高含水率状态下桦木与异氰酸酯的胶接化学反应历程

doi:10.3969/j.issn.0253-2417.2014.01.006

林产化学与工业 ›› 2014, Vol. 34 ›› Issue (1): 31-36.doi: 10.3969/j.issn.0253-2417.2014.01.006

高含水率状态下桦木与异氰酸酯的胶接化学反应历程

韦双颖^1,2,3, 李存鲁², 王砥^1,2, 顾继友^1,2, 曹军³

1. 东北林业大学生物质材料科学与技术教育部重点实验室, 黑龙江哈尔滨 150040;
2. 东北林业大学材料科学与工程学院, 黑龙江哈尔滨 150040;
3. 东北林业大学机械工程博士后流动站, 黑龙江哈尔滨 150040

收稿日期:2013-07-14 出版日期:2014-02-25 发布日期:2014-03-05
通讯作者: 曹军，教授，博士生导师，主要从事机械自动化研究工作；E-mail：zidonghua@163.com。 E-mail:zidonghua@163.com
作者简介:韦双颖（1978-），女，黑龙江哈尔滨人，副教授，博士，主要从事木材科学与技术的研究工作
基金资助:
国家自然科学青年基金项目（31200440）；C类科学前沿与交叉学科创新基金项目（DL12CB08）；中国博士后科学基金第四十九批面上项目（20110491017）

The Chemical Reaction Process of Bonding Birch with Isocyanate at the Condition of High Moisture Content

WEI Shuang-ying^1,2,3, LI Cun-lu², WANG Di^1,2, GU Ji-you^1,2, CAO Jun³

1. Key Laboratory of Bio-based Material Science and Technology, Northeast Forestry University, Harbin 150040, China;
2. Material Science and Engineering College, Northeast Forestry University, Harbin 150040, China;
3. Postdoctoral Research Station in College of Mechanical and Electrical Engineering, Northeast Forestry University, Harbin 150040, China

Received:2013-07-14 Online:2014-02-25 Published:2014-03-05

摘要/Abstract

摘要： 对湿固化异氰酸酯胶黏剂粘接高含水率桦木的胶接机理进行系统研究。利用计算化学方法这一崭新的手段，采用Material Studio软件中DMol3模块，采用基于密度泛函理论的量子化学程序，通过模拟胶接体系中异氰酸酯基团（NCO）与自由水（H₂O）及桦木中不同化学环境羟基（—OH）的反应历程，搜索反应的过渡态，计算反应活化能以及反应总能量，判定反应进行的难易以及先后次序。研究结果表明胶接体系中—NCO基团与自由水反应的活化能与—NCO基团与纤维素中—OH的反应活化能相接近，反应存在竞争关系。胶接体系中—NCO与纤维素上—OH相对来说较容易反应，且反应进行的顺序是C₆ >C₃ >C₁ >C₂，均为放热反应；与木质素上—OH不容易反应，反应进行的顺序是紫丁香基丙烷（Lig-S）>愈创木基丙烷（Lig-G）>对羟苯基丙烷（Lig-H），其中羟基与Lig-S和Lig-G的反应是放热反应，与Lig-H的反应是吸热反应。

关键词: 高含水率, 密度泛函理论, 异氰酸酯基团, 胶接机理

Abstract: The bonding mechanism of birch in high moisture content glued with moisture curing isocyanate adhesive was investigated in this paper. The reaction processes between isocyanate groups (—NCO) in glued systems and free water or hydroxyl (—OH) in different chemical environment of birch were simulated using DMol3 program of Material Studio software. The difficulty and order of reaction were determined by searching the transition state and computation of the activation energy and the total energy of reaction. The investigations showed that the activation energy of reaction between —NCO groups and free water was closed to that between —NCO groups and —OH of cellulose. This indicated that these were a couple of competitive reactions. The reaction between —NCO and —OH of cellulose in the glued system occurs relatively easier than the reaction of —NCO and —OH of lignin. Furthermore, the order of reaction in cellulose is C₆ >C₃ >C₁ >C₂ and all of reactions in cellulose are exothermic. The order of reaction in lignin is lilac propane (Lig-S)> guaiacyl propane (Lig-G)>p-hydroxyphenyl propane (Lig-H). The reactions of Lig-S and Lig-G are exothermic, but the reaction of Lig-H was an endothermic reaction.

Key words: high moisture content, density function theory, isocyanate groups, bonding mechanism

中图分类号:

TQ35

韦双颖, 李存鲁, 王砥, 顾继友, 曹军. 高含水率状态下桦木与异氰酸酯的胶接化学反应历程[J]. 林产化学与工业, 2014, 34(1): 31-36.

WEI Shuang-ying, LI Cun-lu, WANG Di, GU Ji-you, CAO Jun. The Chemical Reaction Process of Bonding Birch with Isocyanate at the Condition of High Moisture Content[J]. Chemistry and Industry of Forest Products, 2014, 34(1): 31-36.

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高含水率状态下桦木与异氰酸酯的胶接化学反应历程

The Chemical Reaction Process of Bonding Birch with Isocyanate at the Condition of High Moisture Content

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