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Mesoporous hollow silicon dioxide nanospheres loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silicon dioxide nanospheres

A technology of mesoporous silica and silica, applied in the field of polymer materials and heterogeneous catalysis, can solve the problems of green chemistry obstacles, collapse, environmental pollution, etc., and achieve the effect of overcoming difficult activation.

Active Publication Date: 2020-12-25
CHONGQING UNIV OF POSTS & TELECOMM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Silica mesoporous nanospheres can provide a specific surface area of ​​30-150m2 g-1, for Catalytic reactions with large loading requirements are far from enough. In order to increase its specific surface area, reducing the shell thickness is also a common method in addition to passing through mesopores. However, the support force of nanospheres is limited, and the shell thickness is too thin. its collapse or rupture
Because the amount of prolinol catalyst added in the catalytic reaction is large (10-30mol%), it is difficult to separate, recycle and reuse the prolinol catalyst after the reaction, which increases the subsequent separation cost, pollutes the environment, and plays an important role in the development of green chemistry. to hinder

Method used

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  • Mesoporous hollow silicon dioxide nanospheres loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silicon dioxide nanospheres
  • Mesoporous hollow silicon dioxide nanospheres loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silicon dioxide nanospheres
  • Mesoporous hollow silicon dioxide nanospheres loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silicon dioxide nanospheres

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Weigh 0.35g of cetyltrimethylammonium bromide and 0.15g of 1,3,5-triisopropylbenzene, dissolve in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, add the dispersed PS / AA 20mL (200mg), kept heated in a water bath at 60°C, and stirred by magnetic force at 400r / min for 30min. Add 8 mL of tetraethyl orthosilicate dropwise within 15 minutes, keep the rotation speed and continue the reaction for 2 hours, then centrifuge the milky white solution to obtain solid particles. After washing with distilled water 2×8mL times and absolute ethanol 2×8mL times, put them into an oven at 80°C to dry for 24h. The dried product was then placed in a muffle furnace and calcined at 600 °C for 15 h (heating rate 2 °C min -1 ), cooled to room temperature to obtain hollow mesoporous silica nanospheres.

Embodiment 2

[0033]Weigh 0.35g of cetyltrimethylammonium bromide (CTAB) and 0.10g of 1,3,5-triisopropylbenzene, dissolve in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, add The dispersed PS / AA (400mg) was kept heated in a water bath at 60°C, and stirred by magnetic force at 400r / min for 30min. 8 mL of tetraethyl orthosilicate (TEOS) was added dropwise within 15 min, and the reaction was continued for 2 h while maintaining the rotational speed, and then the milky white solution was centrifuged to obtain solid particles. After washing with distilled water 2×8mL times and absolute ethanol 2×8mL times, put them into an oven at 80°C to dry for 24h. The dried product was then placed in a muffle furnace and calcined at 350 °C for 15 h (heating rate 3 °C min -1 ), cooled to room temperature to obtain hollow mesoporous silica nanospheres.

Embodiment 3

[0035] Weigh 0.35g of cetyltrimethylammonium bromide and 0.20g of 1,3,5-triisopropylbenzene, dissolve in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, add the dispersed PS / AA (1000mg), kept heated in a water bath at 60°C, and stirred by magnetic force at 400r / min for 30min. Add 8 mL of tetraethyl orthosilicate dropwise within 15 minutes, keep the rotation speed and continue the reaction for 2 hours, then centrifuge the milky white solution to obtain solid particles. After washing with distilled water 2×8mL times and absolute ethanol 2×8mL times, put them into an oven at 80°C to dry for 24h. The dried product was then placed in a muffle furnace and calcined at 800 °C for 15 h (heating rate 3 °C min -1 ), cooled to room temperature to obtain hollow mesoporous silica nanospheres.

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Abstract

The invention discloses mesoporous hollow silicon dioxide nanospheres loaded with a prolinol catalyst as well as a preparation method and application of the mesoporous hollow silicon dioxide nanospheres. Mesoporous silicon dioxide with an ultra-large specific surface area is firstly prepared, a shell layer is very thin, and the maximization of the loading capacity is ensured. The mesoporous hollowsilicon dioxide nanospheres are effectively combined with the prolinol catalyst, and the defect that silicon dioxide is not easy to activate is overcome. The hollow silicon dioxide nanospheres and the prolinol catalyst are effectively combined and successfully applied to Michael / Michael / aldol cascade reaction with strict catalytic requirements, and a good result (ee is close to 100%, and Dr is 98: 2) is obtained. The catalytic effect is decreased progressively only after the catalyst is recycled for 8 times, which indicates that the structure of the silicon dioxide spheres is stable and a method for combining a hydrolysis method and an organic group is very suitable.

Description

technical field [0001] The invention belongs to the field of macromolecular materials and heterogeneous catalysis, and relates to a mesoporous hollow silicon dioxide nanosphere with a super large specific surface area loaded with a catalyst, a preparation method, and an application in an asymmetric series reaction. Background technique [0002] In recent years, hollow nanospheres have attracted increasing attention and research due to their unique properties, such as low density, good thermal stability and surface permeability, and large internal space. Many materials such as inorganic materials (zeolite, hydroxyapatite, titanium dioxide, alumina, gallium oxide, gallium nitride, etc.), organic polymer materials (polystyrene, etc.), have been made into hollow spherical structures and present conventional The special functions that materials do not have, are widely used in many fields such as drug sustained / controlled release systems, chromatographic separation, catalysts, coa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07D307/94
CPCB01J31/0271B01J31/0254C07D307/94B01J2231/328Y02P20/584
Inventor 谢广新张灵周贤菊李丽唐笑罗小兵江莎曹中民凌发令李艳虹姚璐
Owner CHONGQING UNIV OF POSTS & TELECOMM
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