镁离子催化合成木质素-酚醛树脂的结构与固化特性

doi:10.3969/j.issn.0253-2417.2018.04.012

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (4): 74-78.doi: 10.3969/j.issn.0253-2417.2018.04.012

镁离子催化合成木质素-酚醛树脂的结构与固化特性

杨昇¹, 王钧², 李改云¹, 范东斌¹

1. 中国林业科学研究院木材工业研究所, 北京 100091;
2. 山东省林业科学研究院, 山东济南 250014

收稿日期:2018-01-23 出版日期:2018-08-25 发布日期:2018-08-10
通讯作者: 范东斌,硕士生导师,研究领域为生物质胶黏剂;E-mail:fandongbin8@163.com。 E-mail:fandongbin8@163.com
作者简介:杨昇(1989-),男,内蒙古乌兰察布人,助理研究员,博士,从事木质素高值化利用研究
基金资助:
国家林业公益性行业科研专项（201504602）

Molecular Structure and Curing Characteristics of Lignin-phenol-formaldehyde Resin Prepared with the Use of Magnesian Ion as Catalyst

YANG Sheng¹, WANG Jun², LI Gaiyun¹, FAN Dongbin¹

1. Research Institute of Wood Industry, Chinese Academy of Forestry, Beijing 100091, China;
2. Shandong Academy of Forestry, Jinan 250014, China

Received:2018-01-23 Online:2018-08-25 Published:2018-08-10

摘要/Abstract

摘要： 以纳米氧化镁（MgO）为催化剂，通过在酶解木质素（EHL）、苯酚、甲醛和NaOH反应的初期添加纳米MgO合成MgO催化的木质素-酚醛（MLPF）树脂。采用傅里叶红外光谱（FT-IR）、核磁共振（¹³C NMR）及差示扫描量热（DSC）技术手段表征MLPF树脂的分子结构与固化反应热行为，并与未添加MgO的对照样木质素-酚醛（LPF）树脂及酚醛（PF）树脂进行对比分析，研究Mg²⁺对MLPF树脂结构与固化特性的影响，结果表明：Mg²⁺有效促进了MLPF树脂中羟甲基基团形成，增加了分子结构中亚甲基连接结构数量，抑制了亚甲基醚键生成，使MLPF树脂结构的缩合程度高于LPF树脂；Mg²⁺可以实现MLPF树脂快速固化，降低树脂的固化反应温度。

关键词: 氧化镁, 木质素, 酚醛树脂, 分子结构, 固化

Abstract: The narometer magnesium oxide (MgO) was used as catalysis for the preparation of lignin-phenol-formaldehyde (MLPF) resin. MgO was added in the initial stage of resin reaction. The molecular structure and thermal behavior of the curing reaction of MLPF resin were characterized by Fourier transform infrare spectroscopic (FT-IR), ¹³C nuclear magnetic resonance (¹³C NMR) and different scanning calorimetry (DSC), respectively. A comparisons to phenol-formaldehyde (PF) resin and lignin-phenol-formaldehyde(LPF) resin without adding MgO were also carried out to investigate the effects of Mg²⁺ on the structure and curing characteristics of MLPF resin. The research results indicated that Mg²⁺ could promote the formation of hydroxymethyl group, increase the amounts of methylene, restrict the formation of ether bond bridge during MLPF resin synthesis, and lead to the higher structure condensation degree of MLPF resin than that of LPF resin. MgO seemed to make MLPF resin cure faster and decrease its curing reaction temperature.

Key words: magnesium oxide, lignin, phenol-formaldehyde resin, molecular structure, curing

中图分类号:

TQ35

杨昇, 王钧, 李改云, 范东斌. 镁离子催化合成木质素-酚醛树脂的结构与固化特性[J]. 林产化学与工业, 2018, 38(4): 74-78.

YANG Sheng, WANG Jun, LI Gaiyun, FAN Dongbin. Molecular Structure and Curing Characteristics of Lignin-phenol-formaldehyde Resin Prepared with the Use of Magnesian Ion as Catalyst[J]. Chemistry and Industry of Forest Products, 2018, 38(4): 74-78.

参考文献

[1] 顾继友. 我国木材胶黏剂的开发与研究进展[J]. 林产工业,2017,44(1):6-9. GU J Y. The Development and research progress of domestic wood adhesives[J]. China Forest Products Industry,2017,44(1):6-9.
[2] 唐晓红,毛雅君. 人造板胶黏剂的研究进展和发展趋势[J]. 河南教育学院学报:自然科学版,2017,26(1)30-33. TANG X H,MAO Y J. Research progress and development trend of adhesive for wood-based panels[J]. Journal of Henan institute of Education:Natural Science Edition,2017,26(1):30-33.
[3] YANG S,WEN J L,YUAN T Q,et al. Characterization and phenolation of biorefinery technical lignins for lignin-phenol-formaldehyde resin adhesive synthesis[J]. RSC Advances,2014,101(4):57996-58004.
[4] 杜官本,雷洪,PIZZI A. PF和PUF树脂分子结构对比研究[J]. 林产化学与工业,2013,33(1):27-31. DU G B,LEI H,PIZZI A. Comparison of the molecular structure between phenol-formaldehyde and phenol-urea-formaldehyde resins[J]. Chemistry and Industry of Forest Products,2013,33(1):27-31.
[5] FAN D B,LI G Y,QIN T F,et al. Synthesis and structure characterization of phenol-urea-formaldehyde resins in the presence of magnesium oxide as catalyst[J]. Polymers,2014,6(8):2221-2231.
[6] 霍淑平,孔振武. 木质素的化学改性及其在合成树脂中的应用进展[J]. 林产化学与工业,2009,29(增刊):213-218. HUO S P,KONG Z W. Progress of chemical modification of lignin and its application in synthetic resins[J]. Chemistry and Industry of Forest Products,2009,29(Supplement):213-218.
[7] ZAKZESKI J,BRUIJNINCX P C A,JONGERIUS A L,et al. The catalytic valorization of lignin for the production of renewable chemicals[J]. Chemical Reviews,2010,110(6):3552-3599.
[8] HUSSIN M H,RAHIM A A,MOHAMAD M N,et al. Physicochemical characterization of alkaline and ethanol organosolv lignins from oil palm (Elaeis guineensis) fronds as phenol substitutes for green material applications[J]. Industrial Crops and Products,2013,49:23-32.
[9] PANG B,YANG S,FANG W,et al. Structure-property relationships for technical lignins for the production of lignin-phenol-formaldehyde resins[J]. Industrial Crops and Products,2017,108:316-326.
[10] GHAFFAR S H,FAN M. Lignin in straw and its applications as an adhesive[J]. International Journal of Adhesion and Adhesives,2014,48:92-101.
[11] KNOP A,PILATO L A. Phenolic Resins:Chemistry,Applications and Performance[M]. New York:Springer-Verlag Berlin Heidelberg GmbH,1985.
[12] FAN D,CHANG J,GOU J,et al. On the cure acceleration of oil-phenol-formaldehyde resins with different catalysts[J]. The Journal of Adhesion,2010,86(8):836-845.
[13] 王钧,李改云,范东斌. 纳米氧化镁催化合成木素-酚醛树脂的工艺及性能[J]. 木材工业,2017,31(2):34-37. WANG J,LI G Y,FAN D B. Preparation and performance of lignin-phenol-formaldehyde resin catalyzed with nanometer magnesium oxide[J]. China Wood Industry,2017,31(2):34-37.
[14] HALLAC B B,SANNIGRAHI P,PU Y,et al. Biomass characterization of Buddleja davidii:A potential feedstock for biofuel production[J]. Journal of Agricultural and Food Chemistry,2009,57(4):1275-1281.
[15] DANIELSONA B,SIMONSONB R. Kraft lignin in phenol formaldehyde resin. Part 1:Partial replacement of phenol by kraft lignin in phenol formaldehyde adhesives for plywood[J]. Journal of Adhesion Science and Technology,1998,9(12):923-939.
[16] 雷洪,杜官本,PIZZI A,等. 碱性环境下苯酚-尿素-甲醛共缩聚树脂结构形成研究[J]. 林产化学与工业,2009,29(3):63-68. LEI H,DU G B,PIZZI A,et al. Structural progressing of phenol-urea-formaldehyde resin under alkaline condition[J]. Chemistry and Industry of Forest Products,2009,29(3):63-68.
[17] PANG B,YANG S,FANG W,et al. Structure-property relationships for technical lignins for the production of lignin-phenol-formaldehyde resins[J]. Industrial Crops and Products,2017,108:316-326.
[18] ZHANG W,MA Y F,XU Y Z,et al. Lignocellulosic ethanol residue-based lignin-phenol-formaldehyde resin adhesive[J]. International Journal of Adhesion and Adhesives,2013,40:11-18.
[19] QAO W,LI S J,GUO G W,et al. Synthesis and characterization of phenol-formaldehyde resin using enzymatic hydrolysis lignin[J]. Journal of Industrial and Engineering Chemistry,2015,21:1417-1422.

镁离子催化合成木质素-酚醛树脂的结构与固化特性

Molecular Structure and Curing Characteristics of Lignin-phenol-formaldehyde Resin Prepared with the Use of Magnesian Ion as Catalyst

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