氟磺酸改性磺酸型聚合物催化剂在甲醛羰基化中的性能研究

采用水热合成、原位磺化法制备了固体磺酸型聚合物PDS-1.0催化剂,以三氟甲烷磺酸对其进行接枝改性得到PDS-1.0-F催化剂;采用N_2吸附-脱附、TG、FT-IR、~(31)P M AS NMR和XPS等技术对催化剂的物理和化学性质进行了表征,以甲醛羰基化制乙醇酸为探针反应对其催化性能进行了评价研究。结果表明,与PDS-1.0催化剂相比,氟磺酸改性后的PDS-1.0-F催化剂的比表面积、孔容积和酸量均降低,但是酸强度和热稳定性显著增加,由此对甲醛羰基化反应具有较好的催化性能,乙醇酸收率达到91.2%。

Study on the performance of CF3SO3H modified sulfonic polymer-based catalyst in formaldehyde carbonylation reaction

A sulfonic polymer-based catalyst (PDS-1.0) was synthesized by the hydrothermal and in situ sulfonation method, which is further modified by grafting with CF₃SO₃H, to get the PDS-1.0-F catalyst. The physical and chemical properties of the PDS-1.0 and PDS-1.0-F catalysts were characterized by N₂ sorption, TG, FT-IR, ³¹P MAS NMR and XPS; the effect of CF₃SO₃H modification on the catalytic performance of PDS-1.0-F in the carbonylation of formaldehyde to glycolic acid was then investigated. The results show that after the CF₃SO₃H modification, the framework of PDS-1.0-F catalyst was grafted with strong electron withdrawing groups. In comparison with PDS-1.0, the CF₃SO₃H-modified PDS-1.0-F catalyst has a lower surface area, pore volume and concentration of acid sites, but much stronger acidity and higher thermal stability. As a result, the PDS-1.0-F catalyst exhibits excellent performance in the carbonylation of formaldehyde and over it the yield of glycolic acid reaches 91.2%.