Synthesis of polyoxymethylene dimethyl ethers from dimethoxymethane and trioxane catalyzed by ionic liquids encapsulated in caged mesoporous KIT-5 material
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摘要: 采用包埋法将离子液体封装在分子筛KIT-5孔笼内，制备了四种负载型离子液体催化剂，用于甲缩醛和三聚甲醛合成聚甲醛二甲醚（PODEn），研究了不同条件对三聚甲醛转化率和目标产物PODE3-5选择性的影响。结果表明，催化合成PODEn的最佳反应条件为：反应时间2 h、100 ℃、甲缩醛与三聚甲醛物质的量比1.5、催化剂含量3%，在此条件下，四种催化剂均表现出了很好的催化效果。与离子液体催化剂相比，负载型催化剂的催化活性基本保持不变，而且性能稳定，可多次使用，具有一定的实用价值。Abstract: Four kinds of supported ionic liquid catalysts were prepared by encapsulation of ionic liquids within the nanocage of KIT-5 and were used in the synthesis of polyoxymethylene dimethyl ether (PODEn) from dimethoxymethane and trioxane; the effects of conditional parameters on the conversion of trioxane and the selectivity to targeted PODE3-5 were systematically investigated. The results show that the optimum reaction parameters for the synthesis of polyoxymethylene dimethyl ether were: reaction time of 2 h, 100 ℃, dimethoxymethane to trioxane molar ratio of 1.5, and catalyst content of 3%. Under the optimum conditions, the encapsulated catalysts are efficient in the synthesis of polyoxymethylene dimethyl ether, with a similar catalytic activity to the homogeneous counterparts. Moreover, the encapsulated catalysts can be reused several times without remarkable loss of activity and product selectivity, which makes it a promising catalyst for practical applications.
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Key words:
- polyoxymethylene dimethyl ethers /
- ionic liquids /
- KIT-5 /
- catalysts
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图 1 KIT-5或KIT-5-X的吸收光谱谱图
Figure 1 UV-vis spectra of KIT-5 or KIT-5-X
a: IL2 in methanol solution; b: after adsorption with KIT-5-C12; c: after adsorption with KIT-5-C8; d: after adsorption with KIT-5-C3; e: after adsorption with KIT-5
图 2 不同样品的XRD谱图
Figure 2 XRD patterns of various samples
a: KIT-5; b: KIT-5-C12; c: IL1@KIT-5-C12; d: IL2@KIT-5-C12; e: IL3@KIT-5-C12; f: IL4@KIT-5-C12
图 3 KIT-5、KIT-5-C12和IL3@KIT-5-C12的N2吸附-脱附等温线
Figure 3 N2 adsorption-desorption isotherms of KIT-5(a), KIT-5-C12 (b) and IL3@KIT-5-C12 (c)
图 4 KIT-5、KIT-5-C12和IL3@KIT-5-C12孔径分布
Figure 4 Pore diameter distributions of KIT-5 (a), KIT-5-C12 (b) and IL3@KIT-5-C12 (c)
图 5 不同样品的FT-IR谱图
Figure 5 FT-IR spectra of various samples
a: KIT-5; b: IL1@KIT-5-C12; c: IL2@KIT-5-C12; d: IL3@KIT-5-C12; e: IL4@KIT-5-C12
图 6 不同样品的TGA曲线
Figure 6 TGA curves of different samples
a: KIT-5; b: KIT-5-C12; c: IL1@KIT-5-C12; d: IL2@KIT-5-C12; e: IL4@KIT-5-C12; f: IL3@KIT-5-C12
图 7 不同反应条件下合成PODE3-5的催化活性
Figure 7 Catalytic tests for the synthesis of PODE3-5 under different conditions
(a): varying reaction time (100 ℃, dimethoxymethane/trioxane molar ratio of 1.5, and 3% catalyst); (b): varying reaction temperature (dimethoxymethane/trioxane molar ratio of 1.5, and 3% catalyst, reaction for 2 h); (c): varying catalyst dosage (100 ℃, dimethoxymethane/trioxane molar ratio of 1.5, reaction for 2 h); (d): varying molar ratio of dimethoxymethane and trioxane (100 ℃, 3% catalyst, and reaction for 2 h)
图 8 IL3@KIT-5-C12的循环实验
Figure 8 Recycling tests of IL3@KIT-5-C12 under 100 ℃, dimethoxymethane/trioxane molar ratio of 1.5, catalyst dosage of 3%, and reaction for 2 h
: x(TOX); : w(PODE3-5)
图 9 不同催化剂的催化性能比较
Figure 9 Comparison of different catalysts in their activity
a: IL4@KIT-5-C12; b: IL3@KIT-5-C12; c: IL2@KIT-5-C12; d: IL1@KIT-5-C12 reaction conditions: 2 h, 100 ℃, catalyst dosage 3%, dimethoxymethane and trioxane molar ratio of 1.5 : x(TOX); : w(PODE3-5)
表 1 不同样品的结构参数
Table 1 Textural properties of different samples
Sample BET surface area A/ (m2·g-1) Pore volume v/ (cm3·g-1) BJH pore diameter d/nm KIT-5 852 0.50 2.7 KIT-5-C12 235 0.29 2.4 IL3@KIT-5-C12 130 0.17 2.0 
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表 2 不同样品的元素分析
Table 2 Elemental analysis of different samples
Sample w(S)/% w(ILs)/% KIT-5-C12 0.00 0.00 IL1@KIT-5-C12 2.04 10.17 IL2@KIT-5-C12 1.77 10.39 IL3@KIT-5-C12 2.16 10.18 IL4@KIT-5-C12 1.96 10.83
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表 3 游离催化剂和负载催化剂的性能比较
Table 3 Performance comparison between free IL4 catalyst and supported IL4@KIT-5-C12 catalyst
Catalyst x(TOX)/% w(PODE3-5)/% KIT-5 0.00 0.00 IL4 83.69 44.43 IL4@KIT-5-C12 82.97 43.36
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