Developing efficient catalysts for the synthesis of 5-hydroxymethylfurfural (HMF) from biomass resources is very demanding as it is an important renewable platform chemical for the synthesis of biofuels, polymers and fine chemicals. Here, we have designed two new crystalline microporous bi-functional porous organic polymers through the extended aromatic substitution reaction under refluxing conditions. Porous polymers containing sulfonic acid and secondary amine groups are two reactive catalytic centres for carrying out the bi-functional heterogeneously catalysed reactions. Bifunctionalized porous polymers POPDS and POPSDS are synthesized through the reaction of 2,2′-benzidinedisulfonic acid and 4,4′-diaminostilbene-2,2′-disulfonic acid with cyanuric chloride, respectively. The materials were characterized thoroughly using powder X-ray diffraction, N₂ sorption, FTIR, solid state ¹³C CP MAS NMR spectroscopy, FE-SEM, HR-TEM, XPS and TG/DTA analysis. These two crystalline porous polymers possesses good surface acidic and basic sites, and having flower-like and spherical particle morphologies. POPDS and POPSDS exhibited superior catalytic activity for the conversion of different small carbohydrates to 5-hydroxymethylfurfural (HMF) under microwave irradiation. Moreover, the recyclability tests of these catalysts revealed good durability up to sixth consecutive reaction cycles, suggesting the future potential of these catalysts in the sustainable synthesis of HMF.

开发用于从生物质资源中合成 5-羟甲基糠醛 (HMF) 的高效催化剂的要求非常高，因为它是合成生物燃料、聚合物和精细化学品的重要可再生平台化学品。在这里，我们通过回流条件下的扩展芳族取代反应设计了两种新型结晶微孔双功能多孔有机聚合物。含有磺酸和仲胺基团的多孔聚合物是进行双功能非均相催化反应的两个反应性催化中心。双官能化多孔聚合物 POPDS 和 POPSDS 分别通过 2,2'-联苯二磺酸和 4,4'-二氨基二苯乙烯-2,2'-二磺酸与氰尿酰氯反应合成。使用粉末 X 射线衍射对材料进行了彻底表征，₂吸附、FTIR、固态¹³ C CP MAS NMR 光谱、FE-SEM、HR-TEM、XPS 和 TG/DTA 分析。这两种结晶多孔聚合物具有良好的表面酸性和碱性位点，并具有花状和球形颗粒形态。POPDS 和 POPSDS 在微波辐射下对不同的小碳水化合物转化为 5-羟甲基糠醛 (HMF) 表现出优异的催化活性。此外，这些催化剂的可回收性测试显示，在连续第六个反应周期内具有良好的耐久性，表明这些催化剂在 HMF 可持续合成中的未来潜力。