CN115872952A - Preparation method and system of glycidyl methacrylate - Google Patents
Preparation method and system of glycidyl methacrylate Download PDFInfo
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- CN115872952A CN115872952A CN202111140311.4A CN202111140311A CN115872952A CN 115872952 A CN115872952 A CN 115872952A CN 202111140311 A CN202111140311 A CN 202111140311A CN 115872952 A CN115872952 A CN 115872952A
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- glycidyl methacrylate
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 42
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 11
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 230000005405 multipole Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims 1
- 239000012973 diazabicyclooctane Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 8
- -1 methacrylic acid alkali metal salt Chemical class 0.000 description 7
- 238000000066 reactive distillation Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention provides a preparation method of glycidyl methacrylate, which is characterized in that epoxy propanol and methyl methacrylate are produced by adopting an open-flow reactor under the action of a catalyst. The invention also provides a preparation system of the glycidyl methacrylate, which comprises a reaction unit assembly and a rectifying tower; the reaction unit assembly comprises a reaction unit; the reaction unit comprises a plug flow reactor and a flash column. The invention not only improves the reaction efficiency of the glycidyl methacrylate, but also substantially reduces the aggregation effect of the by-products, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method and a system of glycidyl methacrylate. The invention utilizes plug flow to produce glycidyl methacrylate.
Background
Glycidyl methacrylate, GMA for short, because the molecule has two functional groups of active vinyl and epoxy group with ionic reaction, can be polymerized in a functional group mode and also can be polymerized in an ionic reaction mode, therefore, the glycidyl methacrylate can be used for modifying ethylene polymers and condensation polymers, and is an excellent material modifier. It is widely used in the industries of paint, adhesive, plastic modifier, semiconductor and the like.
Currently, there are two main methods for the preparation of GMA. Firstly, epoxy chloropropanol and methacrylic acid alkali metal salt are used for reaction, and secondly, epoxy chloropropanol and methyl methacrylate are used as raw materials for ester exchange reaction, and finally, glycidyl methacrylate is obtained.
1. A process for producing a copolymer by using epichlorohydrin and an alkali metal methacrylate (Method of producing a glycidyl ester, am. Cyanamide Co. US2556075,1948; method of polymerizing a glycidyl compound, am. Cyanamide Co. US2537981, 1949):
methyl methacrylate and hydroxide of alkali metal react in low molecular alcohol and high boiling point solvent in the presence of polymerization inhibitor to produce alkali metal (methyl) acrylate, and after drying to eliminate water, low molecular alcohol and other volatile matter, epichlorohydrin (ECH) and phase transfer catalyst are added for esterification to obtain coarse (methyl) acrylate product.
As can be seen from the reaction formula, the method firstly needs to convert methyl methacrylate into alkali metal methacrylate, (M can be sodium or potassium), and the process produces lower alcohol or water and other byproducts; then reacting with epoxy chloropropanol under the action of a catalyst to generate glycidyl methacrylate with alkali metal salt by-products.
2. A process for producing a copolymer of glycidol and methyl methacrylate (Priyank N.Shah, namjoon Kim, zhuangong Huang et al, environmental friendly benign synthesis of vinyl ester resin from biological glycerin, RSC adv.,2015,5, 38673):
and the glycidyl methacrylate can also be obtained by the ester exchange of the epoxy propanol and the methyl methacrylate. In the literature reports, 50g of methyl methacrylate is reacted with 7.4g of epoxypropanol, 0.05g of 2, 4-dimethyl-6-tert-butylphenol is added as a polymerization inhibitor, 0.055g of potassium cyanide is added as a catalyst and reacted for 2h at 70-80 ℃, and finally the obtained reaction solution is distilled, so that glycidyl methacrylate can be obtained with a yield of only 25.3%, which is quite low.
Disclosure of Invention
In order to improve the reaction effect of preparing glycidyl methacrylate by using epoxypropanol and methyl methacrylate, the inventors tried to perform the transesterification reaction by means of reactive distillation. The conversion rate and yield of the reaction can be greatly improved by the reactive distillation method, however, as the reactive distillation mode inevitably causes part of materials to stay in the reactive distillation device for a long time (natural characteristics of a full mixed flow reactor), and the epoxypropanol is a particularly unstable material (epoxy is easy to open a ring), by-products are accumulated in the reactive distillation device during long-time continuous reaction, and the long-term reaction effect of the reactive distillation device is reduced.
It can be seen that the inventors tried to improve the conversion rate and yield by means of reactive distillation, and although the success is achieved, the inventors have brought about new problems, and finally, the long-term reaction effect is affected. To overcome this difficulty, the inventors continued to try and eventually arrived at new solutions. The method specifically comprises the following steps:
in one aspect, the invention provides a method for preparing glycidyl methacrylate, which comprises the step of producing glycidyl methacrylate by using an extrusion flow reactor under the action of a catalyst by using epoxy propanol and methyl methacrylate.
Further, the plug flow reactor is a tubular reactor or a microchannel reactor.
Further, the equivalent ratio of the epoxypropanol to the methyl methacrylate is 1 to 10.
Further, the catalyst is selected from one or more of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, 1, 8-diazabicycloundec-7-ene (1, 8-Diazabicyclo [5.4.0] undec-7-ene, DBU), triethylenediamine (DABCO), 4-Dimethylaminopyridine (DMAP).
Further, the catalyst is loaded on the particles to prepare solid base which is used for catalyzing the reaction of the epoxypropanol and the methyl methacrylate; the particles are selected from one or more of zirconia, alumina, magnesia, zinc oxide and molecular sieves.
Further, the molecular sieve is selected from one or more of SBA-15 and MCM-41.
Further, the reaction temperature is 40-80 ℃.
Further, the method comprises the following steps:
step one, mixing methyl methacrylate and epoxypropanol and entering the plug flow reactor; a fixed bed is arranged in the plug flow reactor as a catalytic system; the catalytic system comprises a solid base made with the catalyst supported on particles;
and step two, feeding the material out of the plug flow reactor in the step one into a flash tower to remove methanol and partial methyl methacrylate.
Further, the third step of subjecting the materials subjected to the first-stage reaction to a multi-stage series reaction to obtain the glycidyl methacrylate;
the material subjected to the first-stage reaction is treated in the first step and the second step; the multipole series reaction refers to processing in the first step and the second step for a plurality of times.
Further, the multi-stage series reaction plus the first stage reaction is at most 10 stages.
Further, the reaction time in the plug flow reactor of each stage of reaction is 10-30min; the flash column pressure is from 100 to 500mbar.
And further, the fourth step of extracting the flash-evaporated material in a first-stage extraction tower to obtain the glycidyl methacrylate.
And further, feeding the residual materials obtained in the fifth step and the fourth step into a secondary extraction tower to recover the epoxypropanol.
Further, the extracted extraction liquid is selected from one or more of petroleum ether, diethyl ether, acetone, ethyl acetate, tetrahydrofuran, methanol, ethanol and water.
In another aspect, the present invention provides a system for preparing glycidyl methacrylate, comprising a reaction unit assembly and a rectification column; the reaction unit assembly comprises a reaction unit; the reaction unit comprises a plug flow reactor and a flash tower;
the inlet of the plug flow reactor is used for adding reactants; the outlet of the plug flow reactor is connected with the inlet of the flash tower; the first outlet of the flash tower is connected with the inlet of the rectifying tower and is used for discharging methanol and part of methyl methacrylate to the rectifying tower; a second outlet of the flash column for the outflow of reaction product and the reactants not yet involved in the reaction; the first outlet of the rectifying tower is used for discharging methanol; the second outlet of the rectifying tower is connected with the inlet of the plug flow reactor and is used for sending the methyl methacrylate in the rectifying tower into the plug flow reactor;
the reactants are epoxypropanol and methyl methacrylate; the reaction product is glycidyl methacrylate; and a catalyst is fixed on a fixed bed of the plug flow reactor and is used for catalyzing epoxy propanol and methyl methacrylate to generate glycidyl methacrylate.
Glycidyl methacrylate and methanol are obtained after epoxy propanol (glycidol) reacts with methyl methacrylate, the glycidyl methacrylate is taken as a product, and the methanol is taken as a byproduct to be separated, so that a preparation system of the glycidyl methacrylate needs to separate the methanol.
In one embodiment, the number of reaction units is n, 2. Ltoreq. N.ltoreq.10; each of the reaction units is connected in series such that reactants are maintained flowing from the plug flow reactor to the flash column throughout each of the reaction units.
In one embodiment, the second outlet of the flash column is connected to the inlet of the plug flow reactor; the preparation system of the glycidyl methacrylate is set to enable the reactants to circularly pass through the reaction unit for multiple times and react in the reaction unit, wherein one-stage reaction is completed after every time of passing through the reaction unit, and at most 10-stage reaction is carried out.
In one embodiment, further comprising an extraction device component; the extraction device assembly is connected to the outlet of the reaction unit assembly and is used for extracting the materials flowing out of the reaction unit assembly.
In one embodiment, the extraction plant assembly comprises a primary extraction column and a secondary extraction column; a first-stage extraction tower and a second-stage extraction tower; the inlet of the primary extraction tower is connected with the outlet of the reaction unit component; the first outlet of the primary extraction tower is used for discharging the prepared glycidyl methacrylate; the second outlet of the primary extraction tower is connected with the inlet of the secondary extraction tower; and the outlet of the secondary extraction tower is used for discharging the recovered epoxy propanol.
Further, the plug flow reactor is a tubular reactor or a microchannel reactor.
Further, the equivalent ratio of the epoxypropanol to the methyl methacrylate is 1 to 10.
Further, the catalyst is selected from one or more of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, DBU, DABCO and DMAP.
Further, the catalyst is loaded on the particles to prepare solid base which is used for catalyzing the reaction of the epoxypropanol and the methyl methacrylate; the particles are selected from one or more of zirconia and alumina.
In view of the economic and environment-friendly advantages of the ester exchange method and the comprehensive consideration of the characteristics of the full mixed flow reactor, the invention provides the method for producing the glycidyl methacrylate by utilizing plug flow, which not only improves the reaction efficiency, but also substantially reduces the aggregation effect of the by-products.
In the reaction, the catalyst used in the invention comprises sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, DBU, DABCO, DMAP and the like, or the catalyst is loaded on particles of zirconia, alumina and the like to prepare solid alkali, and the catalyst has small toxic and side effects and can be mechanically applied or removed by the subsequent process.
In terms of process, the synthesis of the glycidyl methacrylate is carried out by the tubular reactor or the microchannel reactor, so that an intermittent operation mode is avoided, the whole production process is more efficient, and the long-time reaction effect deterioration caused by the accumulation of byproducts in the reactor is avoided. In the process, raw materials (methyl methacrylate and epoxypropanol) are mixed and enter a tubular reactor or a microchannel reactor, a fixed bed module is arranged in the tubular reactor or the microchannel reactor as a catalytic system, the materials enter a flash tower after exiting the tubular reactor to remove methanol and part of Methyl Methacrylate (MMA), the tubular reactor and the flash tower can be connected in series in a multistage manner to obtain a better reaction effect, the flashed materials enter an extraction tower to be extracted to obtain glycidyl methacrylate, and the rest materials enter a second extraction tower to recover epoxypropanol. However, if the reaction efficiency is higher after the tubular reactor and the flash tower are connected in series in a multi-stage manner, an extraction tower can be omitted, and the discharged material can be directly used as a glycidyl methacrylate product.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
Fig. 1 is a system for producing glycidyl methacrylate in one embodiment of the present invention.
Detailed Description
In order to make the technical means, the characteristics, the purposes and the functions of the invention easy to understand, the invention is further described with reference to the specific drawings. However, the present invention is not limited to the following embodiments.
It should be understood that the structures, ratios, sizes, etc. shown in the drawings and attached to the description are only for understanding and reading the disclosure of the present invention, and are not intended to limit the practical conditions of the present invention, so that the present invention has no technical significance, and any modifications of the structures, changes of the ratio relationships, or adjustments of the sizes, should still fall within the scope of the technical contents of the present invention without affecting the efficacy and the achievable purpose of the present invention.
The process is illustrated by taking fig. 1 as an example, firstly, mixing epoxypropanol and methyl methacrylate according to the proportion of 1. After the reaction is finished, the mixed material is introduced into a continuous extraction tower (such as a first-stage extraction tower 3 and a second-stage extraction tower 4 in fig. 1) to obtain glycidyl methacrylate, and the rest material enters a second-stage extraction tower 4 to recycle the epoxypropanol.
Preparation system of glycidyl methacrylate
Example 1
Fig. 1 also shows a system for preparing glycidyl methacrylate according to the embodiment, which comprises a reaction unit component, a rectifying tower 5 and an extraction device component. The reaction unit assembly includes a reaction unit. The reaction unit comprises a plug flow reactor 1 and a flash column 2.
The inlet 12 of the plug flow reactor is used for the addition of reactants. The outlet 13 of the plug flow reactor is connected to the inlet 21 of the flash column. The first outlet 22 of the flash column is connected to the inlet 53 of the rectification column for discharging methanol and part of the methyl methacrylate to the rectification column 5. The second outlet 23 of the flash column is used to discharge the reaction product and reactants not yet involved in the reaction. The first outlet 52 of the rectification column is used for discharging methanol. The second outlet 51 of the rectifying column is connected with the inlet 12 of the plug flow reactor for feeding the methyl methacrylate in the rectifying column 5 into the plug flow reactor 1.
Reactants are epoxypropanol and methyl methacrylate; the reaction product is glycidyl methacrylate. The fixed bed 11 of the plug flow reactor is fixed with a catalyst for catalyzing epoxypropanol and methyl methacrylate to generate glycidyl methacrylate.
The extraction device component comprises a primary extraction tower 3 and a secondary extraction tower 4. The inlet 31 of the primary extraction column is connected to the outlet of the reaction unit assembly, in this case the second outlet 23 of the flash column. The first outlet 33 of the primary extraction column is used for discharging the glycidyl methacrylate obtained by the preparation. The second outlet 32 of the primary extraction column is connected to the inlet 41 of the secondary extraction column. The outlet 42 of the secondary extraction tower and the inlet 12 of the plug flow reactor, and the reclaimed epoxypropanol is added into the plug flow reactor 1 again for reaction. The plug flow reactor 1 is a tubular reactor or a microchannel reactor.
Example 2
In the embodiment, the number of the reaction units is n, wherein n is more than or equal to 2 and less than or equal to 10; each reaction unit is connected in series such that the reactants are maintained flowing from the plug flow reactor to the flash column throughout each reaction unit. Otherwise, the procedure was as in example 1.
Example 3
In this example, the second outlet of the flash column is connected to the inlet of the plug flow reactor. The preparation system of the glycidyl methacrylate is set to be that reactants circulate through the same or a plurality of reaction units for a plurality of times and react in the reaction units, the first-stage reaction is completed after each time of passing through the reaction units, and at most 10-stage reaction is carried out. The rest of the process was the same as in example 1.
Preparation method of glycidyl methacrylate
Example 4
Mixing 37g of epoxypropanol with 100g of methyl methacrylate, adding the mixture into a microchannel reactor or a tubular reactor, controlling the temperature to be 55 ℃, using solid alkali as a filler of a fixed bed, enabling fluid to flow in a pipeline at the speed of 0.2ml/min, controlling the temperature in a flash evaporation device (such as a flash tower) to be 55 ℃, controlling the vacuum to be 100mbar, supplementing 100g of methyl methacrylate when entering the next pipeline, and continuously passing through 5 reaction units, wherein the conversion rate of the epoxypropanol is 51%,68%,80%,89% and 95% in sequence.
Example 5
Mixing 37g of epoxypropanol and 100g of methyl methacrylate, adding the mixture into a microchannel reactor or a tubular reactor, controlling the temperature to be 55 ℃, taking solid alkali as a filler of a fixed bed, enabling fluid to flow in a pipeline at the speed of 0.2ml/min, controlling the temperature in a flash evaporation device (such as a flash tower) to be 55 ℃, controlling the vacuum to be 100mbar, supplementing 100g of methyl methacrylate when the mixture enters the next pipeline, continuously passing through 5 reaction units, and then extracting the reaction system in an extraction tower by using a petroleum ether/ethyl acetate/water mixed solution, so as to finally obtain 99% of glycidyl methacrylate.
Example 6
Mixing 37g of epoxypropanol and 100g of methyl methacrylate, adding the mixture into a microchannel reactor or a tubular reactor, controlling the temperature to be 55 ℃, using solid alkali as a filler of a fixed bed, enabling fluid to flow in a pipeline at the speed of 0.2ml/min, controlling the temperature in a flash evaporation device (such as a flash tower) to be 55 ℃, controlling the vacuum to be 100mbar, supplementing 100g of methyl methacrylate when the mixture enters the next pipeline, and extracting the reaction system through an extraction tower of petroleum ether/ethyl acetate/water to obtain 96% of glycidyl methacrylate.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (18)
1. The preparation method of glycidyl methacrylate is characterized in that epoxy propanol and methyl methacrylate are subjected to glycidyl methacrylate production by adopting an advection-type plug flow reactor under the action of a catalyst.
2. The method of claim 1, wherein the plug flow reactor is a tubular reactor or a microchannel reactor.
3. The method for producing glycidyl methacrylate according to claim 1, wherein the equivalent ratio of epoxypropanol to methyl methacrylate is 1.
4. The method of claim 1, wherein the catalyst is one or more selected from the group consisting of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, DBU, DABCO, and DMAP.
5. The method for preparing glycidyl methacrylate according to claim 4, wherein the catalyst is supported on the particles to prepare a solid base, and then the solid base is used for catalyzing the reaction of epoxypropanol and methyl methacrylate; the particles are selected from one or more of zirconia, alumina, magnesia, zinc oxide and molecular sieves.
6. The method for preparing glycidyl methacrylate according to claim 1, wherein the reaction temperature is 40 to 80 ℃.
7. The method of preparing glycidyl methacrylate according to claim 1, comprising the steps of:
step one, mixing methyl methacrylate and epoxy propanol and entering the plug flow reactor; a fixed bed is arranged in the plug flow reactor as a catalytic system; the catalytic system comprises a solid base made by supporting the catalyst on particles;
and step two, feeding the material out of the plug flow reactor in the step one into a flash tower to remove methanol and part of methyl methacrylate.
8. The method for preparing glycidyl methacrylate according to claim 7, further comprising a third step of subjecting the first-stage reacted material to a multi-stage series reaction to obtain the glycidyl methacrylate;
the material subjected to the first-stage reaction is treated in the first step and the second step; the multipole series reaction refers to processing in the first step and the second step for a plurality of times.
9. The method of claim 8, wherein the multi-stage series reaction plus the first stage reaction is at most 10 stages of reaction.
10. The method for producing glycidyl methacrylate according to claim 8, wherein the reaction time in the plug flow reactor of each stage of the reaction is 10 to 30min; the flash column pressure is from 100 to 500mbar.
11. The method for preparing glycidyl methacrylate according to claim 7, further comprising a fourth step of extracting the flashed material in a first extraction column to obtain the glycidyl methacrylate.
12. The method of claim 11, further comprising a fifth step of feeding the remaining material of the fourth step into a second-stage extraction column to recover the epoxypropanol.
13. The method of claim 11, wherein the extracted liquid is one or more selected from the group consisting of petroleum ether, diethyl ether, acetone, ethyl acetate, tetrahydrofuran, methanol, ethanol, and water.
14. The system for preparing the glycidyl methacrylate is characterized by comprising a reaction unit assembly and a rectifying tower; the reaction unit assembly comprises a reaction unit; the reaction unit comprises an extrusion flow reactor and a flash tower;
the inlet of the plug flow reactor is used for adding reactants; the outlet of the plug flow reactor is connected with the inlet of the flash tower; the first outlet of the flash tower is connected with the inlet of the rectifying tower and is used for discharging methanol and part of methyl methacrylate to the rectifying tower; a second outlet of the flash column for the outflow of reaction product and the reactants not yet involved in the reaction; the first outlet of the rectifying tower is used for discharging methanol; the second outlet of the rectifying tower is connected with the inlet of the plug flow reactor and is used for sending the methyl methacrylate in the rectifying tower into the plug flow reactor;
the reactants are epoxypropanol and methyl methacrylate; the reaction product is glycidyl methacrylate; and a catalyst is fixed on a fixed bed of the plug flow reactor and is used for catalyzing epoxy propanol and methyl methacrylate to generate glycidyl methacrylate.
15. The glycidyl methacrylate production system according to claim 14, wherein the number of the reaction units is n, wherein n is 2. Ltoreq. N.ltoreq.10; each of the reaction units is connected in series such that reactants are maintained flowing from the plug flow reactor to the flash column throughout each of the reaction units.
16. The system for preparing glycidyl methacrylate according to claim 14, wherein the second outlet of the flash column is connected to the inlet of the plug flow reactor; the preparation system of the glycidyl methacrylate is set to enable the reactants to circularly pass through the reaction unit for multiple times and react in the reaction unit, wherein one-stage reaction is completed after every time of passing through the reaction unit, and at most 10-stage reaction is carried out.
17. The system for producing glycidyl methacrylate according to claim 14, further comprising an extraction device module; the extraction device assembly is connected to the outlet of the reaction unit assembly and is used for extracting the materials flowing out of the reaction unit assembly.
18. The system for preparing glycidyl methacrylate according to claim 17, wherein the extraction device module comprises a primary extraction column and a secondary extraction column; the inlet of the primary extraction tower is connected with the outlet of the reaction unit component; the first outlet of the first-stage extraction tower is used for discharging the prepared glycidyl methacrylate; the second outlet of the primary extraction tower is connected with the inlet of the secondary extraction tower; the outlet of the secondary extraction tower is used for discharging the recovered epoxy propanol; and the outlet of the secondary extraction tower is connected with the inlet of the reaction unit component.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580643A (en) * | 2011-12-30 | 2012-07-18 | 微楷化学（大连）有限公司 | Micro-reaction device and application thereof in synthesis of glycidyl methacrylate |
| CN108707126A (en) * | 2018-07-03 | 2018-10-26 | 山东柳湾新材料有限公司 | Using the method for microchannel reaction unit synthesizing methyl glycidyl acrylate |
| CN112625007A (en) * | 2019-10-09 | 2021-04-09 | 佳化化学(上海)有限公司 | Method for preparing glycidyl methacrylate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580643A (en) * | 2011-12-30 | 2012-07-18 | 微楷化学（大连）有限公司 | Micro-reaction device and application thereof in synthesis of glycidyl methacrylate |
| CN108707126A (en) * | 2018-07-03 | 2018-10-26 | 山东柳湾新材料有限公司 | Using the method for microchannel reaction unit synthesizing methyl glycidyl acrylate |
| CN112625007A (en) * | 2019-10-09 | 2021-04-09 | 佳化化学(上海)有限公司 | Method for preparing glycidyl methacrylate |
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