CN103599815A - Activated-carbon-supported perfluorosulfonic resin catalyst and application thereof in catalytic synthesis of alkoxy ethyl (meth)acrylate - Google Patents
Activated-carbon-supported perfluorosulfonic resin catalyst and application thereof in catalytic synthesis of alkoxy ethyl (meth)acrylate Download PDFInfo
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Abstract
The invention relates to an activated-carbon-supported perfluorosulfonic resin catalyst which is prepared through taking activated carbon as a carrier and taking a perfluorosulfonic resin solution, extracted and prepared from waste ion exchange membranes of the chlor-alkali industry, as an active ingredient. According to a method for synthesizing alkoxy ethyl (meth)acrylate, the mole ratio of reactants, namely (meth)acrylic acid to ethylene glycol monoalkyl ether, is (1: 1) to (1: 2), the dosage of a dehydrating agent toluene in percentage by mass accounts for 10-40% of the total mass of the reactants, the dosage of a polymerization inhibitor phenothiazine in percentage by mass accounts for 0.05-0.30% of the total mass of the reactants, the dosage of the activated-carbon-supported perfluorosulfonic resin catalyst according to claim 1 to claim 3 accounts for 1-5% of the total mass of the reactants, the reaction temperature is 124-140 DEG C, and the reaction time is 3-5 hours. The catalyst disclosed by the invention has the advantages of rich pore structure, relatively large specific surface area and good thermal stability and chemical stability.
Description
Technical field
The present invention relates to the preparation method of the immobilized perfluorinated sulfonic resin catalyst of a kind of active carbon, for catalyzing and synthesizing (methyl) acrylic acid alcoxyl base ethyl ester, belong to field of chemical technology.
Background technology
(methyl) acrylic acid alcoxyl base ethyl ester [CH
2=C (CH
3) COOCH
2cH
2oR; R can be methyl, ethyl, butyl, phenyl etc.] be important organic active monomer, because containing unsaturated carbon-carbon double bond in structure, can with many monomer generation copolymerization and homopolymerization, and this monomer contains ehter bond side chain, its polymer or copolymer are having important effect aspect resin, coating, adhesive, medical material.
At present, the synthetic route of (methyl) acrylic acid alcoxyl base ethyl ester have that ester-interchange method, (methyl) acryloyl chloride react with ethylene glycol monoalkyl ether, direct esterification etc.CN102351693A and CN102850217A have introduced with ester-interchange method and have prepared methoxyethyl methacrylate, take methyl methacrylate and glycol monoethyl ether as raw material, under the condition of catalyst and polymerization inhibitor existence, adopt reactive distillation ester exchange process to react, the methyl alcohol that reaction is generated removes in time by azeotropic distillation, and the product that contains methoxyethyl methacrylate obtaining is distilled under reduced pressure, remove after excessive methyl methacrylate, Removal of catalyst and polymerization inhibitor, obtain methoxyethyl methacrylate product again.
Catalyst for esterification reaction is the focus of research always, the homogeneous acid catalysts such as industrial conventional sulfuric acid, p-methyl benzenesulfonic acid, niter cake are post-treated simply gradually, esterification yield is high, eco-friendly solid acid catalyst replaces, as series of new solid catalysts such as molecular sieve, carried heteropoly acid, acidic resins, solid super-strong acids.
CN101475475 has introduced the SO that utilizes preparation
4 2-/ TiO
2solid super acid catalyst direct esterification catalyzes and synthesizes (methyl) acrylic acid alcoxyl base ethyl ester, and (methyl) acrylic acid one way esterification yield reaches 99 %, but the stability of its catalyst is not good, and acidic-group easily comes off, and can not be cycled to used in this reaction system.
Nearly ten years, active carbon is quite subject to people's concern as cheap environment protection catalytic carrier, especially in the research of the aspects such as activated carbon surface microstructure, activated carbon modified, surface active groups qualitative and quantitative.The pore structure of active carbon prosperity, larger specific area and good heat endurance, chemical stability are given it becomes good catalyst carrier.
Perfluorinated sulfonic resin (Nafion-H) is researched and developed by du pont company, is " heart " of chlorine industry---the main component of perfluorinated sulfonic acid ion exchange membrane.Perfluorinated sulfonic resin is green solid acid catalyst, and many reactions are had to good catalytic activity and selective.But because perfluorinated sulfonic resin specific surface is lower, the acid centre burying in fluorocarbon radical body is difficult for being approached by reactant, greatly reduces its catalytic activity.
CN1699450A and ZL200510046751.8 have introduced the method for being extracted high-purity perfluor sulfoacid resin solution by discarded amberplex, for the recycling of expensive perfluorinated sulfonic resin provides a good thinking.
The defects such as perfluorinated sulfonic resin specific area is little in order to overcome, activated centre exposed amount is low, the present invention be take active carbon as carrier, develop the immobilized perfluorinated sulfonic resin novel catalyst system of a kind of active carbon, to extract perfluorinated sulfonic resin in discarded amberplex, and make purer perfluor sulfoacid resin solution, in conjunction with the feature that active carbon hole is flourishing, specific area is large, prepare the immobilized perfluorinated sulfonic resin catalyst of active carbon.This catalyst preparation process is simple, and this catalyst belongs to hydrophobic material simultaneously, and it can effectively absorb organic molecule and not absorb water.When having water to exist, it has been avoided Bronsted acid position easily aquation to occur and has reduced the problem of catalytic activity, and contributes to reactant to promote reaction to carry out with contacting of acid position.
Summary of the invention
One of object of the present invention is to overcome above-mentioned deficiency, provide a kind of active carbon immobilized perfluorinated sulfonic resin catalyst, it is novel, green solid superacid as catalyst system, this catalyst has good catalytic performance in (methyl) acrylic acid alcoxyl base ethyl ester synthetic, and catalyst can repeatedly circulate.
Two of object of the present invention is to provide the immobilized perfluorinated sulfonic resin of a kind of active carbon to catalyze and synthesize the method for (methyl) acrylic acid alcoxyl base ethyl ester.
The present invention is achieved in that
The immobilized perfluorinated sulfonic resin catalyst of active carbon, it is to take active carbon as carrier, the discarded amberplex of chlorine industry extract and the perfluor sulfoacid resin solution prepared as active component.
First carry out Activated Carbon Pretreatment: the wood activated charcoal that base charcoal selects phosphoric acid activation method to prepare, first at 500 ~ 800 ℃ of roasting 2 ~ 4 h of Muffle furnace, 40 ~ 70 ℃ of dipping backflow 3 ~ 5 h of nitric acid that the concentration of take is again 5 ~ 30 %, after suction filtration, with distilled water, active carbon is washed till to cleaning solution pH and is neutral, dry 100 ~ 120 ℃ of activation 2 ~ 3 h.The object of carrying out Activated Carbon Pretreatment is reaming and the oxyacid group that increases activated carbon surface.
Take that the discarded amberplex of a certain amount of pretreated active carbon and chlorine industry extracts and the perfluor sulfoacid resin solution prepared (concentration mass fraction is about 4.5 %, preparation method is with reference to ZL200510046751.8) in the water-baths of 70 ~ 80 ℃, reflux and flood 0.5 ~ 2 h, solvent evaporated at 80 ~ 95 ℃ again, in 100 ~ 120 ℃ of baking ovens, be dried to constant weight, standby after grinding.
Catalyst after grinding mixes with the ratio of mass ratio 1 ︰ 10 with 5 ~ 30 % inorganic acid aqueous solutions, dipping backflow 2 ~ 3 h at 45 ~ 80 ℃, suction filtration and be neutral to cleaning solution pH with distilled water washing catalyst, suction filtration is dried to constant weight, 100 ~ 120 ℃ of activation 2 ~ 3 h, obtain the immobilized perfluorinated sulfonic resin catalyst of prepared active carbon.
The suitable load capacity of the immobilized perfluorinated sulfonic resin catalyst of described active carbon is that 5 ~ 40 %(active components account for catalyst gross mass percentage).
The immobilized perfluorinated sulfonic resin of a kind of active carbon catalyzes and synthesizes the method for (methyl) acrylic acid alcoxyl base ethyl ester, the molar ratio of this reaction is: (methyl) acrylic acid and ethylene glycol monoalkyl ether mol ratio are 1 ︰ 1 ~ 1 ︰ 2, and the suitable mol ratio of (methyl) acrylic acid and ethylene glycol monoalkyl ether is 1 ︰ 1.2 ~ 1 ︰ 1.4;
(methyl) acrylic acid described in literary composition is acrylic acid or methacrylic acid.
Because part ethylene glycol monoalkyl ether can aqua going along with and the azeotropic of water and being taken out of on a small quantity, ethylene glycol monoalkyl ether excessive few, is unfavorable for the balance movement that moves to right, and causes reacting esterification yield too low; Ethylene glycol monoalkyl ether excessive large, esterification yield increases limited, but it is large to cause removing the energy consumption of excessive ethylene glycol monoalkyl ether, and esterification reaction equipment utilization rate is lower, inadvisable economically.
Described azeotropic aqua toluene mass percent consumption is 10 ~ 40 % of reactant gross mass, and suitable toluene consumption is 25 ~ 30 % of reactant gross mass.
Band aqua consumption is too low, can not fully form azeotropic mixture with reacting the water generating, and causes being with water poor effect; Simultaneously closely related with reaction temperature with the consumption of aqua, band aqua amount is crossed conference reduces the too low esterification yield that causes of reaction system equilibrium temperature.
Described polymerization inhibitor phenthazine mass percent consumption is 0.05 ~ 0.30 % of reactant gross mass, suitable phenthazine consumption is 0.15 ~ 0.30 %, because in course of reaction, polymerization inhibitor phenthazine has a linear process consuming, and the amount of polymerization inhibitor crosses that I haven't seen you for ages makes reaction produce polymerism.
The suitable reaction temperature of reaction system is 124 ~ 140 ℃, and the too high meeting of reaction temperature makes to react side reaction to be increased.For easy azeotropic, take raw material alcohol ether out of, can reduce by the mode of temperature programming ethylene glycol monoalkyl ether and together take out of with the water generating, thereby can improve esterification yield.
Optimum reacting time is 3 ~ 5 h, and long meeting of reaction time is because of the consumption of polymerization inhibitor, and polymerization even occurs in byproduct of reaction increase.
The immobilized perfluorinated sulfonic resin catalyst amount of described active carbon accounts for 1 ~ 5 % of reactant gross mass, and suitable catalyst amount is 2 ~ 3 % of reactant gross mass.
Advantage of the present invention is: developed the immobilized perfluorinated sulfonic resin solid super acid catalyst of novel active carbon, it take active carbon as carrier, discarded amberplex extracts and the perfluor sulfoacid resin solution prepared is active component, adopt the method for dipping-solvent evaporated, make the immobilized perfluorinated sulfonic resin catalyst of active carbon.This catalyst has good catalytic performance in (methyl) acrylic acid alcoxyl base ethyl ester synthetic, and with product convenient separation, and catalyst can repeatedly circulate.The immobilized perfluorinated sulfonic resin catalyst of active carbon prepared by the present invention has abundant pore structure, larger specific area, good heat endurance and chemical stability, has good application prospect.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail.
Acrylic acid, methacrylic acid, phenthazine that the present invention uses are technical grade, Chemical Reagent Co., Ltd., Sinopharm Group; Glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether are technical grade, and Jiangsu is happy reaches chemical limited company; Active carbon is technical grade, Jiangsu Zhu Hai active carbon Co., Ltd; Toluene is SILVER REAGENT, Nanjing Chemistry Reagent Co., Ltd.; The former producer of perfluorinated sulfonic acid ion exchange membrane is E.I.Du Pont Company.
Example 1: the preparation of the immobilized perfluorinated sulfonic resin catalyst of active carbon
Take wood activated charcoal prepared by 15.0 g phosphoric acid activation methods, 500 ℃ of roasting 2 h in Muffle furnace, nitric acid 100.0 g that the concentration of take is again 30 % 3 h that reflux in 40 ℃ of water-baths, suction filtration is also washed with distilled water to cleaning solution pH and is neutral, 100 ℃ of oven for drying are to constant weight, and 120 ℃ activate 2 h.
BET analyzes the specific area of modified support by 935.6 original m
2/ g brings up to 1086.9 m
2/ g; Boehm titration determination modified support surface carboxyl-content is brought up to 2.4445 mmol/g by 1.4775 original mmol/g simultaneously, lactone group content is reduced to 0.0780 mmol/g by 0.0955 original mmol/g, and phenolic hydroxyl group is brought up to 0.0992 mmol/g by 0.0446 mmol/g.
The perfluor sulfoacid resin solution (mass fraction is 4.5%) that adds respectively the pretreated active carbon of 10.0 g and 100.0 g to extract from discarded perfluorinated sulfonic acid ion exchange membrane in the there-necked flask of 500 ml that thermometer is housed, magnetic agitation dipping backflow 1 h in 80 ℃ of water-baths, at 90 ℃, solvent evaporated is taken out solid again, dry to constant weight for 100 ℃, the catalyst that grinding is sieved after (100 order) mixes with the solid-to-liquid ratio of 1 ︰ 10 with 5 % aqueous sulfuric acids, dipping backflow 2 h at 45 ℃, suction filtration is also neutral with distilled water washing catalyst to cleaning solution pH, suction filtration is dried to constant weight, 120 ℃ of activation 3 h, weigh solid 14.3 g, obtaining load capacity is the immobilized perfluorinated sulfonic resin catalyst of active carbon (that is: PFSA/AC catalyst) of 30 %.
Example 2
Take wood activated charcoal prepared by 15.0 g phosphoric acid activation methods, 500 ℃ of roasting 2 h in Muffle furnace, nitric acid 100.0 g that the concentration of take is again 20 % 3 h that reflux in 60 ℃ of water-baths, suction filtration is also washed with distilled water to cleaning solution pH and is neutral, 100 ℃ of oven for drying are to constant weight, and 120 ℃ activate 2 h.
BET analyzes the specific area of modified support by 935.6 original m
2/ g brings up to 1141.0 m
2/ g; Boehm titration determination modified support surface carboxyl-content is brought up to 2.3252 mmol/g by 1.4775 original mmol/g simultaneously, lactone group content is reduced to 0.0792 mmol/g by 0.0955 original mmol/g, and phenolic hydroxyl group is brought up to 0.0988 mmol/g by 0.0446 mmol/g.
The perfluor sulfoacid resin solution (mass fraction is 4.5%) that adds respectively the pretreated active carbon of 10.0 g and 25.5 g to extract from discarded perfluorinated sulfonic acid ion exchange membrane in the there-necked flask of 500 ml that thermometer is housed, magnetic agitation dipping backflow 2 h in 80 ℃ of water-baths, at 90 ℃, solvent evaporated is taken out solid again, dry to constant weight for 100 ℃, the catalyst that grinding is sieved after (100 order) mixes with the solid-to-liquid ratio of 1 ︰ 10 with 10 % aqueous sulfuric acids, dipping backflow 2 h at 80 ℃, suction filtration is also neutral with distilled water washing catalyst to cleaning solution pH, suction filtration is dried to constant weight, 120 ℃ of activation 3 h, weigh solid 11.1 g, obtaining load capacity is the immobilized perfluorinated sulfonic resin catalyst of active carbon of 10 %.
Example 3
Take wood activated charcoal prepared by 15.0 g phosphoric acid activation methods, 500 ℃ of roasting 2 h in Muffle furnace, nitric acid 100.0 g that the concentration of take is again 10 % 3 h that reflux in 60 ℃ of water-baths, suction filtration is also washed with distilled water to cleaning solution pH and is neutral, 100 ℃ of oven for drying are to constant weight, and 120 ℃ activate 2 h.
BET analyzes the specific area of modified support by 935.6 original m
2/ g brings up to 1159.1 m
2/ g; Boehm titration determination modified support surface carboxyl-content is brought up to 2.3056 mmol/g by 1.4775 original mmol/g simultaneously, lactone group content is reduced to 0.0803 mmol/g by 0.0955 original mmol/g, and phenolic hydroxyl group is brought up to 0.0937 mmol/g by 0.0446 mmol/g.
The perfluor sulfoacid resin solution (mass fraction is 4.5%) that adds respectively the pretreated active carbon of 10.0 g and 150.0 g to extract from discarded perfluorinated sulfonic acid ion exchange membrane in the there-necked flask of 500 ml that thermometer is housed, magnetic agitation dipping backflow 2 h in 80 ℃ of water-baths, at 95 ℃, solvent evaporated is taken out solid again, dry to constant weight for 100 ℃, the catalyst that grinding is sieved after (100 order) mixes with the solid-to-liquid ratio of 1 ︰ 10 with 10 % aqueous sulfuric acids, dipping backflow 2 h at 80 ℃, suction filtration is also neutral with distilled water washing catalyst to cleaning solution pH, suction filtration is dried to constant weight, 120 ℃ of activation 3 h, weigh solid 16.4 g, obtaining load capacity is the immobilized perfluorinated sulfonic resin catalyst of active carbon of 40 %.
Example 4
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively methacrylic acid and ethylene glycol monobutyl ether mol ratio is 1 ︰ 1.2,35 %PFSA/AC catalyst 3 %(of example 1 preparation account for raw material gross mass, lower same), band aqua toluene 30 %(account for raw material gross mass, lower same), polymerization inhibitor phenthazine 0.15 %(accounts for raw material gross mass, lower same), magnetic agitation is also controlled 124～140 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 4 h, the esterification yield of methacrylic acid is 83.1 %.
Example 5
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively acrylic acid and glycol monoethyl ether mol ratio is 1 ︰ 1.4,20 %PFSA/AC catalyst 3 % of example 2 preparations, band aqua toluene 30 %, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 120～130 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 4 h, acrylic acid esterification yield is 87.9 %.
Example 6
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively methacrylic acid and ethyleneglycol monophenylether mol ratio is 1 ︰ 1.2,30 %PFSA/AC catalyst 3 % of example 1 preparation, band aqua toluene 30 %, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 140～160 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 3 h, the esterification yield of methacrylic acid is 90.5 %.
Example 7
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively acrylic acid and ethyleneglycol monophenylether mol ratio is 1 ︰ 1.2,35 %PFSA/AC catalyst 2 % of example 1 preparation, band aqua toluene 25 %, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 140～160 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 3 h, acrylic acid esterification yield is 88.1 %.
Example 8
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively methacrylic acid and glycol monoethyl ether mol ratio is 1 ︰ 1.4,20 %PFSA/AC catalyst 3 % of example 2 preparations, band aqua toluene 30 %, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 120～130 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 6 h, the esterification yield of methacrylic acid is 81.0 %.
Example 9
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively methacrylic acid and ethylene glycol monobutyl ether mol ratio is 1 ︰ 1.2,10 %PFSA/AC catalyst 1% of example 3 preparations, band aqua toluene 30%, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 124～140 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 8 h, the esterification yield of methacrylic acid is 75.6 %.
Example 10
In the 500 ml there-necked flasks that water knockout drum, reflux condenser φ 2.5 * 70 packed towers, thermometer are housed, adding respectively methacrylic acid and ethylene glycol monobutyl ether mol ratio is 1 ︰ 1.2,20 %PFSA/AC catalyst 3 % of example 2 preparations, band aqua toluene 30 %, polymerization inhibitor phenthazine 0.15 %, magnetic agitation is also controlled 124～140 ℃ of reaction temperatures, keep reaction all the time in fluidized state, back flow reaction 8 h, the esterification yield of methacrylic acid is 78.7 %.
Claims (9)
1. the immobilized perfluorinated sulfonic resin catalyst of active carbon, is characterized in that: it is to take active carbon as carrier, the discarded amberplex of chlorine industry extracts and the perfluor sulfoacid resin solution prepared as active component, the method for employing dipping-solvent evaporated makes.
2. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 1, is characterized in that: its preparation method comprises the steps:
First carry out Activated Carbon Pretreatment: the wood activated charcoal that base charcoal selects phosphoric acid activation method to prepare, first at 500 ~ 800 ℃ of roasting 2 ~ 4 h of Muffle furnace, 40 ~ 70 ℃ of dipping backflow 3 ~ 5 h of nitric acid that the concentration of take is again 5 ~ 30 %, after suction filtration, with distilled water, active carbon is washed till to cleaning solution pH and is neutral, dry 100 ~ 120 ℃ of activation 2 ~ 3 h;
Take the perfluor sulfoacid resin solution that the discarded amberplex of a certain amount of pretreated active carbon and chlorine industry extracts and prepares, the concentration mass fraction of described perfluor sulfoacid resin solution is 4.0 ~ 5.0 %, in the water-baths of 70 ~ 80 ℃, reflux and flood 0.5 ~ 2 h, solvent evaporated at 80 ~ 95 ℃ again, in 100 ~ 120 ℃ of baking ovens, be dried to constant weight, standby after grinding;
Catalyst after grinding mixes with the ratio of mass ratio 1 ︰ 8-12 with 5 ~ 30 % inorganic acid aqueous solutions, dipping backflow 2 ~ 3 h at 45 ~ 80 ℃, suction filtration and be neutral to cleaning solution pH with distilled water washing catalyst, suction filtration is dried to constant weight, 100 ~ 120 ℃ of activation 2 ~ 3 h, obtain the immobilized perfluorinated sulfonic resin catalyst of prepared active carbon.
3. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 2, is characterized in that: the load capacity of the immobilized perfluorinated sulfonic resin catalyst of described active carbon is 5 ~ 40 %.
4. the immobilized perfluorinated sulfonic resin catalyst of active carbon is for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, it is characterized in that, reactant: (methyl) acrylic acid and ethylene glycol monoalkyl ether mol ratio are 1 ︰ 1 ~ 1 ︰ 2, toluene mass percent consumption is 10 ~ 40 % of reactant gross mass, polymerization inhibitor phenthazine mass percent consumption is 0.05 ~ 0.30 % of reactant gross mass, the immobilized perfluorinated sulfonic resin catalyst amount of the described active carbon of one of claims 1 to 3 accounts for 1 ~ 5 % of reactant gross mass, reaction temperature is 124 ~ 140 ℃, reaction time is 3 ~ 5 h,
(methyl) acrylic acid is wherein methacrylic acid or acrylic acid.
5. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 4 is for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, it is characterized in that, the suitable mol ratio of (methyl) acrylic acid and ethylene glycol monoalkyl ether is 1 ︰ 1.2 ~ 1 ︰ 1.4.
6. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 4, for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, is characterized in that, dehydrating agent toluene consumption is 25 ~ 30 % of reactant gross mass.
7. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 4, for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, is characterized in that, polymerization inhibitor phenthazine consumption is 0.15 ~ 0.30 %.
8. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 4, for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, is characterized in that, catalyst amount accounts for 2 ~ 3 % of reactant gross mass.
9. the immobilized perfluorinated sulfonic resin catalyst of active carbon according to claim 4, for the synthesis of the method for (methyl) acrylic acid alcoxyl base ethyl ester, is characterized in that, described ethylene glycol monoalkyl ether also can be ethylene glycol list phenyl ether.
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| CN111097553A (en) * | 2019-11-26 | 2020-05-05 | 南京源泉环保科技股份有限公司 | Solid material for treating cyaniding cadmium plating wastewater and preparation method and application thereof |
| CN113117750A (en) * | 2021-03-17 | 2021-07-16 | 南京福昌环保有限公司 | Preparation and application of continuous esterification composite catalyst for acrylic acid and ester waste oil recovery device |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016095207A1 (en) * | 2014-12-19 | 2016-06-23 | Rhodia Operations | Carbon/fluoropolymer composite and manufacturing methods thereof |
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| CN111097553A (en) * | 2019-11-26 | 2020-05-05 | 南京源泉环保科技股份有限公司 | Solid material for treating cyaniding cadmium plating wastewater and preparation method and application thereof |
| CN111097553B (en) * | 2019-11-26 | 2022-07-26 | 南京源泉环保科技股份有限公司 | Solid material for treating cyanided cadmium plating wastewater and preparation method and application thereof |
| CN113117750A (en) * | 2021-03-17 | 2021-07-16 | 南京福昌环保有限公司 | Preparation and application of continuous esterification composite catalyst for acrylic acid and ester waste oil recovery device |
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| CN103599815B (en) | 2015-08-26 |
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