Strengthening and Toughening Phenolic Resin-Based Bamboo-Plastic Composites via Boronate Ester Dynamic Bonds

MA Xin; HE Yin; WANG Runqi; HU Tiantian; ZHANG Yi; GUO Xi; SUN Weisheng; YAN Yutao

doi:10.12326/j.2096-9694.2025113

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Strengthening and Toughening Phenolic Resin-Based Bamboo-Plastic Composites via Boronate Ester Dynamic Bonds
College of Chemistry and Materials Engineering，Zhejiang A&F University，Hangzhou 311300，Zhejiang，China
Vol. 40, Issue 1, Pages: 41-50(2026)
DOI： 10.12326/j.2096-9694.2025113
稿件说明：

移动端阅览

马新,何银,王润起等.硼酸酯动态键强韧化酚醛树脂基竹塑复合材料研究[J].木材科学与技术,2026,40(01):41-50. DOI： 10.12326/j.2096-9694.2025113.

MA Xin,HE Yin,WANG Runqi,et al.Strengthening and Toughening Phenolic Resin-Based Bamboo-Plastic Composites via Boronate Ester Dynamic Bonds[J].Chinese Journal of Wood Science and Technology,2026,40(01):41-50. DOI： 10.12326/j.2096-9694.2025113.

摘要

为解决酚醛树脂固化后脆性大及竹塑复合材料界面应力集中的问题，研究提出一种基于共价/动态共价键的协同交联改性策略。采用苯硼酸（phenylboronic acid，PBA）和六亚甲基四胺（hexamethylenetetramine，HMTA）作为固化剂制备改性酚醛树脂基竹塑复合材料，并分析复合材料的力学性能、润湿性、热稳定性及回收再利用性能。结果表明，当热塑性酚醛树脂（novolac resin，NR）、PBA、HMTA与毛竹竹粉的质量比为100∶15∶5.5∶60时，制备的改性酚醛树脂基竹塑复合材料综合性能最佳，弯曲强度、拉伸强度和抗冲击强度分别为124.60 MPa、31.40 MPa和3.63 kJ/m

，断裂能达到1 433.7 kJ/m

。其弯曲强度和断裂能比HMTA单独改性酚醛树脂基竹塑复合材料提升43.7%和168.3%，表明硼酸酯动态共价键改性对复合材料的强度和韧性具有显著增强作用。其原因是酚醛树脂基竹塑复合材料体系中引入硼

酸酯键，构建共价/动态共价协同交联网络，在有效能量损耗的基础上实现基体增强和界面结合能力提升，从而提高复合材料的强度与韧性。改性酚醛树脂基竹塑复合材料还具有良好的热稳定性与耐水性（72 h吸水率仅为2.5%），且呈现良好的可回收潜力。研究可为高性能、可持续的生物基复合材料开发利用提供新思路。

Abstract

To address the brittleness of phenolic resin after curing and the stress concentration at the interface of bamboo-plastic composites

this study proposes a synergistic crosslinking modification strategy based on dynamic covalent bonds. Phenylboronic acid (PBA) and hexamethylenetetramine (HMTA) were used as curing agents to prepare modified phenolic resin-based bamboo-plastic composites

and their mechanical properties

wettability

thermal stability

and recyclability were investigated. The results showed that when the mass ratio of novolac resin (NR)

PBA

HMTA

and bamboo powder (

Phyllostachys edulis

) was 100∶15∶5.5∶60

the modified phenolic resin-based bamboo-plastic composites exhibited the best overall performance. The flexural strength

tensile strength

impact strength and fracture energy reached 124.60 MPa

31.40 MPa

3.63 kJ/m

and 1 433.7 kJ/m

respectively. Compared with HMTA-modified composites

the flexural strength and fracture energy increased by 43.7 % and 168.3 %

respectively

indicating that modification with boronate ester dynamic covalent bonds significantly improved both the strength and toughness of the composites. The reason could be attributed to the introduction of boronate ester bonds into the composites

which constructed a synergistic cross-linked network

enabling effective energy dissipation and achieving matrix and interfacial bonding strength improvement

thereby enhancing both strength and toughness of composites. In addition

the modified composites also exhibits excellent thermal stability and water resistance (the water absorption rate after 72 h was only 2.5%)

and demonstrates good recyclability potential. This research can provide new approach for the development and utilization of high-performance and sustainable bi

o-based composites.

关键词

Keywords

references

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