CN109776311A - The preparation method and device of 2- isopropyl -2- adamantanol (methyl) acrylate - Google Patents
The preparation method and device of 2- isopropyl -2- adamantanol (methyl) acrylate Download PDFInfo
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- CN109776311A CN109776311A CN201910143133.7A CN201910143133A CN109776311A CN 109776311 A CN109776311 A CN 109776311A CN 201910143133 A CN201910143133 A CN 201910143133A CN 109776311 A CN109776311 A CN 109776311A
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- isopropyl
- adamantanol
- acrylate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of preparation methods of 2- isopropyl -2- adamantanol (methyl) acrylate, it is characterized by: using (methyl) acrylate and isopropyl adamantanol as reaction raw materials, using alkali compounds as catalyst, in the presence of solvent, ester exchange reaction is carried out at 40~120 DEG C, wherein, basic compound catalysis agent is carried on porous carrier；Reaction solution is cooled to -60~0 DEG C at 60~80 DEG C after leaf filter filters, and the solid of precipitation is 2- isopropyl -2- adamantanol (methyl) acrylate.For the present invention with the supported porous catalyst of alkali compounds, production craft step is simple, and thoroughly, yield is up to 95% or more, and purifying process is simple, and product purity reaches 98% or more for reaction；Solvent and catalyst can be recycled, and save production cost, realize pollutant " zero " discharge, are a kind of Green production methods.
Description
Technical field
The present invention relates to a kind of preparation methods of adamantane derivative, and in particular to a kind of 2- isopropyl -2- adamantanol
The preparation method of (methyl) acrylate.
Background technique
Adamantane is a kind of with high degree of symmetry and the extremely stable tetrahedral compound of ring-type, special cage structure
So that it is shown excellent physical and chemical properties, has important application in fields such as bio-pharmaceuticals, organic synthesis, electronic materials.
Adamantane is used for the synthesis etc. of the specific medicaments such as a variety of anticancers, antitumor in biological medicine；It is used extensively in terms of chemical synthesis
In preparing quality lubricant, efficient pesticides, catalyst, speciality polymer additive etc.；In field of electronic materials, adamantane spreads out
Manufacture of the biology because optical film material can be widely used in excellent optics and etch-resistance.
In recent years, with the fast development of China's IC industry, the demand to semiconductor electronic material is increasing.
Wherein, it is quicklyd increase as the adamantane of one of adamantane derivative (methyl) acrylate product market demand, before market
Scape is huge.
Clean green production process be always chemical industry production pursue target, at home labor cost it is continuous on
Under the increasingly strict background of liter, enterprise technology transition and upgrade, environmental requirement, improving production efficiency, reduce cost payout gradually at
The direction made great efforts for Corporation R & D and production.The manufacturing process for being related to manufacturing adamantane (methyl) acrylate product at present is logical
Often reacted for grignard reagent to the compound containing corresponding (methyl) acrylic acid groups.This kind of chemical raw material used that reacts is more,
And need to prepare target compound by the cumbersome aftertreatment technology of multistep, complex process, and generate a large amount of useless
Gurry.
For example, the Chinese invention patent of Publication No. CN104628557A discloses 2- methyl -2- adamantanol acrylic acid
The preparation method of ester uses grignard reagent and acid anhydrides for reaction raw materials, by liquid separation, extraction, rotary evaporation, washing, cross silica gel,
Vacuum distillation and etc. complete production, produce the waste materials such as waste water, n-hexane, silica gel, production craft step is more, generate
A large amount of wastes.The Chinese invention patent of Publication No. CN104628561A discloses 2- ethyl -2- adamantanol methyl-prop
The preparation method of olefin(e) acid ester, has used grignard reagent and methacrylic chloride is to answer raw material, also passes through liquid separation, extraction, rotation
Evaporation, alkali cleaning, washing, cross silica gel, crystallization and etc. complete production, produce the waste materials such as waste water, n-hexane, silica gel.
In production technology, having used highly toxic methacrylic chloride is reaction raw materials, and pollution is very big, and severe corrosion to equipment.
Accordingly, it is desirable to provide a kind of preparation method of new adamantane derivative reduces ring to realize green cleaning preparation
Border pollution.
Summary of the invention
Goal of the invention of the invention is to provide a kind of preparation side of 2- isopropyl -2- adamantanol (methyl) acrylate
Recycling for method, realization solvent and catalyst, reduces the discharge of pollutant.Another object of the present invention is to provide one kind
Device for the preparation method.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of 2- isopropyl -2- adamantanol (first
Base) acrylate preparation method, comprising the following steps:
(1) using (methyl) acrylate and isopropyl adamantanol as reaction raw materials, using alkali compounds as catalyst, molten
In the presence of agent, ester exchange reaction is carried out at 40~120 DEG C, wherein basic compound catalysis agent is carried on porous carrier；
(2) after the reaction was completed, reaction solution filters at 60~80 DEG C by leaf filter；
(3) -60~0 DEG C is cooled the filtrate to, the solid of precipitation is 2- isopropyl -2- adamantanol (methyl) acrylate.
In above-mentioned technical proposal, (methyl) acrylate and isopropyl adamantanol are under the conditions of basic compound catalysis agent
New isopropyl adamantane (methyl) acrylate and corresponding alcohol are generated, since ester exchange reaction is reversible reaction, the present invention
It is middle that basic compound catalysis agent is carried on porous carrier, it is demonstrated experimentally that the porous catalyst loaded using alkali compounds
High yield can be obtained.
Above scheme can be expressed as following reaction formula:
。
In above-mentioned technical proposal, the alkali compounds is alkali metal, alkaline-earth metal, the oxide of rare earth element, hydrogen-oxygen
Compound or salt.
Preferably, the alkali compounds is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, carbon
One of sylvite and sodium salt of the alkalinity such as sour hydrogen sodium, sodium methoxide, sodium ethoxide, sodium isopropylate, potassium tert-butoxide are a variety of.
The porous carrier is selected from active carbon, molecular sieve, diatomite or porous aluminas.
In above-mentioned technical proposal, the structural formula of (methyl) acrylate is
In formula, R1For the alkyl containing 1~20 carbon atom；R2For H or methyl；
The molar ratio of (methyl) acrylate, isopropyl adamantanol and alkali compounds is (0.8-2.0): 1: (0.005-
0.1mol)。
Preferably, (methyl) acrylate, isopropyl adamantanol, alkali compounds molar ratio be (0.9-1.3): 1:
(0.01-0.05mol)。
Preferably, transesterification reaction temperature is 60~80 DEG C, and the reaction time is 5~40 hours.
When carrying out product solid precipitation, preferred scheme, filtrate is cooled to -30~-10 DEG C.
Further technical solution, the liquid after product is precipitated separates acquisition solvent and by-product alcohols through distillation, described
Solvent is recycled in ester exchange reaction.
In above-mentioned technical proposal, reaction solution is filtered at 60~80 DEG C with 0.01~20 micron of leaf filter, and preferably 1
The aperture of micron.
In above-mentioned technical proposal, the solvent is selected from benzene,toluene,xylene, tetrahydrofuran, methyltetrahydrofuran, dioxy
Six rings, ethyl acetate, petroleum ether, methyl tertiary butyl ether(MTBE), ether, butanone, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, chlorine
One of imitative, methylene chloride, glycol dimethyl ether, tetraethyleneglycol dimethyl ether or n-hexane are a variety of.Solvent and isopropyl fund
The molar ratio of rigid alkanol is (5~15): 1.
Invention also provides a kind of preparation facilities of 2- isopropyl -2- adamantanol (methyl) acrylate, including
First reaction kettle and the second reaction kettle, the leaf filter that the outlet tube road via hole diameter of the first reaction kettle is 0.01~20 micron connect
It is connected to the second reaction kettle；Equipped with collecting tank, the mother liquor separated in second reaction kettle is delivered to collecting tank through collecting；Institute
It states in the first reaction kettle and the second reaction kettle and is respectively arranged with blender.
Preferably, the aperture of leaf filter is 1 micron.
Above-mentioned first reaction kettle is for carrying out ester exchange reaction；It is anti-that reaction solution enters second after leaf filter filters
Answer kettle；Product is precipitated for carrying out decrease temperature crystalline in second reaction kettle；After product is precipitated, mother liquor enters collecting tank, for further
Separation is to reuse, and fixed product takes out after drying, as required 2- isopropyl -2- adamantanol (methyl) propylene
Acid esters.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1, present invention uses ester exchange reaction principles, and with the supported porous catalyst of alkali compounds, production craft step is simple,
Thoroughly, yield is up to 95% or more, and purifying process is simple, and product purity reaches 98% or more for reaction.
2, solvent of the invention can be recycled, and catalyst can be recycled, and has saved mass production cost, has realized dirt
Object " zero " discharge is contaminated, is a kind of Green production method.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram in embodiment；
Fig. 2 is the method flow schematic diagram of embodiment.
In figure: 1, the first reaction kettle；2, leaf filter；3, the second reaction kettle；4, collecting tank；5, blender.
Specific embodiment
The present invention will be further described below with reference to examples, and used base catalysis device has been supported on porous in advance
On aluminium oxide.
Embodiment one: the preparation of isopropyl adamantyl methacrylate
Referring to attached drawing 1, the apparatus structure schematic diagram used for the present embodiment.
Device includes the first reaction kettle 1 and the second reaction kettle 3, and the outlet tube road via hole diameter of the first reaction kettle 1 is 1 micron
Leaf filter 2 is connected to the second reaction kettle 3；Equipped with collecting tank 4, the mother liquor separated in the second reaction kettle 3 is defeated through collecting
It send to collecting tank 4；Blender 5 is respectively arranged in first reaction kettle 1 and the second reaction kettle 3.
Preparation process can be expressed with following formula:
It is the preparation method flow diagram of the present embodiment referring to attached drawing 2.Specifically:
Weigh methyl methacrylate 120g(1.2mol), isopropyl adamantanol 194g(1mol), sodium hydroxide catalyst
3.4g(0.02mol), butanone 720g(10mol) investment 5L reaction kettle, 79 DEG C of reaction temperature are set, reaction stops after 24 hours,
1 micron of leaf filter of reaction solution is filtered at 79 DEG C, collection sodium hydroxide catalyst leaves secondary stand-by.
Filtrate imports in reaction kettle, opens refrigerator and stirring, -23 DEG C of set temperature, a large amount of solids is precipitated after about 3h, stop
It only stirs, stands 1 hour, conduit is inserted into reaction kettle, vacuumizes and exports liquid, solid product is taken out, is placed on vacuum
It is 24 hours dry at 25 DEG C in drying box, collect weighing products 256g, yield 97.7%, purity 99.9%(HPLC), nuclear-magnetism knot
Fruit1H NMR (400M, C6D6): δ=5.502 (1H), 6.512 (1H), 0.883 (6H), 2.005 (3H), 1.073~
1.808(15H).Liquid is collected into butanone 716g, purity 99.4%(HPLC by distillation), methanol 40g, purity 99.6%
(HPLC).
Embodiment two: the preparation of isopropyl adamantyl methacrylate
Weigh ethyl methacrylate 250g(2.2mol), isopropyl adamantanol 388g(2mol), sodium methoxide catalyst 9.3g
(0.03mol), tetrahydrofuran 1440g(20mol) investment 10L reaction kettle, stop after setting 77 DEG C of reaction temperature, 24 hours anti-
It answers, filters 1 micron of leaf filter of reaction solution at 77 DEG C, collection sodium methoxide catalyst leaves secondary stand-by.
Filtrate imports in reaction kettle, opens refrigerator and stirring, -20 DEG C of set temperature, a large amount of solids is precipitated after about 5h, stop
It only stirs, stands 1 hour, conduit is inserted into reaction kettle, vacuumizes and exports liquid, solid product is taken out, is placed on vacuum
It is 24 hours dry at 25 DEG C in drying box, collect weighing products 513g, yield 98.0%, purity 99.5%(HPLC), nuclear-magnetism knot
Fruit1H NMR(400M, C6D6): δ=5.506 (1H), 6.511 (1H), 0.885 (6H), 2.008 (3H), 1.074~
1.810(15H).Liquid is collected into tetrahydrofuran 1423g, purity 99.0%(HPLC by distillation), ethyl alcohol 154g, purity is
99.8%(HPLC).
Embodiment three: the preparation of isopropyl adamantane acrylate
Weigh methyl acrylate 103g(1.2mol), isopropyl adamantanol 194g(1mol), sodium methoxide catalyst 6.2g
(0.02mol), methylene chloride 880g(10mol) investment 5L reaction kettle, after setting 77 DEG C of reaction temperature, 24 hours, stop reaction,
1 micron of leaf filter of reaction solution is filtered at 77 DEG C, sodium methoxide catalyst is collected and leaves time stand-by, filtrate importing reaction kettle
It is interior, it opens refrigerator and stirring, -30 DEG C of set temperature, a large amount of solids is precipitated after about 2h, stops stirring, stands 1 hour, to anti-
It answers and is inserted into conduit in kettle, vacuumize and export liquid, solid product is taken out, be placed in vacuum oven, dry 24 at 25 DEG C
Hour, collect weighing products 251g, yield 95.8%, purity 99.2%(HPLC), nuclear-magnetism result1H NMR(400M, C6D6) :
δ=5.660 (1H), 6.438 (1H), 0.866 (6H), 1.173~1.909 (15H).Liquid is collected into dichloro by distillation
Methane 865g, purity 98.1%(HPLC), methanol 42g, purity 99.8%(HPLC).
Claims (10)
1. a kind of preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate, which is characterized in that including following step
It is rapid:
(1) using (methyl) acrylate and isopropyl adamantanol as reaction raw materials, using alkali compounds as catalyst, molten
In the presence of agent, ester exchange reaction is carried out at 40~120 DEG C, wherein basic compound catalysis agent is carried on porous carrier；
(2) after the reaction was completed, reaction solution filters at 60~80 DEG C by leaf filter；
(3) -60~0 DEG C is cooled the filtrate to, the solid of precipitation is 2- isopropyl -2- adamantanol (methyl) acrylate.
2. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: the alkali compounds is alkali metal, alkaline-earth metal, the oxide of rare earth element, hydroxide or salt；Preferably hydroxide
Sodium, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, sodium isopropylate, in potassium tert-butoxide
It is one or more.
3. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: the porous carrier is selected from active carbon, molecular sieve, diatomite or porous aluminas.
4. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: the structural formula of (methyl) acrylate is
In formula, R1For the alkyl containing 1~20 carbon atom；R2For H or methyl.
5. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 4, feature exist
In the molar ratio of: (methyl) acrylate, isopropyl adamantanol, alkali compounds be (0.9-1.3): 1: (0.01-
0.05mol)。
6. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: transesterification reaction temperature is 60~80 DEG C, and the reaction time is 5~40 hours.
7. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: in step (2), the aperture of leaf filter is 0.01~20 micron；In step (3), filtrate is cooled to -30~-10 DEG C.
8. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: the liquid after product is precipitated separates acquisition solvent and by-product alcohols through distillation, and the solvent is recycled anti-in transesterification
It answers.
9. the preparation method of 2- isopropyl -2- adamantanol (methyl) acrylate according to claim 1, feature exist
In: the solvent is benzene,toluene,xylene, tetrahydrofuran, methyltetrahydrofuran, dioxane, ethyl acetate, petroleum ether, first
Base tertbutyl ether, ether, butanone, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, chloroform, methylene chloride, glycol dinitrate
One of ether, tetraethyleneglycol dimethyl ether or n-hexane are a variety of.
10. a kind of preparation facilities of 2- isopropyl -2- adamantanol (methyl) acrylate, including the first reaction kettle and second is instead
Answer kettle, it is characterised in that: the outlet tube road via hole diameter of the first reaction kettle is that 0.01~20 micron of leaf filter is connected to the
Two reaction kettles；Equipped with collecting tank, the mother liquor separated in second reaction kettle is delivered to collecting tank through collecting；Described first
Blender is respectively arranged in reaction kettle and the second reaction kettle.
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| CN1830550A (en) * | 2006-03-10 | 2006-09-13 | 厦门大学 | Synthesis reaction catalyst for loading type alkali metal biodiesel oil |
| CN101811963A (en) * | 2009-02-20 | 2010-08-25 | 江苏大成医药化工有限公司 | Method for synthesizing photoresist-monomer carbon-rigid-skeleton acrylic ester compounds by transesterification |
| CN104230712A (en) * | 2014-09-26 | 2014-12-24 | 上海博康精细化工有限公司 | Method for preparing 2-isopropyl-2-adamantyl acrylate |
| CN104628562A (en) * | 2013-11-11 | 2015-05-20 | 傅志伟 | Preparation method for 2-ethyl-2-adamantanol acrylate |
| CN105502501A (en) * | 2015-12-02 | 2016-04-20 | 锦州天桥难熔金属有限公司 | Ammonium dimolybdate automatic continuous crystallization production process |
| CN106674002A (en) * | 2016-12-28 | 2017-05-17 | 天津利安隆新材料股份有限公司 | Preparation method of hindered phenol antioxidant |
-
2019
- 2019-02-26 CN CN201910143133.7A patent/CN109776311B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830550A (en) * | 2006-03-10 | 2006-09-13 | 厦门大学 | Synthesis reaction catalyst for loading type alkali metal biodiesel oil |
| CN101811963A (en) * | 2009-02-20 | 2010-08-25 | 江苏大成医药化工有限公司 | Method for synthesizing photoresist-monomer carbon-rigid-skeleton acrylic ester compounds by transesterification |
| CN104628562A (en) * | 2013-11-11 | 2015-05-20 | 傅志伟 | Preparation method for 2-ethyl-2-adamantanol acrylate |
| CN104230712A (en) * | 2014-09-26 | 2014-12-24 | 上海博康精细化工有限公司 | Method for preparing 2-isopropyl-2-adamantyl acrylate |
| CN105502501A (en) * | 2015-12-02 | 2016-04-20 | 锦州天桥难熔金属有限公司 | Ammonium dimolybdate automatic continuous crystallization production process |
| CN106674002A (en) * | 2016-12-28 | 2017-05-17 | 天津利安隆新材料股份有限公司 | Preparation method of hindered phenol antioxidant |
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