Urethane formation from condensed tannins and biodegradability of the urethane

由缩合单宁形成聚氨酯以及聚氨酯的生物降解性

• 批准号: 10460145
• 负责人: SAKAI Kokki
• 金额: $ 4.48万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10460145/
• 关键词: condensed tannin; model compound; sugi bark; catechin; urethane formation; amine catalyst; dibutyl tin catalyst; hydroxyl group value; カテコール; フロログルシノール; カテコール錫錯体; 樹皮成分; ポリウレタン; 触媒

(1) Simple tannin model compounds were treated with an equivalent phenyl isocyanate (PI) in the presence of DABCO (1,4-diazabicyclo[2,2,2]octane) or DBTDL (di-n-butyltin dilaurate) as a catalyst. It was found that DABCO catalyzed urethane formation from catechol-and resorcinol-types of hydroxyl groups, while DBTDL catalyzed that from alcoholic hydroxyl groups.(2) PI reacted firstly with the hydroxyl groups in ring B and then with those in ring A of catechin, which was employed as a more relevant model, in the presence of DABCO catalyst, while hydroxyl groups in the position 3 of catechin did not react at all. On the contrary, reactivity of catechin with PI was dramatically suppressed in the presence of DBTDL catalyst, due to the formation of a dibutyltin-catechin complex, which precipitated and hence deactivated catechin.(3) In order to liquefy sugi bark, a treatment with sodium bisulfite in an aqueous polyethylene glycol 400 was conducted. Both inner and outer bark liquefied extensively by the treatment at 250℃. At least a part of condensed tannin was degraded to monocyclic aromatic compounds like catechol and protocaechuic acid. A new method of hydroxyl group determination was developed.

(1)在DABCO（1，4-二氮杂双环[2，2，2]辛烷）或DBTDL（二月桂酸二正丁基锡）催化下，用等当量的苯基异氰酸酯（PI）处理简单单宁模型化合物。发现DABCO催化邻苯二酚型和间苯二酚型羟基形成氨基甲酸酯，而DBTDL催化醇羟基形成氨基甲酸酯。(2)在DABCO催化剂存在下，PI首先与儿茶素B环上的羟基反应，然后与儿茶素A环上的羟基反应，而儿茶素3位上的羟基完全不反应。相反，儿茶素与PI的反应性显着抑制在DBTDL催化剂的存在下，由于形成的二丁基锡-儿茶素络合物，沉淀，因此使儿茶素失活。(3)为了去除杉皮，在含水聚乙二醇400中用亚硫酸氢钠进行处理。在250℃处理下，内、外树皮均发生了大面积液化。至少有一部分缩合单宁被降解为单环芳香族化合物，如邻苯二酚和原儿茶酸。建立了一种新的羟基测定方法。

项目成果

T.Ashitani, M.Ujiie, S.Nagahama, T.Ueno, K.Sakai: "Properties of Extractives from sugi bark"Mokuzai Gakkaishi. 47, (in press). (2001)

T.Ashitani、M.Ujiie、S.Nagahama、T.Ueno、K.Sakai：“杉树皮提取物的特性”Mokuzai Gakkaishi。

上野智子,耿興蓮,芦谷竜矢,親泊政二三,坂井克己: "スギ樹皮のポリエチレングリコール・バイサルファイト法による液化"第45回リグニン討論会講演集. 127-130 (2000)

Tomoko Ueno、Ren Kong、Tatsuya Ashiya、Masajizo Oyadomari、Katsumi Sakai：“聚乙二醇亚硫酸氢盐法液化雪松树皮”第 45 届木质素研讨会论文集 127-130（2000 年）。

親泊政二三,坂井克己: "タンニンモデル化合物のウレタン化反応における触媒の効果(III) (+)カテキンを用いた検討"第50回日本木材学会大会発表要旨集. (発表予定). (2000)

Masaji Oyadomari、Katsumi Sakai：“催化剂在单宁模型化合物的氨基甲酸酯化反应中的作用（III）使用（+）儿茶素的研究”在第 50 届日本木材学会会议上发表的摘要集（预定的演示文稿）。

JJ Ge,W Zhong,ZR Guo,WJ Li,K Sakai: "Biodegradable Polyurethane Materials from Bark and Starch.I.Highly Resilient Foams"J Appl Polym Sci. 77. 2575-2580 (2000)

JJ Ge，Wzhong，ZRGuo，WJ Li，K Sakai：“来自树皮和淀粉的可生物降解聚氨酯材料.I.高回弹泡沫”J Appl Polym Sci。

K.Sakai: "Wood and Cellulosic Chemistry (Chemistry of Barkの章p243-273 分担執筆)"Marcel Dekker. 914 (2001)

K.Sakai：“木材和纤维素化学（树皮化学第 243-273 章合著者）”Marcel Dekker 914 (2001)。