CN114163331A - Preparation method of ultra-pure photoresist reagent methyl 3-methoxypropionate - Google Patents
Preparation method of ultra-pure photoresist reagent methyl 3-methoxypropionate Download PDFInfo
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- CN114163331A CN114163331A CN202111590010.1A CN202111590010A CN114163331A CN 114163331 A CN114163331 A CN 114163331A CN 202111590010 A CN202111590010 A CN 202111590010A CN 114163331 A CN114163331 A CN 114163331A
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 title claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 140
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000007259 addition reaction Methods 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 239000003957 anion exchange resin Substances 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 10
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- 229950000688 phenothiazine Drugs 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 56
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002120 nanofilm Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004587 chromatography analysis Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- -1 copper sulfate p-hydroxyanisole Chemical compound 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of an ultra-pure photoresist reagent 3-methoxy methyl propionate, which comprises the following steps: the method comprises the steps of taking anhydrous methanol and methyl acrylate as raw materials, controlling the moisture and the acidity of the raw materials within 5ppm, taking strong-base ion exchange resin, a stabilizer and a cocatalyst as a composite catalyst, carrying out addition reaction at-5-50 ℃ to obtain a crude product, and carrying out reduced pressure rectification and separation on the crude product to obtain the ultra-pure photoresist reagent 3-methyl methoxypropionate. The catalyst can continuously react for more than 12 months, has the service life of 1-2 years and does not need to be regenerated frequently. On the other hand, the conversion per pass of the method is more than 98%, the product separation is simple, the catalyst does not need to be destroyed and then separated, the quality is good, and the purity is more than 99.99%. In addition, through the separation of the small molecular film and the centrifugal action, the metal ions, impurities and the like of the product are controlled within the index range of the electronic grade solvent for the ultra-pure photoresist.
Description
Technical Field
The invention relates to the field of photoresist reagent synthesis, and particularly relates to a preparation method of an ultra-pure photoresist reagent methyl 3-methoxypropionate with high purity, long catalyst service life and high conversion rate.
Background
The ultra-pure methyl 3-methoxypropionate is an important organic solvent and an organic synthesis intermediate, and is widely applied to the coating industry, the electronic industry and the synthesis of medical intermediates.
Methyl 3-methoxypropionate is generally prepared by the addition reaction of methanol and methyl acrylate in the presence of a catalyst. Common catalysts comprise methanesulfonic acid, supported catalysts, alkali metals, strongly basic ion exchange resins and the like, wherein the methanesulfonic acid is used as the catalyst and needs to be carried out under pressure, so that the production is inconvenient, the reaction temperature is high, the side reactions are more, and the cost is high; the use of the supported catalyst requires the use of a solvent, and has the problems of solvent recovery, long reaction time, low production efficiency and the like; the use of alkali metal as a catalyst has the disadvantages that the purity of the product is low and the requirement of an ultra-high-purity electronic grade product cannot be met; the strong-base ion exchange resin used as the catalyst has short service life, generally loses the catalytic effect within 6-8 hours, needs regeneration, and can be regenerated only for 7 times at most, is easy to break and lose the purpose, has low conversion rate which is generally between 70 and 90 percent, generates a large amount of waste water when being regenerated, greatly increases the production cost, and cannot be produced continuously in a large scale. Therefore, how to provide a preparation method of methyl 3-methoxypropionate has the characteristics of high purity, long service life of the catalyst, high conversion rate and the like becomes an objective demand.
Disclosure of Invention
The invention provides a preparation method of an ultra-pure photoresist reagent 3-methyl methoxypropionate, which aims to solve the problems of low purity, short service life of a catalyst, low conversion rate and the like of the existing preparation method of the 3-methyl methoxypropionate.
The embodiment of the invention provides a preparation method of an ultra-pure photoresist reagent 3-methoxy methyl propionate, which comprises the following steps: the method comprises the steps of taking anhydrous methanol and methyl acrylate as raw materials, controlling the moisture and the acidity of the raw materials within 5ppm, taking strong-base ion exchange resin, a stabilizer and a cocatalyst as a composite catalyst, carrying out addition reaction at-5-50 ℃ to obtain a crude product, and carrying out reduced pressure rectification and separation on the crude product to obtain the ultra-pure photoresist reagent 3-methyl methoxypropionate. Wherein the reaction temperature is lower than-5 ℃ and too slow, and the reaction temperature is higher than 50 ℃, so the service life of the catalyst is too short.
Further, in the raw materials, the molar ratio of the anhydrous methanol to the methyl acrylate is 2: 1-100: 1.
further, the raw materials are dehydrated through dehydration resin to control moisture, deacidification is performed on the raw materials through deacidification resin to control acidity, and the weight of the dehydration resin and the weight of the deacidification resin are 0.5-15% of the weight of the methyl acrylate respectively.
Further, the method for dehydration and deacidification treatment comprises the following steps: and placing the dehydrated resin in a first fixed bed reactor, placing the deacidified resin in a second fixed bed reactor, and dehydrating and deacidifying the raw materials in sequence through the first fixed bed reactor and the second fixed bed reactor.
Preferably, the main component of the dehydration resin is a low-crosslinking sodium acrylate high molecular material, and the main component of the deacidification resin is a macroporous anion exchange resin.
Further, the weight of the composite catalyst is 0.1-10% of that of methyl acrylate, the strongly basic ion exchange resin is quaternary ammonium salt anion exchange resin, the cocatalyst is alkaline oxide, and the stabilizer is one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butylphenol, phenothiazine, cuprous chloride and copper sulfate.
Preferably, the promoter is an alkaline oxide which is one or more of potassium oxide, sodium oxide, calcium oxide and magnesium oxide.
Preferably, the addition reaction is a continuous or semi-continuous reaction carried out in a third fixed bed reactor, the reaction temperature is 20-30 ℃, and the addition reaction is carried out under vacuum, normal pressure or pressurization.
Further, the third fixed bed reactor is a tubular reactor or a tower reactor.
Preferably, the separation is performed by a small molecule membrane.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the product 3-methoxy methyl propionate is obtained by carrying out Michael addition reaction on anhydrous methanol and methyl acrylate under the composite catalyst, the continuous reaction can be carried out for more than 12 months, the service life of the catalyst is 1-2 years, and frequent regeneration is not needed. On the other hand, the conversion per pass of the method is more than 98%, the product separation is simple, the catalyst does not need to be destroyed and then separated, the quality is good, and the purity is more than 99.99%. In addition, through the separation of the small molecular film and the centrifugal action, the metal ions, impurities and the like of the product are controlled within the index range of the electronic grade solvent for the ultra-pure photoresist. The method has the characteristics of simple synthesis method, mild reaction conditions, less side reactions, low cost, convenience for continuous production and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A first fixed bed reactor and a second fixed bed reactor which are 2.5 cm in diameter and 25 cm in height are respectively filled with dehydration resin and deacidification resin, a third fixed bed reactor which is 2.5 cm in diameter and 75 cm in height is filled with a composite catalyst, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, calcium oxide and p-hydroxyanisole, and the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for taking away the moisture in the first fixed bed reactor and the second fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. The raw materials are mixed in a proportioning tank according to the molar ratio of absolute ethyl alcohol to methyl acrylate of 2.1:1, then the raw materials are dehydrated through a first fixed bed reactor and deacidified through a second fixed bed reactor, so that the moisture and the acidity in the raw materials are controlled within 5ppm, in the embodiment, the weight of the dehydration resin and the weight of the deacidified resin are respectively 4% of that of the methyl acrylate, and the weight of the composite catalyst is 2% of that of the methyl acrylate. Then cooling the dehydrated and deacidified raw materials to the temperature of 5-12 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 24-28 ℃, introducing the reacted materials into a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99%, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained product back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.1: and 1, entering a fixed bed for cyclic reaction. After continuous operation for 3 months, the methyl acrylate discharged into the receiving tank is measured to be 0.5 percent, the purity of the product is 99.992 percent, the yield of the collected product is 98.5 percent, and the service life of the catalyst is 20 months.
Example 2
A first fixed bed reactor and a second fixed bed reactor which are 2.5 cm in diameter and 25 cm in height are respectively filled with dehydration resin and deacidification resin, a third fixed bed reactor which is 2.5 cm in diameter and 75 cm in height is filled with a composite catalyst, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, potassium oxide, phenothiazine and cuprous chloride, and the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for taking away the moisture in the first fixed bed reactor and the second fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. The raw materials are mixed in a proportioning tank according to the molar ratio of absolute ethyl alcohol to methyl acrylate of 2.1:1, then the raw materials are dehydrated through a first fixed bed reactor and deacidified through a second fixed bed reactor, so that the moisture and the acidity in the raw materials are controlled within 5ppm, in the embodiment, the weight of the dehydration resin and the weight of the deacidified resin are respectively 12% of that of the methyl acrylate, and the weight of the composite catalyst is 0.7% of that of the methyl acrylate. Then cooling the dehydrated and deacidified raw materials to the temperature of 12-20 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 26-30 ℃, the reacted materials enter a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99 percent, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained product back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.1: and 1, entering a fixed bed for cyclic reaction. Continuously operating for 5 months, and measuring that the methyl acrylate discharged into the receiving tank is 0.3 percent, the purity of the product is 99.994 percent, the yield of the collected product is 98.6 percent, and the service life of the catalyst is 21 months.
Example 3
A first fixed bed reactor and a second fixed bed reactor which are 2.5 cm in diameter and 25 cm in height are respectively filled with dehydration resin and deacidification resin, a third fixed bed reactor which is 2.5 cm in diameter and 75 cm in height is filled with a composite catalyst, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, calcium oxide, magnesium oxide, 2, 6-di-tert-butylphenol and copper sulfate p-hydroxyanisole, and the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for taking away the moisture in the first fixed bed reactor and the second fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. The raw materials are mixed in a proportioning tank according to the molar ratio of absolute ethyl alcohol to methyl acrylate of 2.1:1, then the raw materials are dehydrated through a first fixed bed reactor and deacidified through a second fixed bed reactor, so that the moisture and the acidity in the raw materials are controlled within 5ppm, in the embodiment, the weight of the dehydration resin and the weight of the deacidified resin are respectively 13% of that of the methyl acrylate, and the weight of the composite catalyst is 8% of that of the methyl acrylate. Then cooling the dehydrated and deacidified raw materials to the temperature of 20-30 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, introducing the temperature of the third fixed bed reactor to be 26-30 ℃, introducing the reacted materials into a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99%, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained products back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.1: and 1, entering a fixed bed for cyclic reaction. After continuous operation for 6 months, the methyl acrylate discharged into the receiving tank is measured to be 0.6 percent, the purity of the product is 99.991 percent, the yield of the collected product is 98.5 percent, and the service life of the catalyst is 22 months.
Example 4
A first fixed bed reactor and a second fixed bed reactor which are 2.5 cm in diameter and 25 cm in height are respectively filled with dehydration resin and deacidification resin, a third fixed bed reactor which is 2.5 cm in diameter and 75 cm in height is filled with a composite catalyst, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, potassium oxide, magnesium oxide, phenothiazine and p-hydroxyanisole, and the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for taking away the moisture in the first fixed bed reactor and the second fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. The raw materials are mixed in a proportioning tank according to the molar ratio of absolute ethyl alcohol to methyl acrylate of 2.5:1, then the raw materials are dehydrated through a first fixed bed reactor and deacidified through a second fixed bed reactor, so that the moisture and the acidity in the raw materials are controlled within 5ppm, in the embodiment, the weight of the dehydration resin and the weight of the deacidified resin are respectively 15% of that of the methyl acrylate, and the weight of the composite catalyst is 15% of that of the methyl acrylate. Then cooling the dehydrated and deacidified raw materials to 35-45 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 28-32 ℃, introducing the reacted materials into a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99%, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained product back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.5: and 1, entering a fixed bed for cyclic reaction. Continuously operating for 12 months, and measuring that the methyl acrylate discharged into the receiving tank is 0.4 percent, the purity of the product is 99.993 percent, the yield of the collected product is 98.7 percent, and the service life of the catalyst is 25 months.
Comparative example 1
The dehydration resin is filled in a first fixed bed reactor with the diameter of 2.5 cm and the height of 25 cm, the composite catalyst is filled in a third fixed bed reactor with the diameter of 2.5 cm and the height of 75 cm, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, potassium oxide, magnesium oxide, phenothiazine and hydroquinone, and the first fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for carrying away the moisture in the first fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. Mixing the absolute ethyl alcohol and the methyl acrylate into a raw material according to the molar ratio of 2.5:1 in a proportioning tank, and dehydrating the raw material by a first fixed bed reactor to control the water content in the raw material to be within 5ppm, wherein in the comparative example, the weight of the dehydrated resin is 15% of the weight of the methyl acrylate, and the weight of the composite catalyst is 15% of the weight of the methyl acrylate. Then cooling the dehydrated raw materials to 35-45 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, controlling the temperature of the third fixed bed reactor to 28-32 ℃, introducing the reacted materials into a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99%, collecting the product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained product back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to 2.5: and 1, entering a fixed bed for cyclic reaction. The operation is continuously carried out for 1 month, and the methyl acrylate discharged into the receiving tank is 1.6 percent, the purity of the product is 99.91 percent, the yield of the collected product is 96.9 percent, and the service life of the catalyst is 1 month.
Comparative example 2
Deacidifying resin is filled in a second fixed bed reactor with the diameter of 2.5 cm and the height of 25 cm, composite catalyst is filled in a third fixed bed reactor with the diameter of 2.5 cm and the height of 75 cm, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, magnesium oxide, phenothiazine and hydroquinone, and the second fixed bed reactor and the third fixed bed reactor are sequentially connected together. Firstly, absolute ethyl alcohol is used for carrying away the moisture in the second fixed bed reactor until the water content of the coming absolute methyl alcohol is lower than 0.5 percent. Then the composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. Mixing the raw materials in a proportioning tank according to the molar ratio of the absolute ethyl alcohol to the methyl acrylate of 2.4:1, and deacidifying the raw materials by a second fixed bed reactor to control the acidity in the raw materials within 5ppm, wherein in the comparative example, the weight of the deacidified resin is 14% of that of the methyl acrylate respectively, and the weight of the composite catalyst is 14% of that of the methyl acrylate. Then cooling the raw materials after deacidification treatment to the temperature of 35-45 ℃, introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 28-32 ℃, the reacted materials enter a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of over 99.99 percent, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained products back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.4: and 1, entering a fixed bed for cyclic reaction. The operation was continued for 1.5 months, and it was determined that 1.1% of the methyl acrylate discharged into the receiving tank, the purity of the product was 99.96%, the yield of the collected product was 97.2%, and the service life of the catalyst was 1.5 months.
Comparative example 3
And (3) filling a third fixed bed reactor with the diameter of 2.5 cm and the height of 75 cm with a composite catalyst, wherein the composite catalyst is a mixture of quaternary ammonium salt anion exchange resin, potassium oxide, hydroquinone and phenothiazine. The raw materials are mixed in a proportioning tank according to the molar ratio of the absolute ethyl alcohol to the methyl acrylate of 2.2:1, and in the embodiment, the weight of the composite catalyst is 15 percent of that of the methyl acrylate. The composite catalyst is cleaned by absolute ethyl alcohol and then is purged by nitrogen. Introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 30-34 ℃, the reacted materials enter a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of more than 99.99%, collecting the product as a product, calculating the yield, pumping excessive methanol, unreacted methyl acrylate and a small amount of entrained product back to a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2.2: and 1, entering a fixed bed for cyclic reaction. The continuous operation is carried out for 0.3 month, and the methyl acrylate discharged into the receiving tank is measured to be 2.2 percent, the purity of the product is measured to be 99.49 percent, the yield of the collected product is 93.6 percent, and the service life of the catalyst is measured to be 0.3 month.
Comparative example 4
A third fixed bed reactor with the diameter of 2.5 cm and the height of 75 cm is filled with a common catalyst (only a stabilizer is added, and no cocatalyst is added), wherein the common catalyst is a mixture of sodium methoxide catalyst, sodium oxide and hydroquinone. The raw materials are mixed in a proportioning tank according to the molar ratio of the absolute ethyl alcohol to the methyl acrylate of 2:1, and in the embodiment, the weight of the composite catalyst is 12 percent of that of the methyl acrylate. The catalyst was washed with absolute ethanol and purged with nitrogen. Introducing the raw materials into a third fixed bed reactor for addition reaction, wherein the temperature of the third fixed bed reactor is 35-45 ℃, the reacted materials enter a receiving tank, detecting the content of methyl acrylate in the receiving tank, performing reduced pressure rectification on the materials in the receiving tank through a rectifying tower, performing small molecular membrane separation to obtain a product with the purity of more than 99.99%, collecting the product as a product, calculating the yield, returning excessive methanol, unreacted methyl acrylate and a small amount of entrained product into a proportioning tank, adding fresh anhydrous methanol and methyl acrylate, testing the content through chromatography, and adjusting the molar ratio to be 2: and 1, entering a fixed bed for cyclic reaction. The continuous operation is carried out for 0.1 month, and the methyl acrylate discharged into the receiving tank is measured to be 2.8 percent, the purity of the product is 99.36 percent, the yield of the collected product is 92.3 percent, and the service life of the catalyst is 0.1 month.
When the methyl acrylate concentration in the effluent product exceeds 1%, the catalyst is used to the end point and needs to be regenerated. As can be seen from examples 1-4 and comparative examples 1-4, the present application obtains methyl 3-methoxypropionate by Michael addition reaction of absolute ethanol and methyl acrylate under basic catalyst, and the strongly basic anion exchange resin used in the process is easily destroyed by acid and inactivated as the catalyst of the reaction, resulting in reduced conversion rate and reduced service life, and trace amount of water in the raw material reacts with methyl acrylate under basic catalyst to produce by-products, resulting in reduced conversion rate and yield. On the other hand, the promoter is alkaline oxide which is matched with strong-alkaline anion exchange resin for use, so that the system has stronger alkalinity, better catalytic effect and better stability. In addition, methyl acrylate molecules have unstable double bond structures and are easy to polymerize under a heated condition, so that the stabilizer is added to prevent the risk of conversion rate reduction and even tower blockage caused by inactivation due to the fact that a catalyst is wrapped by methyl acrylate polymerization. Therefore, under the conditions of dehydration and deacidification pretreatment and the matched use of a cocatalyst and a stabilizer, the reaction conversion rate is greatly improved, the service life of the catalyst is also greatly prolonged, and the product quality is also greatly improved.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.
Claims (10)
1. A preparation method of ultra-pure photoresist reagent methyl 3-methoxypropionate is characterized by comprising the following steps: the method comprises the steps of taking anhydrous methanol and methyl acrylate as raw materials, controlling the moisture and the acidity of the raw materials within 5ppm, taking strong-base ion exchange resin, a stabilizer and a cocatalyst as a composite catalyst, carrying out addition reaction at-5-50 ℃ to obtain a crude product, and carrying out reduced pressure rectification and separation on the crude product to obtain the ultra-pure photoresist reagent 3-methyl methoxypropionate.
2. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 1, wherein the molar ratio of the anhydrous methanol to the methyl acrylate in the raw materials is 2:1 to 100: 1.
3. the method of claim 1, wherein the raw material is dehydrated with a dehydrating resin to control moisture content and deacidified with a deacidifying resin to control acidity, and the weight of the dehydrating resin and the weight of the deacidifying resin are respectively 0.5-15% of the weight of the methyl acrylate.
4. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 3, wherein the dehydration and deacidification treatment comprises: and placing the dehydrated resin in a first fixed bed reactor, placing the deacidified resin in a second fixed bed reactor, and dehydrating and deacidifying the raw materials in sequence through the first fixed bed reactor and the second fixed bed reactor.
5. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 3 or 4, wherein the main component of the dehydration resin is a low-crosslinking sodium acrylate polymer material, and the main component of the deacidification resin is a macroporous anion exchange resin.
6. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 1, wherein the weight of the composite catalyst is 0.1 to 10% of the weight of the methyl acrylate, the strongly basic ion exchange resin is a quaternary ammonium anion exchange resin, the cocatalyst is a basic oxide, and the stabilizer is one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butylphenol, phenothiazine, cuprous chloride and copper sulfate.
7. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate of claim 6, wherein the promoter is a basic oxide selected from one or more of potassium oxide, sodium oxide, calcium oxide, and magnesium oxide.
8. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 1, wherein the addition reaction is a continuous or semi-continuous reaction carried out in a third fixed bed reactor, the reaction temperature is 20 to 30 ℃, and the addition reaction is carried out under vacuum, normal pressure or pressurization.
9. The method for preparing the ultra-high purity photoresist reagent methyl 3-methoxypropionate according to claim 8, wherein the third fixed bed reactor is a tubular reactor or a tower reactor.
10. The method of claim 1, wherein the separation is performed by a small molecule membrane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4948915A (en) * | 1986-07-22 | 1990-08-14 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic process for production of alkoxylated esters |
| CN111018707A (en) * | 2019-12-19 | 2020-04-17 | 深圳市普利凯新材料股份有限公司 | Preparation method of methyl 3-methoxypropionate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4948915A (en) * | 1986-07-22 | 1990-08-14 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic process for production of alkoxylated esters |
| CN111018707A (en) * | 2019-12-19 | 2020-04-17 | 深圳市普利凯新材料股份有限公司 | Preparation method of methyl 3-methoxypropionate |
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| 余毓增: "高吸水性树脂", 《上海化工》 * |
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