CN114308111A - Preparation method and application of alkaline solid catalyst - Google Patents

Preparation method and application of alkaline solid catalyst Download PDF

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CN114308111A
CN114308111A CN202111620430.XA CN202111620430A CN114308111A CN 114308111 A CN114308111 A CN 114308111A CN 202111620430 A CN202111620430 A CN 202111620430A CN 114308111 A CN114308111 A CN 114308111A
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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
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Wanhua Chemical Group Co Ltd
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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) 3-aminopropyl silane and carbodiimide are subjected to coupling reaction to obtain guanidino silane; 2) and reacting the obtained guanidino silane with the activated molecular sieve to obtain the basic solid catalyst. The invention also provides a method for preparing the decamethylene through the alkaline hydrolysis reaction of the acidolysis product under the action of the alkaline solid catalyst. The method has high selectivity and conversion rate in the 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, molecular formula C10H12O2The carotenoid is a light yellow powdery 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 process routes reported in patents US20020128520, US6673972, US5300658, US5382732 and the like, furan is used as a starting material and is subjected to two-step addition with methanol to obtain 1,1,4, 4-tetramethoxy-2-butene, 1,1,4, 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 alkali treatment is carried out to eliminate methanol to form a double bond so as to obtain a product. Bromine is used in the route, the price is high, the toxicity is high, the chemical property is active and unstable, in addition, side reactions are more in the addition reaction of acetal, the addition product is still in a diacetal structure, and the side reaction can further generate telomerization reaction with propenyl methyl ether to form a polymer, so that the impurity content of the finally obtained product is higher.
Patent US5276209 uses 1-ethoxy-1-propene as starting material, and adds with triethyl orthoformate under lewis acid catalysis to obtain 1,1,3, 3-tetraethoxy-2-methylpropane, eliminates ethanol under acid promotion to form 2-methyl-3-ethoxy-2-butenal compound, adds with acetylene double Grignard reagent, dehydrates to form olefinic bond, partial hydrogenation of triple bond forms double bond, finally removes protection of acetal, and synthesizes deca-dialdehyde through seven steps of reaction, the process has long reaction steps, the former three steps of reaction are difficult to control, the total yield of deca-dialdehyde is only 21%, and is not suitable for industrial production.
The method for synthesizing the decamethylene of the patent often has overlong steps, so that the total yield is low; or the used compound has high toxicity and is not environment-friendly.
The Chinese patent CN100460378C synthesizes the deca-dialdehyde with high efficiency through three steps of addition, acidolysis and alkaline hydrolysis, and in the alkaline hydrolysis elimination reaction, the accelerator sodium bicarbonate has poor thermal stability, is easy to decompose when heated and has continuously reduced catalytic efficiency. Meanwhile, the organic phase water-soluble impurities bring more problems to the production.
In conclusion, in the method for preparing the decamethylene by condensing the enol ether, the elimination reaction has higher requirement on equipment due to the use of strong base, the product quality of the decamethylene can be reduced, and the use of weak base can cause the increase of three wastes. Therefore, it is necessary to develop an environmentally friendly, high-quality, low-cost production process for synthesizing decadialdehyde.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a basic solid catalyst and an application of the basic solid catalyst in catalytic synthesis of decamethylene. The catalyst has high selectivity and conversion rate in alkaline hydrolysis reaction, is not easy to generate byproducts, has small environmental pollution, can be recycled for multiple times, has small corrosion to equipment, and is suitable for industrial production.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of an alkaline solid catalyst, which comprises the following steps:
1) 3-aminopropyl silane and carbodiimide are subjected to coupling reaction to obtain guanidino silane;
2) and reacting the obtained guanidino silane with the activated molecular sieve to obtain the basic solid catalyst.
The 3-aminopropylsilane in the step (1) of the present invention is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-aminopropyltripropoxysilane, and 3-aminopropyltriethoxysilane is preferably used.
In the step (1), the carbodiimide 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 in the presence of a copper-based metal catalyst, such as copper chloride, copper sulfate, copper trifluoromethanesulfonate 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-aminopropylsilane is 0.01-0.1: 1, preferably 0.05-0.08: 1.
In the present invention, the coupling reaction in step (1) is carried out 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 dichloromethane, trichloromethane, dichloroethane or chlorobenzene; ester solvents such as ethyl acetate, methyl propionate, and mixtures of these solvents. Aromatic hydrocarbons, particularly preferably toluene, are preferably used as reaction solvent.
Preferably, the reaction temperature of the step (1) is 30-80 ℃, and the reaction time is 8-15 h.
Preferably, the molar ratio of the 3-aminopropylsilane to the carbodiimide added in the step (1) is 1:0.9-1.5, and the preferred molar ratio is 1: 1.1-1.2.
According to the invention, the molecular sieve in the step (2) is one or more of SBA-15, SBA-16, ZSM-12 or ZSM-23, and an SBA-15 type molecular sieve is preferably used.
According to the invention, the mass ratio of the guanidinosilane to the molecular sieve in step (2) is 1:0.5-2.0, preferably 1: 0.9-1.1.
According to the present invention, 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 10-20 h.
The molecular sieve activation mode in the step (2) is drying for 2-10h in a muffle furnace at 300-.
According to the invention, the catalyst obtained in the step (2) can be collected by filtration; the filtered product is preferably rinsed with a solvent and dried in vacuo.
The invention relates to a preparation method of decarbyl dialdehyde, which adopts acidolysis product with structural formula I as raw material, and generates the decarbyl dialdehyde by alkaline hydrolysis elimination reaction under the alkaline solid catalyst.
The acidolysis product has a structure shown in formula I, wherein the substituent R can be methyl, ethyl, isopropyl, tert-butyl or phenyl, preferably methyl.
Figure BDA0003437808480000041
The alkaline hydrolysis reaction is carried out in a solvent, wherein the solvent is a protic solvent, such as water, tert-butanol alcohol, isopropanol or hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons, such as dichloromethane, trichloromethane, dichloroethane or chlorobenzene; ester solvents such as ethyl acetate, methyl propionate, and mixtures of these solvents. Preferably, a protic solvent, particularly preferably water, is used as reaction solvent.
The deca-dialdehyde is usually prepared by using a strong base catalyst, but the deca-dialdehyde is easily disproportionated 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 is combined with a molecular sieve, so that the catalytic surface area is increased, and the active component of the amine group has no catalytic effect on aldehyde groups of the decarburized dialdehyde, so that the active component of the amine group can exist stably. When the alkoxy is eliminated, the synergistic effect is obvious, and no intermediate product exists, so that the purity of the product is ensured.
The molecular equation of the disproportionation reaction is shown below.
Figure BDA0003437808480000042
In the present invention, the basic solid catalyst is used in an amount of 0.01 to 0.5 times, preferably 0.05 to 0.1 times the amount of the acidolysis substance.
In the present invention, the alkaline hydrolysis elimination reaction temperature is-20 to 100 deg.C, preferably 0 to 50 deg.C, more preferably 10 to 30 deg.C, and the reaction time is 1 to 20 hours, preferably 5 to 10 hours.
The invention has the positive effects that:
1) the prepared alkaline catalyst is a supported organic base catalyst, has stable structure, strong selective catalytic performance, no intermediate product generation, high catalytic efficiency and no excessive reaction of the product;
2) the reaction condition is mild, the catalyst can be recycled, the reaction efficiency can be well maintained after the catalyst is applied for more than 20 times, and the method is environment-friendly;
3) simple technological operation, low production cost and contribution to industrial production.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
Gas chromatography conditions: performing online measurement on a polysiloxane column HP-5 of an Agilent gas chromatography, performing second-order temperature programming, 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 was increased to 250 ℃ at a rate of 15 ℃/min. Carrier gas high purity N2The split ratio is 150: 1. the sample introduction temperature is 250 ℃, the detector is FID, and the detector temperature is 260 ℃. The amount of the sample was 0.2. mu.L.
The raw material sources are as follows:
name of reagent Reagent specification Manufacturer of the product
Acidolysis product 99％,HPLC New and new
Dichloromethane, toluene, ethyl acetate 99％,AR Annaiji (Annaiji)
3-aminopropyltriethoxysilane 98％,AR Aladdin reagent
Polyoxyethylene-polyoxypropylene-polyoxyethylene (P123) - Annaiji (Annaiji)
Tetraethoxysilane (TEOS) 99％，AR Shanghai crystal pure practice
Dicyclohexylcarbodiimide 98％,AR Aladdin reagent
Diisopropylcarbodiimide 98％,AR Aladdin reagent
Preparation of SBA-15 molecular sieve
50g of P123 was weighed out and transferred to a 5L beaker, 1500mL of 2mol/L hydrochloric acid and 380mL of deionized water were added, respectively, and the mixture was magnetically stirred at room temperature for 6h until the P123 was completely dissolved. 105.3g of tetraethyl orthosilicate (TEOS) was weighed out and added dropwise to the solution, and the mixture was stirred for 24 hours to react sufficiently. And transferring the mixed solution into a stainless steel hydrothermal reaction kettle, crystallizing in an oven (100 ℃) for 48 hours, cooling to room temperature, performing vacuum filtration and deionized water washing to obtain a white filter cake, and naturally drying. Calcining for 2h in a muffle furnace at 400 ℃ to obtain the activated SBA-15.
Example 1
Preparing a supported SBA-15 basic solid catalyst I:
0.11mol of 13.9g of diisopropylcarbodiimide and 0.1mol of 22.1g of 3-aminopropyltriethoxysilane were placed in a 1000mL three-necked flask, and 500mL of dry toluene was added simultaneously, followed by addition of 0.01mol of 1.3g of copper chloride, and the mixture was reacted for 10 hours under magnetic stirring at a temperature of 80 ℃ under a nitrogen atmosphere. Then 50mL of absolute ethanol and 32.4g of previously activated SBA-15 were added, and the mixture was magnetically stirred at 45 ℃ and then reacted for 12 hours with continuous introduction of nitrogen. Cooling to room temperature after the reaction is stopped, carrying out suction filtration, and washing by using absolute ethyl alcohol. And (3) drying the product at 40 ℃ for 6h in vacuum to finally obtain the solid base catalyst I.
Example 2
Preparing a supported SBA-15 alkaline solid catalyst II:
0.15mol of 30.9g of dicyclohexylcarbodiimide and 0.1mol of 22.1g of 3-aminopropyltriethoxysilane were placed in a 1000mL three-necked flask while 500mL of dry ethyl acetate was added, followed by addition of 0.005mol of 0.7g of copper chloride, and reacted for 15 hours under magnetic stirring at a temperature of 50 ℃ under a nitrogen atmosphere. 50mL of isopropanol and 58.3g of previously activated SBA-15 were then added, magnetically stirred at 55 ℃ and nitrogen was allowed to continue to flow through for 20 h. After the reaction is stopped, cooling to room temperature, carrying out suction filtration, and washing with isopropanol. And (3) drying the product at 40 ℃ for 6h in vacuum to finally obtain the solid base catalyst II.
Example 3
Preparing a 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-aminopropyltriethoxysilane were placed in a 1000mL three-necked flask while adding 500mL of dry ethyl acetate, followed by addition of 0.01mol of 1.3g of copper chloride, and reacted for 12 hours under magnetic stirring at a temperature of 60 ℃ under a nitrogen atmosphere. 50mL of isopropanol and 58.3g of previously activated SBA-15 were then added, magnetically stirred at 55 ℃ and nitrogen was allowed to continue to flow through for 20 h. After the reaction is stopped, cooling to room temperature, carrying out suction filtration, and washing with isopropanol. And (3) drying the product at 40 ℃ for 6h in vacuum to finally obtain the solid base catalyst III.
Example 4
Preparation of deca-dialdehyde:
A1.0L three-necked flask was used as a reaction vessel, to which 22.8g of an acid hydrolyzate, 100g of pure water, and 2.3g of a basic 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 10.0h 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
Preparation of deca-dialdehyde:
the catalyst obtained in example 4 was filtered, washed with absolute ethanol, and then air-dried, to obtain the catalyst of example 5.
A1.0L three-necked flask is used as a reaction kettle, 22.8g of acidolysis product, 200g of water and 2.2g of recovered basic solid catalyst I are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath kettle at 50 ℃ and stirred to start reaction. After 8.0h 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
Preparation of deca-dialdehyde:
the catalyst I in example 5 was filtered, and the obtained catalyst was washed with absolute ethanol and then air-dried to obtain the catalyst of example 6.
A1.0L three-necked flask is used as a reaction kettle, 22.8g of acidolysis product, 200g of toluene and 2.0g of recovered basic solid catalyst I are sequentially added into the reaction kettle, and the reaction system is placed in an oil bath kettle at 40 ℃ and stirred to start reaction. After 8.0h 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
Preparation of deca-dialdehyde:
A2.0L three-neck flask is taken as a reaction kettle, 68.4g of acidolysis product, 1000g of ethanol and 3.4g of alkaline solid catalyst I are sequentially added into the reaction kettle, the reaction system is placed in an oil bath kettle at 60 ℃, and the reaction is started by stirring. After 10.0h 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
Preparation of deca-dialdehyde:
A1.0L three-neck flask is taken as a reaction kettle, 22.8g of acidolysis product, 300g of water and 4.6g of alkaline solid catalyst II are sequentially added into the reaction kettle, the reaction system is placed in an oil bath kettle at the temperature of 90 ℃, and the reaction is started by stirring. After 4.0h 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
Preparation of deca-dialdehyde:
the catalyst II obtained in example 8 was filtered, washed with absolute ethanol and then air-dried, to obtain the catalyst of example 9.
A1.0L three-necked flask was used as a reaction vessel, and 11.4g of an acid hydrolyzate, 500g of methylene chloride and 4.4g of a recovered basic solid catalyst II were sequentially added thereto, and the reaction system was placed in a 10 ℃ low-temperature tank and stirred to start the reaction. After 8.0h 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
Preparation of deca-dialdehyde:
A1.0L three-neck flask was used as a reaction vessel, 11.4g of an acid hydrolyzate, 200g of methylene chloride, and 3.5g of a basic solid catalyst III were sequentially added thereto, and the reaction system was placed in an oil bath at 60 ℃ and stirred to start the reaction. After 15.0h 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
Preparation of deca-dialdehyde:
the catalyst III obtained in example 10 was filtered, washed with absolute ethanol, and then air-dried, to obtain the catalyst of example 11.
A2.0L three-necked flask was used as a reaction vessel, and 22.8g of an acid hydrolyzate, 1000g of methylene chloride and 3.5g of a recovered basic solid catalyst III were sequentially added thereto, and the reaction system was placed in an oil bath at 80 ℃ and stirred to start the reaction. After 10.0h 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
Preparation of deca-dialdehyde:
A1.0L three-necked flask was used as a reaction vessel, and 22.8g of an acid hydrolyzate, 100.0g of water and 46.5g of a 5% aqueous sodium hydrogencarbonate solution were sequentially added thereto, and the reaction system was placed in an oil bath at 30 ℃ and stirred to start the reaction. After 10.0h 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 (9)

1. The preparation method of the alkaline solid catalyst is characterized by comprising the following steps:
1) 3-aminopropyl silane and carbodiimide are subjected to coupling reaction to obtain guanidino silane;
2) and reacting the obtained guanidino silane with the activated molecular sieve to obtain the basic solid catalyst.
2. The method according to claim 1, wherein the 3-aminopropylsilane in the step (1) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-aminopropyltripropoxysilane, preferably 3-aminopropyltriethoxysilane;
preferably, the carbodiimide in step (1) is one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
3. The process according to claim 1, wherein the coupling reaction in step (1) is carried out in the presence of a copper-based metal catalyst, preferably copper chloride, copper sulfate, copper trifluoromethanesulfonate and copper nitrate, more preferably copper chloride as a catalyst;
preferably, the molar ratio of the copper-based catalyst used in the step (1) to the 3-aminopropylsilane is 0.01-0.1: 1, preferably 0.05-0.08: 1.
4. The preparation method according to claim 1, wherein the reaction temperature of the step (1) is 30-80 ℃, and the reaction time is 8-15 h;
preferably, in the step (1), the molar ratio of the 3-aminopropylsilane to the carbodiimide added is 1:0.9-1.5, and the preferred molar ratio is 1: 1.1-1.2.
5. The process of claim 1, wherein the molecular sieve in step (2) is one or more of SBA-15, SBA-16, ZSM-12 or ZSM-23, preferably a molecular sieve of SBA-15 type;
preferably, the mass ratio of the guanidinosilane to the molecular sieve in step (2) is 1:0.5-2.0, preferably 1: 0.9-1.1.
6. The method of claim 1, wherein the reaction in step (2) is carried out in an alcoholic solvent, preferably one or more of ethanol, methanol, isopropanol, and hexafluoroisopropanol;
preferably, the reaction temperature of the step (2) is 30-60 ℃, and the reaction time is 10-20 h;
preferably, the molecular sieve activation mode of the step (2) is drying for 2-10h in a muffle furnace at 300-500 ℃.
7. A preparation method of deca-dialdehyde is characterized in that acidolysis product with a structural formula I is used as raw material, and under the alkaline solid catalyst of any one of claims 1-6, alkaline hydrolysis elimination reaction is carried out to generate deca-dialdehyde;
preferably, the acidolysis product has a structure shown in formula I, wherein the substituent R is methyl, ethyl, isopropyl, tert-butyl or phenyl, preferably methyl.
Figure FDA0003437808470000021
8. The process according to claim 7, wherein the basic solid catalyst is used in an amount of 0.01 to 0.5 times, preferably 0.05 to 0.1 times the amount of the acid hydrolyzate.
9. The process according to claim 7, wherein the temperature of the alkaline hydrolysis elimination reaction is-20 to 100 ℃, preferably 0 to 50 ℃, more preferably 10 to 30 ℃ and the reaction time is 1 to 20 hours, preferably 5 to 10 hours.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8414767D0 (en) * 1984-06-09 1984-07-11 Bp Chem Int Ltd Catalysis by supported catalysts
CN105349520A (en) * 2015-11-26 2016-02-24 青岛大学 Hollow microsphere immobilized laccase and preparation method thereof
CN106410229A (en) * 2016-10-14 2017-02-15 三峡大学 Method for preparing loaded carbon-based anode catalysts for fuel batteries and application of loaded carbon-based anode catalysts
US20180327549A1 (en) * 2015-12-15 2018-11-15 Sika Technology Ag Catalyst having a polysiloxane structural unit for hardenable compositions
CN110801859A (en) * 2019-11-12 2020-02-18 山东益丰生化环保股份有限公司 Guanidyl modified mesoporous molecular sieve, and preparation method and application thereof
CN111943819A (en) * 2020-08-13 2020-11-17 万华化学集团股份有限公司 Method for preparing deca-dialdehyde intermediate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8414767D0 (en) * 1984-06-09 1984-07-11 Bp Chem Int Ltd Catalysis by supported catalysts
CN105349520A (en) * 2015-11-26 2016-02-24 青岛大学 Hollow microsphere immobilized laccase and preparation method thereof
US20180327549A1 (en) * 2015-12-15 2018-11-15 Sika Technology Ag Catalyst having a polysiloxane structural unit for hardenable compositions
CN106410229A (en) * 2016-10-14 2017-02-15 三峡大学 Method for preparing loaded carbon-based anode catalysts for fuel batteries and application of loaded carbon-based anode catalysts
CN110801859A (en) * 2019-11-12 2020-02-18 山东益丰生化环保股份有限公司 Guanidyl modified mesoporous molecular sieve, and preparation method and application thereof
CN111943819A (en) * 2020-08-13 2020-11-17 万华化学集团股份有限公司 Method for preparing deca-dialdehyde intermediate

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