CN109776311B - Method and device for preparing 2-isopropyl-2-adamantanol (methyl) acrylate - Google Patents
Method and device for preparing 2-isopropyl-2-adamantanol (methyl) acrylate Download PDFInfo
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- CN109776311B CN109776311B CN201910143133.7A CN201910143133A CN109776311B CN 109776311 B CN109776311 B CN 109776311B CN 201910143133 A CN201910143133 A CN 201910143133A CN 109776311 B CN109776311 B CN 109776311B
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Abstract
The invention discloses a preparation method of 2-isopropyl-2-adamantanol (methyl) acrylate, which is characterized by comprising the following steps: taking (methyl) acrylate and isopropyl adamantanol as reaction raw materials, taking an alkaline compound as a catalyst, and carrying out an ester exchange reaction at 40-120 ℃ in the presence of a solvent, wherein the alkaline compound catalyst is loaded on a porous carrier; filtering the reaction solution at 60-80 ℃ by a plate filter, cooling to-60-0 ℃, and separating out solids, namely 2-isopropyl-2-adamantanol (methyl) acrylate. The invention uses alkaline compound to load porous catalyst, the production process steps are simple, the reaction is thorough, the yield is up to more than 95%, the purification process is simple, and the product purity is up to more than 98%; the solvent and the catalyst can be recycled, so that the production cost is saved, zero emission of pollutants is realized, and the method is a green production method.
Description
Technical Field
The invention relates to a preparation method of an adamantane derivative, and in particular relates to a preparation method of 2-isopropyl-2-adamantanol (methyl) acrylate.
Background
Adamantane is a compound with highly symmetrical and extremely stable cyclic tetrahedron, and the special cage structure of the compound enables the compound to show excellent physical and chemical properties, so that the compound has important application in the fields of biological pharmacy, organic synthesis, electronic materials and the like. The adamantane is used for synthesizing various special medicines for resisting cancers, tumors and the like in biomedicine; widely used for preparing high-grade lubricants, high-efficiency insecticides, catalysts, special polymer additives and the like in the aspect of chemical synthesis; in the field of electronic materials, adamantane derivatives are widely used for the production of optical film materials because of their excellent optical and etching resistance.
In recent years, with the rapid development of the integrated circuit industry in China, the demand for semiconductor electronic materials is increasing. Among them, the market demand for adamantane-based (meth) acrylate products, which are one of adamantane derivatives, is rapidly increasing, and the market prospect is huge.
The clean green production process is always the target of the production pursuit of the chemical industry, and under the background of the continuous increase of the labor cost in China, the transformation and upgrade of the enterprise technology and the increasingly strict environmental protection requirement, the improvement of the production efficiency and the reduction of the cost expenditure gradually become the directions of the research and development and the production efforts of the enterprises. The current manufacturing processes involved in the manufacture of adamantane-based (meth) acrylate products typically involve the reaction of a Grignard reagent with a compound containing the corresponding (meth) acrylic group. The reaction uses a large amount of chemical raw materials, and a plurality of complicated post-treatment processes are needed to prepare the target compound, so that the process is complex and a large amount of waste is generated.
For example, chinese patent publication No. CN104628557A discloses a method for preparing 2-methyl-2-adamantanol acrylate, which uses Grignard reagent and acid anhydride as reaction raw materials, and completes the production of the product through the steps of liquid separation, extraction, rotary evaporation, water washing, silica gel passing, reduced pressure distillation, etc., thereby generating waste water, n-hexane, silica gel, etc., and generating a large amount of waste due to many production process steps. Chinese patent publication No. CN104628561A discloses a method for preparing 2-ethyl-2-adamantanol methacrylate, which uses Grignard reagent and methacryloyl chloride as raw materials, and also completes the production through the steps of liquid separation, extraction, rotary evaporation, alkali washing, water washing, silica gel passing, crystallization, and the like, thereby generating waste water, n-hexane, silica gel, and other waste materials. In the production process, high-toxicity methacryloyl chloride is used as a reaction raw material, so that the pollution is great and the corrosion to equipment is serious.
Therefore, it is required to provide a novel method for preparing adamantane derivatives, so as to realize green clean preparation and reduce environmental pollution.
Disclosure of Invention
The invention aims to provide a preparation method of 2-isopropyl-2-adamantanol (methyl) acrylate, which realizes the recycling of a solvent and a catalyst and reduces the emission of pollutants. Another object of the present invention is to provide an apparatus for use in the production method.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of 2-isopropyl-2-adamantanol (meth) acrylate comprises the following steps:
(1) taking (methyl) acrylate and isopropyl adamantanol as reaction raw materials, taking an alkaline compound as a catalyst, and carrying out an ester exchange reaction at 40-120 ℃ in the presence of a solvent, wherein the alkaline compound catalyst is loaded on a porous carrier;
(2) after the reaction is finished, filtering the reaction solution at the temperature of 60-80 ℃ by a plate filter;
(3) and cooling the filtrate to-60-0 ℃, and separating out solid, namely the 2-isopropyl-2-adamantanol (methyl) acrylate.
In the technical scheme, the (methyl) acrylate and the isopropyl adamantanol generate new isopropyl adamantane (methyl) acrylate and corresponding alcohol under the condition of the basic compound catalyst, and the ester exchange reaction is a reversible reaction.
The above scheme can be expressed as the following reaction:
in the above technical scheme, the alkaline compound is an oxide, hydroxide or salt of an alkali metal, an alkaline earth metal or a rare earth element.
Preferably, the basic compound is selected from one or more of basic potassium salts and sodium salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, and the like.
The porous carrier is selected from activated carbon, molecular sieve, diatomite or porous alumina.
In the technical scheme, the structural formula of the (methyl) acrylate is shown as
In the formula, R1An alkyl group having 1 to 20 carbon atoms; r2Is H or methyl;
the molar ratio of the (methyl) acrylic ester, the isopropyl adamantanol and the basic compound is (0.8-2.0) to 1 to (0.005-0.1 mol).
Preferably, the molar ratio of (meth) acrylate, isopropyl adamantanol, basic compound is (0.9-1.3) to 1 to (0.01-0.05 mol).
Preferably, the ester exchange reaction temperature is 60-80 ℃, and the reaction time is 5-40 hours.
When the product solid is precipitated, the preferable scheme is that the temperature of the filtrate is reduced to-30 to-10 ℃.
According to the further technical scheme, the liquid after the product is separated out is distilled and separated to obtain a solvent and an alcohol byproduct, and the solvent is recycled for the ester exchange reaction.
In the technical scheme, the reaction solution is filtered by a 0.01-20 micron plate filter at the temperature of 60-80 ℃, and the preferred pore size is 1 micron.
In the above technical scheme, the solvent is selected from one or more of benzene, toluene, xylene, tetrahydrofuran, methyl tetrahydrofuran, dioxane, ethyl acetate, petroleum ether, methyl tert-butyl ether, diethyl ether, butanone, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, chloroform, dichloromethane, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or n-hexane. The molar ratio of the solvent to the isopropyl adamantanol is (5-15) to 1.
The invention also provides a preparation device of the 2-isopropyl-2-adamantanol (methyl) acrylate, which comprises a first reaction kettle and a second reaction kettle, wherein a liquid outlet pipeline of the first reaction kettle is connected to the second reaction kettle through a plate type filter with the pore diameter of 0.01-20 microns; a collecting tank is arranged, and the mother liquor separated in the second reaction kettle is conveyed to the collecting tank through a collecting pipeline; and stirrers are respectively arranged in the first reaction kettle and the second reaction kettle.
Preferably, the pore size of the plate filter is 1 micron.
The first reaction kettle is used for carrying out ester exchange reaction; the reaction liquid is filtered by a plate filter and then enters a second reaction kettle; the second reaction kettle is used for cooling and crystallizing to separate out a product; after the product is separated out, the mother liquor enters a collecting tank for further separation for recycling, and the fixed product is taken out and dried to obtain the required 2-isopropyl-2-adamantanol (methyl) acrylate.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention uses the principle of ester exchange reaction, uses alkaline compound to load porous catalyst, has simple production process steps, thorough reaction, high yield of more than 95 percent, simple purification process and high product purity of more than 98 percent.
2. The solvent and the catalyst can be recycled, so that the method saves the mass production cost, realizes zero emission of pollutants, and is a green production method.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus in the example;
FIG. 2 is a schematic flow chart of an embodiment of a method.
In the figure: 1. a first reaction kettle; 2. a plate filter; 3. a second reaction kettle; 4. a collection tank; 5. a stirrer.
Detailed Description
The invention will be further described with reference to examples in which the basic catalyst used has been previously supported on porous alumina.
The first embodiment is as follows: preparation of isopropyl adamantane methacrylate
Referring to fig. 1, a schematic diagram of the apparatus used in this embodiment is shown.
The device comprises a first reaction kettle 1 and a second reaction kettle 3, wherein a liquid outlet pipeline of the first reaction kettle 1 is connected to the second reaction kettle 3 through a plate filter 2 with the pore diameter of 1 micron; a collecting tank 4 is arranged, and the mother liquor separated in the second reaction kettle 3 is conveyed to the collecting tank 4 through a collecting pipeline; the first reaction kettle 1 and the second reaction kettle 3 are respectively provided with a stirrer 5.
The preparation process can be expressed by the following formula:
referring to FIG. 2, a schematic flow chart of the preparation method of this example is shown. The method specifically comprises the following steps:
weighing 120g (1.2 mol) of methyl methacrylate, 194g (1 mol) of isopropyl adamantanol, 3.4g (0.02 mol) of sodium hydroxide catalyst and 720g (10 mol) of butanone into a 5L reaction kettle, setting the reaction temperature to be 79 ℃, stopping after 24 hours of reaction, filtering the reaction liquid by a 1 micron plate filter at 79 ℃, and collecting the sodium hydroxide catalyst for next use.
Introducing the filtrate into a reaction kettle, starting a refrigerator and stirring, setting the temperature to be-23 ℃, precipitating a large amount of solids after about 3 hours, stopping stirring, standing for 1 hour, inserting a conduit into the reaction kettle, vacuumizing to lead out the liquid, taking out the solid product, placing the solid product in a vacuum drying oven, drying at 25 ℃ for 24 hours, collecting 256g of the product, weighing the product, wherein the yield is 97.7%, the purity is 99.9% (HPLC), and performing nuclear magnetic reaction1H NMR (400M, C6D 6): delta =5.502(1H), 6.512(1H), 0.883(6H), 2.005(3H), 1.073-1.808 (15H). 716g of butanone with the purity of 99.4 percent (HPLC), 40g of methanol with the purity of 99.6 percent (HPLC) are collected after the liquid is distilled.
Example two: preparation of isopropyl adamantane methacrylate
Weighing 250g (2.2 mol) of ethyl methacrylate, 388g (2 mol) of isopropyl adamantanol, 9.3g (0.03 mol) of sodium methoxide catalyst and 1440g (20 mol) of tetrahydrofuran, putting the materials into a 10L reaction kettle, setting the reaction temperature to be 77 ℃, stopping the reaction after 24 hours, filtering the reaction liquid by using a 1 micron plate filter at 77 ℃, and collecting the sodium methoxide catalyst for later use.
Introducing the filtrate into a reaction kettle, starting a refrigerator and stirring, setting the temperature to be 20 ℃ below zero, precipitating a large amount of solid after about 5 hours, stopping stirring, standing for 1 hour, inserting a conduit into the reaction kettle, vacuumizing to lead out the liquid, taking out the solid product, placing the solid product in a vacuum drying oven, drying at 25 ℃ for 24 hours, collecting the product, weighing 513g, obtaining the yield of 98.0 percent and the purity of 99.5 percent (HPLC), and obtaining the nuclear magnetic result1H NMR(400M, C6D6) δ =5.506(1H), 6.511(1H), 0.885(6H), 2.008(3H), 1.074-1.810 (15H). The liquid was distilled to collect 1423g of tetrahydrofuran with 99.0% (HPLC) purity, 154g of ethanol with 99.8% (HPLC) purity.
Example three: preparation of isopropyl adamantane acrylate
Weighing 103g (1.2 mol) of methyl acrylate, 194g (1 mol) of isopropyl adamantanol, 6.2g (0.02 mol) of sodium methoxide catalyst and 880g (10 mol) of dichloromethane, putting the materials into a 5L reaction kettle, setting the reaction temperature to be 77 ℃, stopping the reaction after 24 hours, filtering the reaction liquid at 77 ℃ by using a 1 micron plate filter, collecting the sodium methoxide catalyst for next use, introducing the filtrate into the reaction kettle, starting a refrigerator and stirring, setting the temperature to be-30 ℃, precipitating a large amount of solid after about 2 hours, stopping the stirring, standing for 1 hour, inserting a conduit into the reaction kettle, vacuumizing to lead out the liquid, taking out the solid product, putting the solid product into a vacuum drying box, drying the solid product at 25 ℃ for 24 hours, collecting 251g of the product, weighing the yield to be 95.8%, the purity to be 99.2% (HPLC), and performing nuclear magnetic reaction1H NMR(400M, C6D6) δ =5.660(1H), 6.438(1H), 0.866(6H), 1.173 to 1.909 (15H). The liquid was distilled to collect 865g of methylene chloride with 98.1% purity (HPLC), 42g of methanol with 99.8% purity (HPLC).
Claims (8)
1. A method for preparing 2-isopropyl-2-adamantanol (meth) acrylate, characterized by comprising the steps of:
(1) taking (methyl) acrylate and isopropyl adamantanol as reaction raw materials, taking an alkaline compound as a catalyst, and carrying out an ester exchange reaction at 40-120 ℃ in the presence of a solvent, wherein the alkaline compound catalyst is loaded on a porous carrier; the alkaline compound is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, sodium isopropoxide and potassium tert-butoxide;
(2) after the reaction is finished, filtering the reaction solution at the temperature of 60-80 ℃ by a plate filter;
(3) and cooling the filtrate to-60-0 ℃, and separating out solid, namely the 2-isopropyl-2-adamantanol (methyl) acrylate.
2. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: the porous carrier is selected from activated carbon, molecular sieve, diatomite or porous alumina.
3. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: the structural formula of the (methyl) acrylic ester is shown in the specification
In the formula, R1An alkyl group having 1 to 20 carbon atoms; r2Is H or methyl.
4. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 3, characterized in that: the molar ratio of the (methyl) acrylic ester to the isopropyl adamantanol to the basic compound is (0.9-1.3) to 1 to (0.01-0.05 mol).
5. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: the ester exchange reaction temperature is 60-80 ℃, and the reaction time is 5-40 hours.
6. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: in the step (2), the pore diameter of the plate filter is 0.01-20 microns; in the step (3), the temperature of the filtrate is reduced to-30 to-10 ℃.
7. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: and distilling and separating the liquid after the product is separated out to obtain a solvent and an alcohol byproduct, wherein the solvent is recycled for the ester exchange reaction.
8. The method for producing 2-isopropyl-2-adamantanol (meth) acrylate according to claim 1, characterized in that: the solvent is one or more of benzene, toluene, xylene, tetrahydrofuran, methyl tetrahydrofuran, dioxane, ethyl acetate, petroleum ether, methyl tert-butyl ether, diethyl ether, butanone, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, chloroform, dichloromethane, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or normal hexane.
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| CN104628562A (en) * | 2013-11-11 | 2015-05-20 | 傅志伟 | Preparation method for 2-ethyl-2-adamantanol acrylate |
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