苯酚-尿素-甲醛树脂的合成和机理研究

doi:10.3969/j.issn.0253-2417.2018.01.015

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (1): 101-109.doi: 10.3969/j.issn.0253-2417.2018.01.015

苯酚-尿素-甲醛树脂的合成和机理研究

王荣兴¹, 张祖新¹, 陈日清^1,2, 赵临五¹, 王春鹏^1,2, 储富祥^1,2

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2017-05-17 出版日期:2018-02-25 发布日期:2018-02-28
通讯作者: 陈日清,副研究员,主要从事生物基高分子研究;E-mail:michaelmao77@163.com。 E-mail:michaelmao77@163.com
作者简介:王荣兴(1993-),男,山东桓台人,硕士生,研究方向为高分子材料的合成与应用
基金资助:
“十二五”国家科技支撑计划资助（2015BAD14B03）；木竹产业技术创新战略科研计划课题资助（TIAWBI201506）

Synthesis of Phenol-urea-formaldehyde Resin and Its Reaction Mechanism

WANG Rongxing¹, ZHANG Zuxin¹, CHEN Riqing^1,2, ZHAO Linwu¹, WANG Chunpeng^1,2, CHU Fuxiang^1,2

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Rsearch Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2017-05-17 Online:2018-02-25 Published:2018-02-28

摘要/Abstract

摘要： 制备合成了不同尿素用量的系列尿素改性酚醛（PUF）树脂胶黏剂，探讨了一种PUF树脂胶黏剂较优的配方和合成工艺，并通过¹³C NMR、TG对PUF树脂的反应过程和分解过程进行了研究。结果表明：合成过程中尿素分三批加入，以CaO和NaOH为复合催化剂，在碱性条件下制备的5组尿素用量不同的PUF树脂，以这5组PUF树脂作胶黏剂压制的杨木三合板胶合强度全部符合Ⅰ类胶合板要求，甲醛释放量≤ 0.5 mg/L；¹³C NMR分析结果显示，树脂合成过程中的羟甲基、亚甲基、亚甲基醚键的含量随着尿素添加量和反应时间的不同而变化，PUF树脂合成过程的主要反应为甲醛的亲电加成，TG分析表明热稳定性呈先提高后降低的趋势。

关键词: 尿素改性酚醛树脂, 木材胶黏剂, 反应机理, 残炭率, 胶合强度

Abstract: Phenol-urea-formaldehyde (PUF) resin wood adhesives with different amount of urea instead of phenol were synthesized.and a simple phenol-urea-formaldehyde resin formulation and synthesis technology was investigated.The bonding strength of the five PUF pressed plywoods with different dosage of urea all met the requirements of classⅠ.The cure,decomposition and reaction processes of PUF resin were characterized by ¹³C NMR and TG respectively.¹³C NMR showed the content of hydroxymethyl,methylene and methylene ether bonds in PUF resin varied with the amount of urea and the reaction time during the preparation.Furthermore,the reaction mechanism of PUF synthesis was analyzed and the heat resistance of the synthesized PUF resin was characterized by TG.The results showed that the synthesis process of PUF resin was the electrophilic addition of formaldehyde and the thermostability firstly increased and subsequently reduced.

Key words: urea modified phenolic resin, wood adhesive, reaction mechanism, residual carbon rate, bonding strength

中图分类号:

TQ35

王荣兴, 张祖新, 陈日清, 赵临五, 王春鹏, 储富祥. 苯酚-尿素-甲醛树脂的合成和机理研究[J]. 林产化学与工业, 2018, 38(1): 101-109.

WANG Rongxing, ZHANG Zuxin, CHEN Riqing, ZHAO Linwu, WANG Chunpeng, CHU Fuxiang. Synthesis of Phenol-urea-formaldehyde Resin and Its Reaction Mechanism[J]. Chemistry and Industry of Forest Products, 2018, 38(1): 101-109.

参考文献

[1] 顾继友. 胶黏剂与涂料[M]. 北京:中国林业出版社,1999. GU J Y. Adhesive and Coating[M]. Beijing:China Forestry Publishing,1999.
[2] 范东斌,常建民,林翔. 低成本酚醛树脂胶黏剂研究进展[J]. 林产工业,2008,35(5):14-17. FAN D B,CHANG J M,LIN X. Research progress in reducing the cost of phenol formaldehyde resins[J]. China Forest Produts Industry,2008,35(5):14-17.
[3] 傅深渊. 三聚氰胺、尿素改性酚醛树脂及其生产方法:CN 1974625[P]. 2007-06-06. FU S Y.Melamine and urea modified phenolic resin and its production method:CN 1974625[P]. 2007-06-06.
[4] FORSS K G,FUHRMANN A. Finnish plywood,particleboard,and fiberboard made with a lignin-base adhesive[J]. Forest Products Journal,1979,29(7):39-43.
[5] 孙丰文,张齐生,孙达旺. 落叶松单宁酚醛树脂胶黏剂的研究与应用[J]. 林业科技开发,2006,20(6):50-52. SUN F W,ZHANG Q S,SUN D W.Development of tannin-phenol-formaldehyde resin adhesive from larch and its application[J]. China Forestry Science and Technology,2006,20(6):50-52.
[6] 蒋玉凤. 苯酚尿素甲醛共缩聚树脂的合成、表征及其应用研究[D]. 南京:南京工业大学硕士学位论文,2011. JIANG Y F. Synthesis and characterization of phenol-urea-formaldehyde co-condensed resins and their application[D].Nanjing:Master Degree Thesis of Nanjing University of Technology,2011.
[7] 莫弦丰. 二价金属氧化物催化合成高邻位苯酚-尿素-甲醛树脂及其性能研究[D]. 北京:中国林业科学研究院博士学位论文,2014. MO X F. Synthesis and properties of divalent metal oxides catalyzed high-ortho phenol-urea-formaldehyde resins[J]. Beijing:Doctoral Dissertation of Chinese Academy of Forestry,2014.
[8] 殷勇刚,任蕊,刘春玲,等. 高邻位热塑性酚醛树脂的合成及固化性能[J]. 高分子材料科学与工程,2012,28(4):9-13. YIN Y G,REN R,LIU C L,et al. Synthesis and curing performance of high-ortho thermoplastic phenolic resin[J]. Polymer Material Science and Engineering,2012,28(4):9-13.
[9] FRASER D A,HALL R W,RAUM A L J. Prepartion of high-ortho'novolak resins(Ⅰ):Metal ion catalysis and orientation effect[J]. Journal of Applied Chemistry,1957,12(7):676-689.
[10] PIZZI A. Phenolic and tannin-based adhesive resins by reactions of coordinated metal ligands(Ⅰ):Phenolic chelates[J]. Journal of Applied Polymer Science,1979,24(5):1247-1255.
[11] 李淑君,陶毓博,李坚,等. 用TG-DSC-FTIR联用技术研究酚醛树脂的热解行为[J]. 东北林业大学学报,2007,35(6):56-58. LI S J,TAO Y B,LI J,et al. Pyrolysis of PF resin with TG-DSC-FTIR[J]. Journal of Northeast Forestry University,2007,35(6):56-58.

苯酚-尿素-甲醛树脂的合成和机理研究

Synthesis of Phenol-urea-formaldehyde Resin and Its Reaction Mechanism

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 7

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

[1]	姚奉奇, 陶骏骏, 王海晖, 胡国庆, 陈帅, TAHIR Mudassir Hussian. 茶多酚热解特性及其反应机理研究[J]. 林产化学与工业, 2017, 37(5): 19-27.
[2]	乔治邦, 顾继友, 曹军, 谭海彦, 张彦华. 室温固化型淀粉基木材胶黏剂的热分解动力学[J]. 林产化学与工业, 2016, 36(1): 85-91.
[3]	王淑敏, 时君友. 水性异氰酸酯木材胶黏剂耐久性研究[J]. 林产化学与工业, 2015, 35(2): 25-30.
[4]	孙恩惠, 黄红英, 武国峰, 曲萍, 常志州, 徐跃定. 大豆蛋白基生物质胶黏剂的合成及热力学性能[J]. 林产化学与工业, 2015, 35(2): 147-153.
[5]	张求慧, 赵广杰. 木材的苯酚及多元醇液化反应机理研究进展[J]. 林产化学与工业, 2014, 34(4): 137-143.
[6]	黄志义;冯永顺;于志明;母军. 杨木刨花板的热解动力学分析[J]. 林产化学与工业, 2012, 32(5): 83-87.
[7]	郑志锋;邹局春;张宏健;凌敏. 核桃壳苯酚液化及其产物树脂化制备木材胶黏剂的研究[J]. 林产化学与工业, 2007, 27(04): 31-36.