Formaldehyde-free Olefin-Maleamic Acid Resin Adhesives: New Materials, New Chemistry, High Performance

Jiang-shan Zhou; Kai-yuan Liu; Jun-qiang Shao; Chang-wen Zhao; Dong Chen; Wan-tai Yang

doi:10.11777/j.issn1000-3304.2024.24306

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Formaldehyde-free Olefin-Maleamic Acid Resin Adhesives: New Materials, New Chemistry, High Performance

Research Article | 更新时间：2025-04-28

- Formaldehyde-free Olefin-Maleamic Acid Resin Adhesives: New Materials, New Chemistry, High Performance
- Acta Polymerica Sinica Vol. 56, Issue 5, Pages: 778-788(2025)
- 作者机构：
  
  1.化工资源有效利用国家重点实验室北京化工大学北京 100029
  2.新元化学(山东)股份有限公司威海 264200
- 作者简介：
  
  Chang-wen Zhao, E-mail: zhaocw@buct.edu.cn
  Wan-tai Yang, E-mail: yangwt@buct.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24306
  CLC：
- CSTR：32057.14.GFZXB.2025.7354
- Received：23 December 2024，
  
  Accepted：2025-02-03，
  
  Published Online：28 March 2025，
  
  Published：20 May 2025
- 稿件说明：
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周江山, 刘恺元, 邵军强, 赵长稳, 陈冬, 杨万泰. 烯马树脂无醛胶黏剂：新材料、新化学、高性能. 高分子学报, 2025, 56(5), 778-788

Zhou, J. S.; Liu, K. Y.; Shao, J. Q.; Zhao, C. W.; Chen, D.; Yang, W. T. Formaldehyde-free olefin-maleamic acid resin adhesives: new materials, new chemistry, high performance. Acta Polymerica Sinica, 2025, 56(5), 778-788
周江山, 刘恺元, 邵军强, 赵长稳, 陈冬, 杨万泰. 烯马树脂无醛胶黏剂：新材料、新化学、高性能. 高分子学报, 2025, 56(5), 778-788 DOI： 10.11777/j.issn1000-3304.2024.24306. CSTR： 32057.14.GFZXB.2025.7354.

Zhou, J. S.; Liu, K. Y.; Shao, J. Q.; Zhao, C. W.; Chen, D.; Yang, W. T. Formaldehyde-free olefin-maleamic acid resin adhesives: new materials, new chemistry, high performance. Acta Polymerica Sinica, 2025, 56(5), 778-788 DOI： 10.11777/j.issn1000-3304.2024.24306. CSTR： 32057.14.GFZXB.2025.7354.

摘要

基于缩聚反应合成的以脲醛树脂为代表的热固性甲醛系胶黏剂；由于甲醛残留及解聚反应的限制，用其黏合的人造板存在长期释放甲醛的问题. 开发无醛胶黏剂是从根本上解决人造板甲醛污染难题的有效方法. 本文提出了一种新的制备水溶性无醛胶黏剂的化学方法，首先以低成本的烯烃/混合烯烃和马来酸酐为原料，通过自稳定沉淀聚合(2SP)合成了烯烃/混合烯烃-马来酸酐共聚物微球. 进而利用该微球粒径均一、内部多孔、反应活性高的特点，直接与氨气通过气固反应制备了烯烃/混合烯烃-马来酰胺酸共聚物(简称“烯马树脂”). 烯马树脂可以在与脲醛树脂相同的热压条件下通过与其完全不同的胶合机理粘接木材：在高温条件下，烯马树脂的酰胺酸基团同时发生酰亚胺化反应和与木材羟基的酯化反应，实现其由水溶性向疏水性材料的转变，并同时通过交联木材赋予人造板良好的胶合性能. 以烯马树脂制备的纤维板、刨花板和胶合板综合性能均高于国标要求. 烯马树脂具有水溶性、无甲醛、苯及二甲苯添加、原料来源广泛且成本低、用胶工艺与脲醛树脂基本相同且胶合性能优异的特点，展现出替代传统脲醛树脂的巨大潜力.

Abstract

The synthesis of urea-formaldehyde resin

a representative of thermosetting formaldehyde-based adhesives

is based on the polycondensation reaction. However

due to limitations in its raw materials and depolymerisation reactions

the bonding of wood based panels results in the long-term release of formaldehyde. The development of formaldehyde-free adhesives represents an effective solution to the formaldehyde pollution problem associated with wood based panels. This paper proposes a novel chemical method for the synthesis of water-soluble

formaldehyde-free adhesives. Firstly

the low-cost olefin/mixed olefin and maleic anhydride are employed as the raw materials

and olefin/mixed olefin-maleic anhydride copolymer microspheres are synthesised by self-stabilised precipitation polymerisation (2SP). Subsequently

the uniform particle size

internal porousness and high reactivity of the microspheres were exploited to prepare olefin/mixed olefin-maleic acid copolymers (referred to as OMA resin) directly by gas-solid reaction with ammonia. The OMA resin can bond wood through a completely different gluing mechanism when subjected to the same hot-pressing conditions as those used for urea-formaldehyde resins: under high-temperature conditions

the amide group of the OMA resin undergoes the process involving both imidisation and esterification with the hydroxyl group of the wood

resulting in a transformation from a water-soluble material to a hydrophobic material. Additionally

through cross-linking reaction with wood facilitates excellent gluing performance. The comprehensive performance of fibreboard

particleboard and plywood prepared with allyl resin exceeds the requirements of the national standard. The product is water-soluble

contains no formaldehyde

benzene or xylene

and can be derived from a wide range of raw materials and cost-effective. Furthermore

the gluing process is similar to that of urea-formaldehyde resin and the product exhibits excellent gluing performance. Therefore

OMA resin shows great potential to replace traditional urea-formaldehyde resin.

关键词

Keywords

references

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化工资源有效利用国家重点实验室北京化工大学

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Sinopec (Beijing) Research Institute of Chemical Industry Co., Ltd.

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