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Application of lanthanum-modified chiral nematic mesoporous silicon catalyst in synthesis of borneol

A chiral nematic, mesoporous silicon technology, used in catalyst activation/preparation, physical/chemical process catalysts, hydroxyl compound preparation, etc. The effect of production cost, reduced equipment requirements, and simple preparation process

Active Publication Date: 2020-06-05
KUNMING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Turpentine can be directly used in medicine and as a solvent, but more importantly, it is used in fine chemistry, such as synthesizing daily chemical fragrances, pharmacologically active substances, agricultural and household biologically active substances and functional materials, etc. Turpentine can be processed through esterification-saponification Obtain high-value borneol; borneol has isomers, divided into orthoborneol and isoborneol, because the side effects of isoborneol are far greater than those of orthoborneol, and due to the properties of these two substances and their Similar, there is no effective separation method, which is not conducive to the application of orthoborneol, so the use value of orthoborneol greatly exceeds that of isoborneol; orthoborneol can be used for medicine, fine spices, etc.
[0003] At present, in the research on the synthesis of borneol from α-pinene, boric anhydride and metaboric acid catalysts are the most commonly used in industry, and the production technology is mature, but the reaction process Medium heat exotherm is violent, is not easy to control, and the productive rate of borneol is unsatisfactory, and isoborneol accounts for a higher proportion in borneol total amount, generates a large amount of isoborneols
According to current literature reports, the solid superacid S2O82- / ZrO2 prepared by precipitation method -NiO catalyst, using anhydrous oxalic acid as esterification agent, synthesize borneol by esterification-saponification two-step method, the yield of borneol is as high as 55.8%, and the content of orthoborneol in the total borneol can reach 77.01%. This method Although a high proportion of orthoborneol has been obtained, the reaction is stable, and the catalyst is easy to separate, but there is still isoborneol in the product, which still faces the problem of separation, and S2O8 sub>2- is an active component that has potential safety hazards and is prone to explosion, which is not conducive to industrialization; in the application number 201910589375.9, Al2O3 / CNMS-SO3H is a catalyst for esterification and saponification to generate borneol. The highest yield of borneol is 53.94%, and the content of orthoborneol is 70.5%, but it still needs to face isoborneol Separation problem, not conducive to the recycling of orthoborneol

Method used

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  • Application of lanthanum-modified chiral nematic mesoporous silicon catalyst in synthesis of borneol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1: The method for synthesizing orthoborneol of this lanthanum-modified chiral nematic mesoporous silicon catalyst is as follows:

[0027] (1) Take 10g of microcrystalline cellulose (MCC) and put it into 100g of sulfuric acid with a mass concentration of 60% for ultrasonic treatment for 30 minutes. The ultrasonic temperature does not exceed 40°C, then hydrolyze it under magnetic stirring and water bath constant temperature of 40°C for 30 minutes, and then ultrasonically treat it for 1h. , the ultrasonic temperature does not exceed 40°C; add 500mL ultrapure water to the mixture, sonicate for 30min and the temperature does not exceed 40°C, let it stand for 24h, collect the supernatant by centrifugation, put the supernatant in a dialysis bag and dialyze in ultrapure water to The pH in the bag is 2.5, and the liquid in the bag is collected to obtain a nanocrystalline cellulose (NCC) suspension;

[0028] (2) Using orthomethyl silicate (TMOS) as the silicon source a...

Embodiment 2

[0033] Embodiment 2: The method for synthesizing orthoborneol of this lanthanum-modified chiral nematic mesoporous silicon catalyst is as follows:

[0034] (1) Take 7g of microcrystalline cellulose (MCC) and put it into 100g of sulfuric acid with a mass concentration of 65% for ultrasonic treatment for 25 minutes. The ultrasonic temperature should not exceed 40°C, then hydrolyze for 25 minutes under magnetic stirring and water bath at a constant temperature of 45°C, and then ultrasonically treat for 2 hours. , the ultrasonic temperature does not exceed 40°C; add 600mL ultrapure water to the mixture, sonicate for 35min and the temperature does not exceed 40°C, let it stand for 25h, centrifuge to collect the supernatant, put the supernatant in a dialysis bag and dialyze in ultrapure water to The pH inside the belt is 2.5, and the liquid in the collection bag is obtained as nanocrystalline cellulose (NCC) suspension;

[0035] (2) Using orthomethyl silicate (TMOS) as the silicon sou...

Embodiment 3

[0038] Embodiment 3: The method for synthesizing orthoborneol by this lanthanum-modified chiral nematic mesoporous silicon catalyst is as follows:

[0039] (1) Take 8g of microcrystalline cellulose (MCC) and put it into 100g of sulfuric acid with a mass concentration of 70% for ultrasonic treatment for 35 minutes. The ultrasonic temperature should not exceed 40°C, then hydrolyze for 35 minutes with magnetic stirring and water bath at a constant temperature of 35°C, and then ultrasonically treat for 3h. , the ultrasonic temperature does not exceed 40°C; add 600mL ultrapure water to the mixture, sonicate for 25min and the temperature does not exceed 40°C, let it stand for 25h, centrifuge to collect the supernatant, put the supernatant in a dialysis bag and dialyze in ultrapure water to The pH inside the belt is 2.3, and the liquid in the collection bag is obtained as nanocrystalline cellulose (NCC) suspension;

[0040] (2) Using orthomethyl silicate (TMOS) as the silicon source ...

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Abstract

The invention discloses an application of a lanthanum-modified chiral nematic mesoporous silicon catalyst in synthesis of borneol, and lanthanum-modified chiral nematic mesoporous silicon can catalyzeand synthesize borneol with high selectivity in catalyzing an esterification-saponification reaction of alpha-pinene. According to the method, the problems that in the prior art, alpha-pinene is usedas a raw material for the esterification-saponification reaction, the yield of borneol is low, the catalyst selectivity is poor, and the catalyst is difficult to reuse are solved; according to the present invention, with the catalyst, the borneol can be directly obtained, the difficulty of the borneol separation is avoided, and the preparation process is simple, and is suitable for industrial production and market promotion and application.

Description

technical field [0001] The invention relates to the application of a lanthanum-modified chiral nematic mesoporous silicon catalyst in the selective synthesis of borneol, which belongs to the field of chemical industry. Background technique [0002] Turpentine is a renewable essential oil that contains a variety of terpenes, the main components of which are α-pinene and β-pinene, which are isomers of each other, and the content of α-pinene is more than 90%. Turpentine can be directly used in medicine and as a solvent, but more importantly, it is used in fine chemistry, such as synthesizing daily chemical fragrances, pharmacologically active substances, agricultural and household biologically active substances and functional materials, etc. Turpentine can be processed through esterification-saponification Obtain high-value borneol; borneol has isomers, divided into orthoborneol and isoborneol, because the side effects of isoborneol are far greater than those of orthoborneol, a...

Claims

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Application Information

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IPC IPC(8): B01J27/02B01J35/10B01J37/02B01J37/08C07C29/09C07C35/30
CPCB01J27/02B01J37/0205B01J37/0236B01J37/088C07C29/095C07C67/04B01J35/60C07C35/30C07C69/36
Inventor 王亚明郭炜蒋丽红郑燕娥贾庆明陕绍云刘壁莹
Owner KUNMING UNIV OF SCI & TECH
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