CN114308111B

CN114308111B - Preparation method and application of alkaline solid catalyst

Info

Publication number: CN114308111B
Application number: CN202111620430.XA
Authority: CN
Inventors: 王嘉辉; 孔令晓; 张涛; 沈宏强; 刘英瑞; 张弈宇; 宋军伟; 罗朝辉; 黎源
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2021-12-28
Filing date: 2021-12-28
Publication date: 2023-12-19
Anticipated expiration: 2041-12-28
Also published as: CN114308111A

Abstract

The invention provides a preparation method and application of an alkaline solid catalyst. The preparation method of the catalyst comprises the following steps: 1) Coupling reaction of 3-aminopropyl silane and carbodiimide to obtain guanidyl silane; 2) The obtained guanidinosilane reacts with the activated molecular sieve to obtain the basic solid catalyst. The invention also provides a method for preparing the deca-dialdehyde from acidolysis substances through alkaline hydrolysis under the action of the alkaline solid catalyst. The method has high selectivity and conversion rate in alkaline hydrolysis reaction, is not easy to generate byproducts, has small environmental pollution, can recycle the catalyst for multiple times, has small corrosion to equipment, and is suitable for industrial production.

Description

Preparation method and application of alkaline solid catalyst

Technical Field

The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method and application of an alkaline solid catalyst.

Background

Deca-dialdehyde, 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, has the formula C ₁₀ H ₁₂ O ₂ The solid is yellowish powder solid at normal temperature, is an important key intermediate for synthesizing carotenoid, and plays a key role in synthesizing pigments such as beta-carotene, canthaxanthin, astaxanthin and the like.

In the technological routes reported in patents US20020128520, US6673972, US5300658, US5382732 and the like, furan is taken as a starting material, the furan and methanol are subjected to two-step addition to obtain 1, 4-tetramethoxy-2-butene, the 1, 4-tetramethoxy-2-butene is subjected to condensation reaction with propenyl methyl ether under the catalysis of Lewis acid to obtain a deca-dialdehyde skeleton, and then the double bond of the methanol is eliminated by alkali treatment to obtain the product. Bromine is used in the route, the price is high, the toxicity is high, the chemical property is active and unstable, in addition, the side reaction is more in the addition reaction of the acetal, the added product is still in a diacetal structure, and the product can be further condensed with propenyl methyl ether to generate telomerization reaction to form a polymer, so that the impurity content of the finally obtained product is higher.

Patent US5276209 takes 1-ethoxy-1-propylene as a starting material, and is added with triethyl orthoformate under the catalysis of Lewis acid to obtain 1, 3-tetraethoxy-2-methylpropane, ethanol is eliminated under the promotion of acid to form a 2-methyl-3-ethoxy-2-butenal compound, the 2-methyl-3-butenal compound is added with acetylene double Grignard reagent, then an olefinic bond is formed by dehydration, a triple bond is partially hydrogenated to form double bonds, finally acetal is deprotected, and deca-dialdehyde is synthesized through seven steps of reaction.

The method for synthesizing the deca-dialdehyde has the defects that the steps are too long, and the total yield is low; or the used compound has high toxicity and is not friendly to the environment.

Chinese patent CN100460378C synthesizes deca-dialdehyde with high efficiency through three steps of addition, acidolysis and alkaline hydrolysis, and in the alkaline hydrolysis elimination reaction, the promoter sodium bicarbonate has poor thermal stability, is easy to decompose after being heated, and the catalytic efficiency is continuously reduced. Meanwhile, the water-soluble impurities of the organic phase bring more problems to production.

In summary, in the method for preparing the deca-dialdehyde by enol ether condensation, the use of strong base in the elimination reaction has higher requirements on equipment, the product quality of the deca-dialdehyde can be reduced, and the use of weak base can cause the increase of three wastes. Therefore, development of an environmentally friendly, high product quality, low cost production process is necessary for synthesizing deca-dialdehyde.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a preparation method of an alkaline solid catalyst and application of the alkaline solid catalyst in catalytic synthesis of deca-dialdehyde. The catalyst has high selectivity and conversion rate in alkaline hydrolysis reaction, is not easy to generate byproducts, has little environmental pollution, can be recycled for multiple times, has little corrosion to equipment, and is suitable for industrial production.

In order to achieve the above object, the present invention has the following technical scheme:

the invention provides a preparation method of an alkaline solid catalyst, which comprises the following steps:

1) Coupling reaction of 3-aminopropyl silane and carbodiimide to obtain guanidyl silane;

2) The obtained guanidinosilane reacts with the activated molecular sieve to obtain the basic solid catalyst.

The 3-aminopropyl silane in step (1) of the present invention is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane or 3-aminopropyl tripropoxysilane, preferably 3-aminopropyl triethoxysilane is used.

The carbodiimide in the step (1) is one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.

In the present invention, the coupling reaction in step (1) is carried out under the action of a copper-based metal catalyst such as copper chloride, copper sulfate, copper triflate and copper nitrate, preferably copper chloride as a catalyst.

Preferably, the molar ratio of the copper-based catalyst used in the step (1) to the 3-aminopropyl silane is 0.01-0.1:1, preferably 0.05-0.08:1.

In the present invention, the coupling reaction in step (1) is performed in an organic solvent, which may be a protic solvent such as methanol, ethanol, isopropanol or hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform, dichloroethane or chlorobenzene; ester solvents such as ethyl acetate, methyl propionate, and mixtures of these solvents. Aromatic hydrocarbons are preferably used, toluene being particularly preferred as the reaction solvent.

Preferably, the reaction temperature of the step (1) is 30-80 ℃ and the reaction time is 8-15h.

Preferably, the molar ratio of the 3-aminopropyl silane to the carbodiimide added in step (1) is 1:0.9-1.5, preferably 1:1.1-1.2.

In the invention, the molecular sieve in the step (2) is one or more of SBA-15, SBA-16, ZSM-12 or ZSM-23, and preferably SBA-15 type molecular sieve is used.

According to the invention, the mass ratio of the guanidylsilane to the molecular sieve in the step (2) is 1:0.5-2.0, preferably 1:0.9-1.1.

The reaction in step (2) is carried out in an alcoholic solvent, preferably one or more of ethanol, methanol, isopropanol and hexafluoroisopropanol.

The reaction temperature of the step (2) is 30-60 ℃ and the reaction time is 10-20h.

The molecular sieve in the step (2) is activated by drying in a muffle furnace at 300-500 ℃ for 2-10h.

According to the invention, the catalyst obtained in the step (2) can be collected by filtration; the filtered product is preferably dried in vacuo after rinsing with solvent.

The invention relates to a preparation method of deca-dialdehyde, which adopts acidolysis substance with a structural formula I as raw material, and generates deca-dialdehyde through alkaline hydrolysis elimination reaction under the alkaline solid catalyst.

The acidolysis compound has a structure shown in a formula I, wherein the substituent R can be methyl, ethyl, isopropyl, tertiary butyl and phenyl, preferably methyl.

The alkaline hydrolysis reaction is carried out in a solvent, wherein the solvent is a proton solvent such as water, tertiary butanol, isopropanol or hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform, dichloroethane or chlorobenzene; ester solvents such as ethyl acetate, methyl propionate, and mixtures of these solvents. Preferably, a protic solvent is used, particularly preferably water as the reaction solvent.

In the preparation process of the decamethylene dialdehyde, a strong base catalyst is usually adopted, but the decamethylene dialdehyde is easy to disproportionate under the action of strong base to generate carboxylate and alcohol, so that the yield is reduced. The alkaline solid catalyst prepared by the invention has the advantages that the catalytic surface area is increased after being combined with the molecular sieve, and the active component amino has no catalytic effect on aldehyde groups of deca-dialdehyde, so that the catalyst can exist stably. When the alkoxy is eliminated, the synergistic effect is obvious, and an intermediate product is not present, so that the purity of the product is ensured.

The molecular equation of the disproportionation reaction is shown below.

In the present invention, the amount of the alkaline solid catalyst to be used is 0.01 to 0.5 times, preferably 0.05 to 0.1 times, the amount of the acidolysis product.

In the present invention, the alkaline hydrolysis elimination reaction temperature is from-20 to 100 ℃, preferably from 0 to 50 ℃, more preferably from 10 to 30 ℃, and the reaction time is from 1 to 20 hours, preferably from 5 to 10 hours.

The invention has the positive effects that:

1) The prepared alkaline catalyst is an organic-supported alkaline catalyst, has stable structure, strong selective catalysis, no intermediate product generation, high catalysis efficiency and no excessive reaction of products;

2) The reaction condition is mild, the catalyst can be recycled, the reaction efficiency is kept good after more than 20 times of application, and the catalyst is environment-friendly;

3) The process is simple to operate, the production amount of the three wastes is low, and the production cost is low, thereby being beneficial to industrial production.

Detailed Description

The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.

Gas chromatographic analysis conditions: carrying out on-line measurement on a polysiloxane column HP-5 of Agilent gas chromatography, carrying out second-order temperature programming, and keeping the initial temperature at 50 ℃ for 2 minutes and then raising the temperature to 150 ℃ at a speed of 10 ℃/min; then the temperature is raised to 250 ℃ at a speed of 15 ℃/min. Carrier gas high purity N ₂ Split ratio 150:1. the sample injection temperature is 250 ℃, the detector is FID, and the detector temperature is 260 ℃. The sample injection amount was 0.2. Mu.L.

The raw material sources are as follows:

reagent name	Reagent specification	Manufacturing factories
			Acidolysis product	99％,HPLC	New and become
Dichloromethane, toluene and ethyl acetate	99％,AR	An Naiji
			3-Aminopropyltriethoxysilane	98％,AR	Ara Ding Shiji
Polyoxyethylene-polyoxypropylene-polyoxyethylene (P123)	-	An Naiji
			Tetraethoxysilane (TEOS)	99％，AR	Pure Shanghai crystal industry
Dicyclohexylcarbodiimide	98％,AR	Ara Ding Shiji
			DiisopropylcarbadiimideAmines	98％,AR	Ara Ding Shiji

Preparation of SBA-15 molecular sieves

50g of P123 was weighed into a 5L beaker, 1500mL of 2mol/L hydrochloric acid and 380mL deionized water were added, respectively, and magnetically stirred at room temperature for 6h until P123 was completely dissolved. 105.3g of tetraethyl orthosilicate (TEOS) was weighed and added dropwise to the solution and stirred for 24h for complete reaction. Transferring the mixed solution into a stainless steel water heating reaction kettle, crystallizing for 48 hours in a baking oven (100 ℃), cooling to room temperature, vacuum filtering, washing with deionized water to obtain a white filter cake, and naturally airing. Calcining for 2 hours at 400 ℃ in a muffle furnace to obtain the activated SBA-15.

Example 1

Preparation of a Supported SBA-15 basic solid catalyst I:

0.11mol of 13.9g of diisopropylcarbodiimide and 0.1mol of 22.1g of 3-aminopropyl triethoxysilane were put in a 1000mL three-necked flask, 500mL of dry toluene was added simultaneously, followed by 0.01mol of 1.3g of copper chloride, and the mixture was magnetically stirred under a nitrogen atmosphere at a temperature of 80℃to react for 10 hours. Then 50mL of absolute ethanol and 32.4g of pre-activated SBA-15 were added and stirred magnetically at 45℃and the reaction was continued with nitrogen for 12h. After the reaction is stopped, cooling to room temperature, carrying out suction filtration, and washing by using absolute ethyl alcohol. The product was dried in vacuo at 40℃for 6h to finally give solid base catalyst I.

Example 2

Preparation of supported SBA-15 basic solid catalyst II:

0.15mol of 30.9g dicyclohexylcarbodiimide and 0.1mol of 22.1g of 3-aminopropyl triethoxysilane were put in a 1000mL three-necked flask, while 500mL of dry ethyl acetate was added thereto, followed by 0.005mol of 0.7g of copper chloride, and reacted for 15 hours under a nitrogen atmosphere with magnetic stirring at a temperature of 50 ℃. Then 50mL of isopropanol and 58.3g of pre-activated SBA-15 were added and stirred magnetically at 55deg.C, and the reaction was continued under nitrogen for 20h. After the reaction was stopped, it was cooled to room temperature, filtered off with suction, and washed with isopropanol. The product was dried in vacuo at 40 ℃ for 6h to finally prepare solid base catalyst II.

Example 3

Preparation of supported SBA-15 basic solid catalyst III:

0.15mol of 21.2g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.1mol of 22.1g of 3-aminopropyl triethoxysilane were placed in a 1000mL three-necked flask, 500mL of dry ethyl acetate was added, followed by 0.01mol of 1.3g of copper chloride, and the mixture was magnetically stirred under nitrogen atmosphere at a temperature of 60℃for reaction for 12 hours. Then 50mL of isopropanol and 58.3g of pre-activated SBA-15 were added and stirred magnetically at 55deg.C, and the reaction was continued under nitrogen for 20h. After the reaction was stopped, it was cooled to room temperature, filtered off with suction, and washed with isopropanol. The product was dried in vacuo at 40℃for 6h to finally give solid base catalyst III.

Example 4

Preparing decanal:

A1.0L three-neck flask was used as a reaction vessel, 22.8g of acidolysis product, 100g of pure water and 2.3g of alkaline solid catalyst I were added in this order, and the reaction system was placed in an oil bath at 30℃and stirred to start the reaction. After 10.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 96.8%, the selectivity was 97.3%, and the reaction yield was 94.2%.

Example 5

Preparing decanal:

the catalyst of example 4 was filtered, and the obtained catalyst was washed with absolute ethanol and then air-dried to obtain the catalyst of example 5.

A1.0L three-neck flask is taken as a reaction kettle, 22.8g of acidolysis substances, 200g of water and 2.2g of recovered alkaline solid catalyst I are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 50 ℃ and stirred to start reaction. After 8.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 96.3%, the selectivity was 96.9%, and the reaction yield was 93.3%.

Example 6

Preparing decanal:

catalyst I of example 5 was filtered, and the resulting catalyst was washed with absolute ethanol and then air-dried to give the catalyst of example 6.

A1.0L three-neck flask is taken as a reaction kettle, 22.8g of acidolysis substances, 200g of toluene and 2.0g of recovered alkaline solid catalyst I are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 40 ℃ and stirred to start reaction. After 8.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 94.6%, the selectivity was 95.9%, and the reaction yield was 90.7%.

Example 7

Preparing decanal:

A2.0L three-neck flask is taken as a reaction kettle, 68.4g of acidolysis substances, 1000g of ethanol and 3.4g of alkaline solid catalyst I are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 60 ℃ and stirred to start reaction. After 10.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 95.6%, the selectivity was 85.3%, and the reaction yield was 81.5%.

Example 8

Preparing decanal:

A1.0L three-neck flask is taken as a reaction kettle, 22.8g of acidolysis substances, 300g of water and 4.6g of alkaline solid catalyst II are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 90 ℃ and stirred to start reaction. After 4.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 97.8%, the selectivity was 98.3%, and the reaction yield was 96.1%.

Example 9

Preparing decanal:

the catalyst II of example 8 was filtered, and the obtained catalyst was washed with absolute ethanol and then air-dried to obtain a catalyst of example 9.

A1.0L three-neck flask is taken as a reaction kettle, 11.4g of acidolysis substances, 500g of dichloromethane and 4.4g of recovered alkaline solid catalyst II are sequentially added into the reaction kettle, and the reaction system is placed in a low-temperature tank at 10 ℃ and stirred to start reaction. After 8.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 90.3%, the selectivity was 92.5%, and the reaction yield was 83.5%.

Example 10

Preparing decanal:

A1.0L three-neck flask is taken as a reaction kettle, 11.4g of acidolysis substances, 200g of dichloromethane and 3.5g of alkaline solid catalyst III are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 60 ℃ and stirred to start reaction. After 15.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 93.6%, the selectivity was 94.2%, and the reaction yield was 87.8%.

Example 11

Preparing decanal:

the catalyst III in example 10 was filtered, and the obtained catalyst was washed with absolute ethanol and then air-dried to obtain a catalyst of example 11.

A2.0L three-neck flask is taken as a reaction kettle, 22.8g of acidolysis substances, 1000g of dichloromethane and 3.5g of recovered alkaline solid catalyst III are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath pot at 80 ℃ and stirred to start reaction. After 10.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 92.9%, the selectivity was 93.8%, and the reaction yield was 87.1%.

Comparative example 1

Preparing decanal:

A1.0L three-neck flask was used as a reaction vessel, 22.8g of acidolysis product, 100.0g of water and 46.5g of 5% sodium bicarbonate aqueous solution were sequentially added thereto, and the reaction system was placed in an oil bath pot at 30℃and stirred to start the reaction. After 10.0 hours of reaction, the reaction was stopped and a sample was taken for gas phase analysis. The reaction conversion was 92.6%, the selectivity was 85.6%, and the reaction yield was 79.3%.

Claims

1. The preparation method of the deca-dialdehyde is characterized in that acidolysis substances with the structure shown in the formula I are adopted as raw materials, and an alkaline solid catalyst is used for carrying out alkaline hydrolysis elimination reaction to generate the deca-dialdehyde;

the acidolysis compound has a structure shown in a formula I, wherein a substituent R is methyl, ethyl, isopropyl, tertiary butyl and phenyl;

the preparation method of the alkaline solid catalyst comprises the following steps:

(1) Coupling reaction of 3-aminopropyl silane and carbodiimide to obtain guanidyl silane;

(2) The obtained guanidyl silane reacts with the activated molecular sieve to obtain an alkaline solid catalyst;

the carbodiimide in the step (1) is one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide;

the coupling reaction in the step (1) occurs under the action of a copper-based metal catalyst;

the molecular sieve in the step (2) is one or more of SBA-15, SBA-16, ZSM-12 or ZSM-23.

2. The method of claim 1, wherein the 3-aminopropyl silane in step (1) is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, or 3-aminopropyl tripropoxysilane.

3. The method of claim 2, wherein the 3-aminopropyl silane in step (1) is 3-aminopropyl triethoxysilane.

4. The method according to claim 1, wherein the copper-based metal catalyst is selected from the group consisting of copper chloride, copper sulfate, copper triflate, and copper nitrate.

5. The method according to claim 4, wherein the copper-based metal catalyst is copper chloride.

6. The method according to claim 1, wherein the molar ratio of the copper-based metal catalyst used in the step (1) to the 3-aminopropyl silane is 0.01 to 0.1:1.

7. the process according to claim 6, wherein the molar ratio of the copper-based metal catalyst used in the step (1) to the 3-aminopropyl silane is 0.05 to 0.08:1.

8. The process according to claim 1, wherein the reaction temperature in step (1) is 30 to 80℃and the reaction time is 8 to 15 hours.

9. The process of claim 1 wherein in step (1) the molar ratio of 3-aminopropylsilane to carbodiimide is added in the range of 1:0.9 to 1.5.

10. The process of claim 9 wherein in step (1) the molar ratio of 3-aminopropylsilane to carbodiimide is added in the range of 1:1.1 to 1.2.

11. The method of claim 1, wherein the molecular sieve is an SBA-15 type molecular sieve.

12. The method of claim 1, wherein the mass ratio of guanidinosilane to molecular sieve in step (2) is 1:0.5-2.0.

13. The method of claim 12, wherein the mass ratio of guanidinosilane to molecular sieve in step (2) is 1:0.9-1.1.

14. The process according to claim 1, wherein the reaction in step (2) is carried out in an alcoholic solvent.

15. The method of claim 14, wherein the alcoholic solvent is selected from one or more of ethanol, methanol, isopropanol, and hexafluoroisopropanol.

16. The process according to claim 1, wherein the reaction temperature in step (2) is 30 to 60℃and the reaction time is 10 to 20 hours.

17. The process of claim 1 wherein the molecular sieve in step (2) is activated by drying in a muffle furnace at 300-500 ℃ for 2-10 hours.

18. The preparation method according to claim 1, wherein the amount of the basic solid catalyst is 0.01 to 0.5 times the amount of the acidolysis product.

19. The process according to claim 18, wherein the amount of the basic solid catalyst is 0.05 to 0.1 times the amount of the acidolysis product.

20. The preparation method according to claim 1, wherein the alkaline hydrolysis elimination reaction temperature is 10-100 ℃ and the reaction time is 1-20h.

21. The method according to claim 20, wherein the alkaline hydrolysis elimination reaction temperature is 10 to 50 ℃ and the reaction time is 5 to 10 hours.

22. The process of claim 21, wherein the alkaline hydrolysis elimination reaction temperature is 10-30 ℃.