pb）/NaOH之莫耳比1.8/1/0.4，在85 ℃反應溫度下反應30 min者，其用於合板膠合之膠合剪力最佳，且均能符合合板標準膠合強度大於7 kgf/cm2以上之要求（CNS 1349 , 2008）。以液化竹材產物製備間苯二酚-酚-甲醛樹脂製備時，其合成條件以液化竹材Pb / F1（第一階段所添加福馬林之莫耳比） / F2（第二階段所添加福馬林之莫耳比）/ R=1/0.5/0.34/0.34時，有較佳之膠合強度值。以各種液化產物製備間苯二酚-酚甲醛樹脂，其中除PRPbF-30外，其餘皆能符合CNS 11031結構用集成材之膠合強度要求。

The purpose of this study was intend to use benzenesulfonic acid and p-toluenesulfonic acid as catalysts in phenolation of moso bamboo inner layler shavings trying to find out the suitable liquefaction conditions .Then, what is the most suitable synthetic conditions for preparing PF and RPF from phenolated moso bamboo and the shear bond strength of plywood and glued laminated wood bonded by these phenolic resins were also studied .
The results show that the suitable conditions for phenolation of moso bamboo inner layler shavings were phenol-to-bamboo weight ratio of 3.0/1.0 , with benzenesulfonic acid addition ranging from 7.5-15 % , at the reaction temperature of 130 ℃ for 60 min. And the most suitable condition for preparing water-soluble phenolic resol resin from phenolated moso bamboo is the formulation that with the molar ratio of formaldehyde to phenolated bamboo to NaOH is 1.8/1/0.4 , and at 85 ℃ reaction for 30 min .The shear bond strength of plywood bonded by this phenolic resol resin can be satisfied with the Chinese National Standard （CNS 1349 , 2008）.Its requirement of shear bond strength should be over 7 kgf /cm2.

The most suitable condition for preparing resorcinol phenol formaldehyde resin from phenolated moso bamboo is with the molar ratio of phenolated bamboo / F1 / F2 / R=1/0.5/0.34/0.34. The shear bond strength of those resin were able to satisfy the requirements specified in CNS-11031 structural glued laminated wood .

目 錄
摘 要 I
Abstract Ⅲ
謝 誌……………………………………………………………………... Ⅴ目 錄 Ⅶ
圖表目錄 Ⅸ
壹、 前 言 1
貳、 文獻回顧 2
一、液化處理之原因 2
二、液化反應機制之分類 2
(一) 溶劑 2
(二) 催化劑 4
三、液化過程中主要之反應 6
四、液化之機制 6
五、影響液化效果之因子 9
(一) 重量比 9
(二) 反應溫度 9
(三) 反應時間 10
(四) 催化劑之種類與添加量 10
(五) 木粉含水率 10
(六) 木粉之粒徑 11
六、酚甲醛樹脂之合成 11
七、液化木竹材製產物備酚樹脂性質之影響因子 13
(一) 甲醛/液化木材（F/PW）之莫耳比 13
(二) 合成反應溫度 14
(三) 氫氧化鈉/酚莫耳比 14
八、間苯二酚-酚甲醛樹脂膠合劑 14
參、 材料與方法 16
一、試驗材料 16
(一) 試藥 16
(二) 試材 17
二、試驗方法 18
(一) 孟宗竹酚液化處理及產物性質 18

(二) 液化竹材製備resol型酚甲醛樹脂 22
(三) 液化竹材製備間苯二酚-酚甲醛樹脂合成 30
肆、結果與討論 35
一、酚液化孟宗竹處理 35
(一)孟宗竹之化學組成分 35
　　　　(二)酚液化孟宗竹材產物之基本性質 35
　　二、酚液化產物製備resol型酚甲醛樹脂 47
(一) Resol型酚甲醛樹脂基本性質 47
(二)酚甲醛樹脂之熱硬化性分析 49
(三)酚甲醛樹脂之合板引張膠合強度 51
三、液化竹材製備間苯二酚-酚甲醛樹脂 53
(一)間苯二酚-酚甲醛樹脂之基本性質 53
(二)間苯二酚-酚甲醛樹脂之木材膠合強度 54
伍、結 論 57
參考文獻 58
附 錄 63
作者簡介 .......................................................................................................69

丁昭義 (1990) 木材化學。 國立編譯館 第157-174頁。
李云彩 (2005) 杉木液化產物用於膠合劑製備上之研究。膠接 26(5):24-27。
林正榮(1985) 結構用集成材膠合劑之研究 。國立中興大學森林研究所
碩士論文 第1-36頁。
陳嘉明 (2000) 生物質膠合劑。國立編譯館 第53-71頁。
陳奕君 (2005) 酚液化孟宗竹製備酚樹脂及其在成型材料製造之應用。國立中興大學森林學系碩士學位論文 第19-40頁
張上鎮、吳季玲、王升陽 (1997) 熱分析技術在木材化學研究領域之應用。
林產工業16(1) : 133-148。
张求慧、赵广杰、陈金鹏 ( 2004) 酸性催化剂对木材酚液化能力的影响。北京林业大学学报 26（5）: 66-70。
鄭志峰、劉本安、汪蓉、張宏健 (2007) 核桃殼液化產物制備木材膠合劑的研究。膠接28 (4) : 1-3。
羅蓓、秦特夫、李改云（2005）人工林木材的酚液化及樹脂化研究 。
木材工業 20(5) : 8-10。
傅深淵、余仁廣、杜波、郭飛燕、朱瓊環 (2004) 竹材殘料液化及液化物膠黏劑之製備。林產工業(中國) 3 (10) : 35-38。
山田彦（1999）木材の液化技术の开发と反应机構の解明。木材工業
54 (1) : 2-7。


白石信夫 (1986) 木材のプラスチック化。木材學会誌32(10) : 755-762。
森田光博（1994）酸化处理による化学修饰木材の热可塑性-溶解性の改善 。木材工業49(12):593-598。
Alma, M. H., M . Yoshioka , Y. Yao and N. Shiraishi (1995 a) Some characterizations of hydrochloric acid catalyzed phenolated wood-based materials. Mokuzai Gakkaishi 41(8) : 741-748.
Alma, M. H., M . Yoshioka , Y. Yao and N. Shiraishi (1995 b) Preparation of oxalic acid-catalyzed resinified phenolated wood and its characterization. Mokuzai Gakkaishi 41(12) : 1122-1131.
Alma, M. H., M .Yoshioka , Y. Yao and N. Shiraishi (1995 c) Phenolation of wood using oxalic acid as a catalyst. The effects of temperature and hydrochloric acid addition. Journal of Polymer Science 61(4) : 675-683.
Alma, M. H., M .Yoshioka,Y. Yao and N. Shiraishi (1996) The preparation and flow properties of HCl-catalyzed phenolated wood and its blend with commercial novolak resin. Holzforschung 50(1) : 85-90.
Alma, M. H., M. Yoshioka, Y. Yao and N. Shiraishi (1998) Preparation of sulfuric acid-catalyzed wood resin. Wood Science and Technology 32(4) : 297-308.
Alma M. H and S. S. Kelley (2000a) Tensile properties of molding materials obtained by the condensation of various tree barks and phenol by using sulfuric acid as a catalyst. Journal of Material Science
19 (17) : 1517-1520.
Alma, M. H. and M. A . Basturk (2006) Liquefaction of grapevine cane waste and its application to phenol-formaldehyde type adhesive. Industrial Crops and Products 24(2) : 171-176.

Chow, S. and P. R. Steiner (1979) Comparisons of the cure of phenol-formaldehyde novolak and resol systems by differential scanning calorimetry. Journal of Applied Polymer Science 23：1973-1985.
Houwink, R. G. and G. Salomon (1979) Phenol Formaldehyde Adhesive. Adhesion and Adhesives(Volume1) pp.221-225.
Lee, S. H., M. Yoshioka and N. Shiraishi (2000a) Liquefaction
of corn bran (CB) in the presence of alcohol and preparation of
polyurethane foam its liquefied polyol. Journal of Applied Polymer Science 78(2):319-325.
Lee, S.H., M. Yoshioka and N. Shiraishi (2002b) Resol-type phenolic resin from liquefied phenolated wood and its application to phenolic foam. Journal of Applied Polymer Science 84 (3): 468-472.
Lee, W. J. and C. T. Liu (2003) Preparation of liquefied bark-based resol resin and its application to particle board. Journal of Applied Polymer Science 87(11): 1837-1841.
Lee, S.H.(2003) Phenolic resol resin from phenolated corn bran and its characteristics. Journal of Applied Polymer Science 87(8):1365-1370.
Lee, S. H., M. Yoshioka and N. Shiraishi (2000a) Liquefaction and product identification of corn bran (CB) in phenol. Journal of Applied Polymer Science 78: 311-318.
Lee, S. H., M. Yoshioka and N. Shiraishi (2000b) Liquefaction of corn bran (CB) in the presence of alcohol and preparation of polyurethane foam
from its liquefied polyol. Journal of Applied Polymer Science
78: 319-325.


Lee, S. H., M. Yoshioka and N. Shiraishi (2000c) Preparation and properties of phenolated corn bran (CB)/pheno/formaldehyde cocondensed resin. Journal of Applied Polymer Science 77: 2901-2907
Lee, S.H., M. Yoshioka and N. Shiraishi (2002) Resol-type phenolic resin from liquefied phenolated wood and its application to phenolic foam. Journal of Applied Polymer Science 84(3): 468-472.
Lin, L., Y. Yao, M. Yoshioka and N. Shraishi （1994）Liquefaction of wood in the presence of phenol using phosphoric acid as a catalyst and the flow properties of the liquefied wood. Journal Applied Polymer Science 52(11):1629-1636.
Lin, L., Y. Yao, M. Yoshioka and N. Shraishi (1995a) Physical properties of moldings from liquefied wood resins. Journal of Applied Polymer Science 55(11):1563-1571.
Lin, L., Y. Yao, M. Yoshioka and N. Shraishi (1995b) Preparation and properties of phenolated wood/phenol formaldehyde condensed resins.Journal of Applied Polymer Science 58(8):1297-1304.
Maldas, D.and N. Shiraishi (1996) Liquefaction of wood in the presence of polyol using NaOH as a catalyst and its application to polyurethane foams. International Journal of Polymeric Materials 33 (1): 61-71.
Lin, L., Y. Yao, M. Yoshioka and N. Shraishi (2001) Liquefaction mechanism ofβ-O-4 lignin model compound in the presence of phenol under acid catalysis part 2. reaction behavior and pathways. Holzforschung
55(6): 625-630.
Pu, S. and N. Shiraishi (1993a) Liquefaction of wood without a catalyst I. Time course of wood liquefaction with phenols and effects of wood/phenol ratios. Mokuzai Gakkaishi 39(4): 446-452.
Pu, S. and N. Shiraishi (1993b) Liquefaction of wood without a catalyst II. Weight loss by gasification during wood liquefaction,and effects of temperature and water. Mokuzai Gakkaishi 39(4): 453-458.
Pu, S. and N. Shiraishi (1994) Liquefaction of wood without a catalyst IV. Effect of additives,such as acid, salt, and neutral organic solvent. Mokuzai Gakkaishi 40:824-829
Santana, A. E., G. D. Melissa and A. H. Conner (1996) Phenol-formaldehyde plywood adhesive resin prepared with liquefied bark of Black Wattle. Journal of Wood Chemistry and Technology 16(1) : 1-19.
Zhang,Q. H., G. j. Zhao and S. Y. Hu (2005) Factors Affecting the resinification of liquefied phenolated wood. Forestry Studies in China 7(2): 38-42.
行政院農業委員會林務局 (2007) 森林資源調查-台灣全島森林地林型面
積。2007年12月21日，取自於：http://www.forest.gov.tw/spring.htm