CN109734586B - Treatment method for recycling (methyl) acrylic acid in esterification reaction system - Google Patents

Treatment method for recycling (methyl) acrylic acid in esterification reaction system Download PDF

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CN109734586B
CN109734586B CN201910032567.XA CN201910032567A CN109734586B CN 109734586 B CN109734586 B CN 109734586B CN 201910032567 A CN201910032567 A CN 201910032567A CN 109734586 B CN109734586 B CN 109734586B
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tert
acrylic acid
esterification reaction
alcohol
methyl
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CN109734586A (en
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张春华
庞来兴
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Guangdong Boxing New Materials Technology Co ltd
Hubei Zhongke Bohong New Material Technology Co ltd
Zhang Chunhua
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Guangdong Bossin Novel Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a treatment method for recycling (methyl) acrylic acid in an esterification reaction system. The processing method comprises the following steps: s1: filtering an esterification reaction system containing (methyl) acrylic acid, and washing with water; s2: adding epoxide, catalyst b and polymerization inhibitor 2 to react. The treatment method provided by the invention firstly utilizes filtering and washing to recover the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain a corresponding reaction product, and the reaction product can be used as an accessory ingredient to exist in an original esterification system, thereby realizing the reutilization of the (methyl) acrylic acid; at the moment, the waste of (methyl) acrylic acid can be avoided, alkali washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.

Description

Treatment method for recycling (methyl) acrylic acid in esterification reaction system
Technical Field
The invention relates to the technical field of photocuring materials, in particular to a treatment method for recycling (methyl) acrylic acid in an esterification reaction system.
Technical Field
In the prior report and actual production, when the direct esterification reaction is carried out by the reaction of alcohols and (methyl) acrylic acid, liquid strong acid or compatible strong acid such as sulfuric acid, methane sulfonic acid, p-toluenesulfonic acid and the like is used as a catalyst, the (methyl) acrylic acid is excessively added, and the catalyst and the unreacted (methyl) acrylic acid are difficult to separate after the esterification reaction is finished. The catalyst and (meth) acrylic acid are generally removed by alkaline washing (washing with alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.), thereby producing a salt-containing waste liquid; in addition, in order to remove alkaline substances completely, a large amount of water is needed for washing for many times, the operation is complicated, the reaction process and the production period are prolonged, and a large amount of alkaline substances and water resources are needed to be input. In addition, unreacted (meth) acrylic acid is wasted, and the salt-containing waste liquid is discharged after being treated, which results in high treatment cost. In other reports, a solid catalyst is selected, the catalyst is filtered and removed after the esterification reaction, and unreacted (meth) acrylic acid is recovered by reduced pressure distillation, which has very high requirements on environment-friendly equipment and high energy consumption.
Therefore, the development of a method for recycling unreacted (meth) acrylic acid has important research significance and industrial application value.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, unreacted (methyl) acrylic acid is treated as waste after esterification reaction, so that a large amount of salt-containing waste liquid is caused, the treatment cost is high, and resources are wasted; or purification treatment is carried out, and defects or defects with high requirements on equipment are overcome, so that the treatment method for recycling the (methyl) acrylic acid in the esterification reaction system is provided. The treatment method provided by the invention firstly utilizes filtering and washing to recover the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain a corresponding reaction product, and the reaction product can be used as an accessory ingredient to exist in an original esterification system, thereby realizing the reutilization of the (methyl) acrylic acid; at the moment, the waste of (methyl) acrylic acid can be avoided, alkali washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a treatment method for recycling (methyl) acrylic acid in an esterification reaction system comprises the following steps:
s1: filtering an esterification reaction system containing (methyl) acrylic acid, and washing with water;
s2: adding epoxide, catalyst b and polymerization inhibitor 2 for reaction;
the esterification reaction system is obtained by the following processes: taking alcohols and (methyl) acrylic acid as raw materials, adding a catalyst a, a polymerization inhibitor 1 and a solvent for esterification reaction to obtain an esterification reaction system; the catalyst a is one or more of a solid strong acid catalyst or a water-soluble ionic strong acid catalyst.
The treatment method provided by the invention firstly utilizes filtering and washing to recover the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain a corresponding reaction product, and the reaction product can be used as an accessory ingredient to exist in an original esterification system, thereby realizing the reutilization of the (methyl) acrylic acid; at the moment, the waste of (methyl) acrylic acid can be avoided, alkali washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.
Preferably, the epoxide in S2 is one or more of a monomeric epoxide or a polymeric epoxide.
Epoxides generally have an average of at least 1 epoxy group per molecule which is reactive with a carboxyl group and can be aliphatic, cycloaliphatic, aromatic, or heterocyclic.
More preferably, the monomeric epoxy compound is epichlorohydrin, cyclohexene oxide, 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexanecarboxylate, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, 3, 4-epoxycyclohexyl acrylate, 3, 4-epoxycyclohexyl methacrylate, glycidyl versatate, allyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, C8-C10Alkyl glycidyl ethers, C12Alkyl glycidyl ethers, C12-C14One or more of alkyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidyl ether, benzyl glycidyl ether or p-tertiary phenyl glycidyl ether.
Preferably, the polymeric epoxide is one or more of polymeric aromatic epoxy compound, polymeric alicyclic epoxy compound, polymeric aliphatic epoxy compound or polymeric heterocyclic epoxy compound.
More preferably, the polymerization type aromatic epoxy compound is one or more of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol-Novolak type epoxy resin or cresol-Novolak type epoxy resin;
the polymerization type aliphatic epoxy compound is one or more of neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, propoxylated glycerol triglycidyl ether or pentaerythritol tetraglycidyl ether;
the polymerized alicyclic epoxy compound is one or more of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, diglycidyl hexahydrophthalate or diglycidyl methyltetrahydrophthalate;
the polymeric heterocyclic epoxy compound is one or more of hydantoin epoxy resin, triglycidyl isocyanurate or tetraglycidyl glycoluril.
Both monomeric epoxy compounds and polymeric epoxides, either presently disclosed or commercially available, may be used in the present invention.
Specifically, for example, CYD-128, CYD-118 (the tomb petrochemical), DER-331, DER-332, DER-324 (the Dow chemical company), NPEL-128, NPEL-127 (the south Asia resin), JER828 (the Mitsubishi chemical company), Araldite GY-240, Araldite GY-250 (the Hexion Specialty Chemicals, Inc), etc.; trimethylolpropane triglycidyl ether, diglycidyl ether of neopentyl glycol, and the like, such as XY-636, XY-633, XY-634 (New distal technologies, Anhui), HELOXYM DIFIER 48, HELOXY 68(Hexion Specialty Chemicals, Inc), and the like.
Preferably, the catalyst b in S2 is a tertiary amine or a salt thereof, a quaternary ammonium salt, a sulfonic acid, a phosphine, a phosphonium salt, a metal halide or a metal organic compound.
Preferably, the tertiary amine is one or more of N, N-dimethylaniline, benzylamine, 4-lutidine or triethylamine.
Preferably, the quaternary ammonium salt is one or more of tetramethylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium chloride and triethylbenzylammonium bromide.
Preferably, the sulfonic acid is one or more of methane sulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid.
Preferably, the phosphine is one or more of triphenylphosphine, tributylphosphine, tricyclohexylphosphine or tri-tert-butylphosphine.
Preferably, the phosphonium salt is one or more of tetrabutylphosphonium chloride or tetrabutylphosphonium bromide.
Preferably, the metal halide is one or more of lithium chloride, lithium bromide, stannous chloride or zinc chloride.
Preferably, the metal organic compound is one or more of triphenylantimony, methyl triphenylantimony, chromium 2-ethylhexanoate, chromium octoate, zinc 2-ethylhexanoate, zinc octoate and zirconium octoate.
Preferably, the polymerization inhibitor 2 is one or more of 4-methoxyphenol MEHQ, p-tert-butylcatechol, tert-butylhydroquinone, o-methylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-p-cresol, methylhydroquinone or hydroquinone.
Preferably, the temperature of the reaction in S2 is 85-125 ℃.
More preferably, the reaction temperature in S2 is 90-110 DEG C
Preferably, the process of S1-S2 further comprises a step of recovering the solvent.
The solvent may be recovered before S1, during S1-S2 (e.g., after washing with water), or after S2.
Both solid strongly acidic catalysts and water-soluble ionic strongly acidic catalysts conventional in the art can be used in the present invention.
Preferably, the solid strong acid catalyst is one or more of bisulfate, acidic cation exchange resin or functionalized sulfonic acid.
Preferably, the bisulfate salt is one of lithium bisulfate, sodium bisulfate monohydrate, potassium bisulfate, or tetramethylammonium bisulfate.
Preferably, the acidic cation exchange resin is one or more of Amberlyst macroporous or gel resin series (Downchemical), Lewatit series (Lanxess), T-62MP (Thermax), Diaion series (MCC), NKC-9 (south Dasythesis chemical of Jiangyin), D001 (Jiangsu Suqing group) or KC101 (Kairy environmental protection technology).
More preferably, the Amberlyst macroporous or gel resin series is one or more of Amberlyst 15, Amberlyst16, Amberlyst 35, Amberlyst 36 or Amberlyst 131.
More preferably, the Lewatit series is one or more of Lewatit SP112 or Lewatit SP 118.
More preferably, the Diaion series is one or more of Diaion PK 216 or Diaion PK 208.
More preferably, the functionalized sulfonic acid is 2-acrylamido-2-methylpropanesulfonic acid, AMPS.
Preferably, the bisulfate type ionic liquid is one of 1-ethyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole bisulfate, 1-hydroxyethyl-3-methylimidazole bisulfate and 1-carboxyethyl-3-methylimidazole bisulfate.
Preferably, the sulfonic acid group functionalized imidazolium salt ionic liquid is one or more of 1-butyl sulfonic acid-3-methylimidazole chloride salt, 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate or 1-propyl sulfonic acid-3-methylimidazole hydrogen sulfate.
Preferably, the sulfonic acid group functionalized pyridinium ionic liquid is one or more of N-sulfonic acid butyl pyridine p-toluenesulfonate, N-sulfonic acid butyl pyridine bisulfate or N-sulfonic acid propyl pyridine p-toluenesulfonate.
Preferably, the solvent is recovered by distillation.
The distillation is generally carried out under negative pressure.
Preferably, the distillation pressure is 2 to 70 Kpa.
More preferably, the distillation pressure is 3 to 50 Kpa.
Most preferably, the distillation pressure is 5 to 15 Kpa.
Preferably, the distillation temperature is 40-100 ℃.
More preferably, the distillation temperature is 60-80 ℃.
The inert gas or oxygen-containing gas may be introduced into the distillation apparatus during the distillation.
Preferably, the oxygen-containing gas is air, or a mixture of air and nitrogen (lean air).
The amount of the inert gas or the oxygen-containing gas introduced is 0.1 to 1m3/m3H, preferably 0.2 to 0.8m3/m3H and more preferably 0.3 to 0.7m3/m3H, based on the volume of the reaction mixture.
Preferably, the device selected in the distillation is a distillation device, a falling film or a thin film evaporator.
Preferably, when the epoxide is added in S2, the ratio of the epoxy equivalent of the epoxide to the equivalent of the (meth) acrylic acid in the esterification reaction system is 1: 0.8-1.3.
Under these conditions, (meth) acrylic acid and epoxide can be completely reacted.
Preferably, the alcohol is a monohydric alcohol or a polyhydric alcohol.
More preferably, the monohydric alcohol is lauryl alcohol, C8-C10One or more of alcohol, isooctanol, isodecanol, tetrahydrofuryl alcohol, cyclotrimethylolpropane formal, o-phenylphenoxy ethanol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyethoxyethoxyethanol and ethoxynonylphenol.
The polyhydric alcohol can be conventional dihydric alcohol, trihydric alcohol, tetrahydric alcohol, hexahydric alcohol, hyperbranched polyhydric alcohol and the like in the prior art.
More preferably, the polyol is ethylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 6-hexanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol (methylpropanediol), dipropylene glycol, tripropylene glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, ethoxylated-1, 6-hexanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, ethoxylated bisphenol A (e.g., 2EO-BPA, 3EO-BPA, 4EO-BPA, 10EO-BPA), propoxylated bisphenol A (e.g., 4PO-BPA), 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol phthalate, polyethylene glycol (e.g., PEG200, polyethylene glycol), PEG300, PEG400, PEG600, PEG800, PEG1000), polypropylene glycol (e.g., PPG200, PPG300, PPG400, PPG600, PPG800, PPG1000), polyester diol, polytetrahydrofuran glycol (e.g., PTMEG1000, PTMEG2000, etc.), polycaprolactone glycol (e.g., PCL205, PCL208, PCL210, PCL220, etc., or PLACCEL series products, e.g., Daicel, etc.), trimethylolpropane, trimethylolethane, ethoxylated trimethylolpropane (e.g., 3EO-TMP, 9EO-TMP, 15EO-TMP, 30EO-TMP, etc.), propoxylated trimethylolpropane (e.g., 3PO-TMP, 4.5PO-TMP, etc.), glycerol, ethoxylated glycerol (e.g., 3EO-GLY, 9EO-GLY), propoxylated glycerol (e.g., 3PO-GLY, 3.5PO-GLY, 4.5PO-GLY, 6.6PO-GLY, etc.; or such as Dow Chemical's POLYDOGY-700, POLYDO GY-3000, VORANOLCP450, etc.), tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated isocyanuric acid, propoxylated isocyanuric acid, caprolactone-extended ethoxylated isocyanuric acid, polyester triols, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, caprolactone-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol (e.g. 4EO-PE, 35EO-PE), propoxylated pentaerythritol (e.g. 5PO-PE), caprolactone-extended pentaerythritol, polyester tetrahydric alcohol, dipentaerythritol, ethoxylated dipentaerythritol (e.g. 6EO-DP, 12EO-DP), propoxylated dipentaerythritol, caprolactone-extended dipentaerythritol, polyester hexahydric alcohol or hyperbranched polyester polyol.
Both solid strongly acidic catalysts and water-soluble ionic strongly acidic catalysts conventional in the art can be used in the present invention.
Preferably, the solid strong acid catalyst is one or more of bisulfate, acidic cation exchange resin or functionalized sulfonic acid.
Preferably, the bisulfate salt is one of lithium bisulfate, sodium bisulfate monohydrate, potassium bisulfate, or tetramethylammonium bisulfate.
Preferably, the acidic cation exchange resin is one or more of Amberlyst macroporous or gel resin series (Downchemical), Lewatit series (Lanxess), T-62MP (Thermax), Diaion series (MCC), NKC-9 (south Dasythesis chemical of Jiangyin), D001 (Jiangsu Suqing group) or KC101 (Kairy environmental protection technology).
More preferably, the Amberlyst macroporous or gel resin series is one or more of Amberlyst 15, Amberlyst16, Amberlyst 35, Amberlyst 36 or Amberlyst 131.
More preferably, the Lewatit series is one or more of Lewatit SP112 or Lewatit SP 118.
More preferably, the Diaion series is one or more of Diaion PK 216 or Diaion PK 208.
More preferably, the functionalized sulfonic acid is 2-acrylamido-2-methylpropanesulfonic acid, AMPS.
Preferably, the bisulfate type ionic liquid is one of 1-ethyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole bisulfate, 1-hydroxyethyl-3-methylimidazole bisulfate and 1-carboxyethyl-3-methylimidazole bisulfate.
Preferably, the sulfonic acid group functionalized imidazolium salt ionic liquid is one or more of 1-butyl sulfonic acid-3-methylimidazole chloride salt, 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate or 1-propyl sulfonic acid-3-methylimidazole hydrogen sulfate.
Preferably, the sulfonic acid group functionalized pyridinium ionic liquid is one or more of N-sulfonic acid butyl pyridine p-toluenesulfonate, N-sulfonic acid butyl pyridine bisulfate or N-sulfonic acid propyl pyridine p-toluenesulfonate.
The polymerization inhibitor 1 in S1 is hydroquinone HQ, 4-methoxyphenol MEHQ, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2, 6-dimethylphenol or 2, 5-di-tert-butylphenol; one or more of copper chloride, cuprous chloride, copper oxide, cuprous oxide, basic copper carbonate, copper sulfate, copper acetate, acrylic acid ketone, copper methacrylate, copper salicylate, copper naphthenate, copper acetylacetonate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, cobalt acetate, cobalt carbonate, manganese acetate, manganese carbonate, manganese chloride, manganese sulfate, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, dibutyl phosphite, tricyclohexyl phosphite, hypophosphorous acid or phosphorous acid.
Solvents (i.e., water-carrying agents) conventional in the art may be used in the present invention.
Preferably, the solvent is one or more of toluene, cyclohexane, n-hexane, methylcyclohexane, heptane, n-pentane, isopropyl acetate, isobutyl acetate or sec-butyl acetate.
More preferably, the solvent is one or more of toluene, cyclohexane, n-hexane, heptane or n-pentane.
The control conditions for the esterification reaction in the present invention may be the same as those in the prior art.
Preferably, the temperature of the esterification reaction is 70-130 ℃.
More preferably, the temperature of the esterification reaction is 80-110 ℃.
Preferably, an oxygen-containing gas is introduced during the esterification reaction.
The introduction of gas containing oxygen can further improve the polymerization inhibiting effect, the gas can contain inactive gas besides oxygen, and the content of oxygen is limited by improving the polymerization inhibiting effect and preventing the reaction device from exploding.
More preferably, the gas further comprises one or more of nitrogen, helium or argon.
Preferably, the volume fraction of oxygen in the gas is 0.5-22%.
More preferably, the volume fraction of oxygen in the gas is 5-20%
The esterification reaction may be, but is not limited to, carried out under negative pressure conditions.
Preferably, the absolute pressure of the esterification reaction is 20-80 KPa, and the esterification reaction temperature is 70-100 ℃.
Preferably, the esterification reaction process further comprises the steps of performing dehydration treatment to obtain acid water and a solvent, and returning the solvent to the esterification reaction system.
The acid water obtained after dehydration contains a small amount of (meth) acrylic acid, the concentration of which is generally 1 to 25%, and a reflux column is generally used for washing after esterification, and the acid concentration of which is 1 to 10%. Therefore, the principle of a small amount of times can be adopted, and the generated low-concentration acid water is washed for 3-6 times.
Preferably, washing with the acid water is performed in S1.
Preferably, the washing temperature in S1 is 30-80 ℃.
The solid strong acid catalyst, the water-soluble ionic strong acid catalyst and the polymerization inhibitor 1 were removed by washing, and the catalyst was recovered.
More preferably, the washing temperature in S1 is 40-60 ℃.
Preferably, filtration is performed after the temperature is reduced to below 40 ℃ in S1.
More preferably, filtration is performed after the temperature is reduced to below 30 ℃ in S1.
The solid strongly acidic catalyst can be completely removed, or mostly removed, by filtration.
The filtering process comprises the following steps: filtering with closed filtering equipment.
Preferably, when the alcohol is a monohydric alcohol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to the (meth) acrylic acid is 1:1.1 to 1.5.
Preferably, when the alcohol is a polyol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to (meth) acrylic acid is 1:0.8 to 1.3.
More preferably, when the alcohol is a polyol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to (meth) acrylic acid is 1:0.9 to 1.15.
Compared with the prior art, the invention has the following beneficial effects:
the treatment method provided by the invention firstly utilizes filtering and washing to recover the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain a corresponding reaction product, and the reaction product can be used as an accessory ingredient to exist in an original esterification system, thereby realizing the reutilization of the (methyl) acrylic acid; at the moment, the waste of (methyl) acrylic acid can be avoided, alkali washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides a method for recycling (meth) acrylic acid in an esterification reaction system, which is specifically as follows.
In a 1000mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter and a water separator (connected with a condenser) are added, 228g of trimethylolpropane, 400g of acrylic acid, 112g of heptane, 28g of toluene, 32g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 1.3g of cuprous chloride, 1.0g of 4-methoxyphenol and 3.5g of hypophosphorous acid are sequentially added, 1.8-2.5 mL/min of air is introduced, heating is carried out until the esterification reaction is in a reflux state, water generated by the azeotropic reaction of toluene and heptane is taken out of an esterification reaction bottle through the water separator until the water generated per hour is less than 1mL and the temperature of the reaction solution is stable, and the temperature is taken as the end point of the esterification reaction.
Cooling the esterification reaction mixture to below 40 ℃, adding 200g of toluene, stirring, standing and filtering; and washing the esterification reaction mixture for three times by 96.2g (containing 8.9 percent of acid) of acid generated in the esterification reaction at the washing temperature of 55-60 ℃.
And then evaporating the solvent at 1340KPa and 60-85 ℃. 531g of the reaction mixture was obtained, which had an acid value of 35.2 mgKOH/g.
In a 1000ml four-mouth reaction flask, stirring electrically, heating with a thermometer, a reflux condenser and a constant temperature oil bath, adding 531g of esterification reaction mixture with an acid value of 35.2mgKOH/g, adding 63g of CYD-128 epoxy resin (ba Ling petrochemical), 2.8g of triphenylphosphine and 1.0g of 4-methoxyphenol, reacting at 90-110 ℃ until the acid value is less than 3.0mgKOH/g, and stopping the reaction.
Example 2
This example provides a method for recycling (meth) acrylic acid in an esterification reaction system, which is specifically as follows.
The preparation method is as follows.
In a 1000mL four-mouth reaction flask, electric stirring, a thermometer and a water separator (connected with a condenser) are added, 342g of tripropylene glycol, 260g of acrylic acid, 128g of toluene, 22g of 1-sulfopropyl-3-methylimidazolium chloride, 2.8g of copper sulfate pentahydrate, 1.0g of 4-methoxyphenol, 3.9g of hypophosphorous acid and 1.0g of triphenylphosphine are sequentially added, the mixture is heated until the esterification reaction is in a reflux state, and the water generated by the reaction is brought out of an esterification reaction bottle through the water separator by the azeotropic boiling of the toluene and the water until the water generated by the reaction is less than 1mL per hour and the temperature of the reaction liquid is stable, which is taken as the end point of the esterification reaction.
Cooling the esterification reaction mixture to below 40 ℃, adding 220g of toluene, stirring, standing and filtering; and washing the esterification reaction mixture for three times by 64.7g (containing 6.3 percent of acid) of acid generated in the esterification reaction at the washing temperature of 40-55 ℃.
And then evaporating the solvent at the temperature of between 60 and 85 ℃ under the condition of 13 to 40 KPa. A reaction mixture (526 g) was obtained, which had an acid value of 12.2 mgKOH/g.
In a 1000ml four-mouth reaction flask, electric stirring, a thermometer, a reflux condenser and a constant temperature oil bath are carried out, 526g of esterification reaction mixture with the acid value of 12.2mgKOH/g, 10.9g of epoxy chloropropane, 1.5g of 4-lutidine and 1.0g of 4-methoxyphenol are added, and the reaction is stopped at the temperature of 85-100 ℃ until the acid value is less than 5.0 mgKOH/g.
Example 3
This example provides a method for recycling (meth) acrylic acid in an esterification reaction system, which is specifically as follows.
In a 1000mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter and a water separator (connected with a condenser) are added with 320g of pentaerythritol propoxide (5PO), 230g of acrylic acid, 140g of cyclohexane, 36g of sodium bisulfate monohydrate, 1.5g of cuprous oxide, 0.9g of copper dibutyldithiocarbamate, 1.6g of 4-methoxyphenol and 5.2g of phosphorous acid in sequence, 2.8-3.5 mL/min of air is introduced, heating is carried out until the esterification reaction is in a reflux state, the water generated by the azeotropic reaction of cyclohexane and water is taken out of an esterification reaction bottle through the water separator until the water generated per hour is less than 1mL and the temperature of the reaction solution is stable, and the temperature is taken as the end point of the esterification reaction.
Cooling the esterification reaction mixture to below 40 ℃, adding 300g of toluene, stirring, standing and filtering; washing the esterification reaction mixture for three times by using 59.3g (containing 10.3 percent of acid) of acid generated in the esterification reaction, wherein the washing temperature is 40-55 ℃. 886g of a reaction mixture was obtained, having an acid value of 16.7 mgKOH/g.
In a 1000ml four-mouth reaction flask, stirring electrically, heating with a thermometer, a reflux condenser, and heating in a constant temperature oil bath, 600 g of esterification reaction mixture (containing solvent) with an acid value of 16.7mgKOH/g, 25.2g of pentaerythritol tetraglycidyl ether, 2.5g of triphenylphosphine, and 1.6g of 4-methoxyphenol are added, and the reaction is terminated at 90-115 ℃ until the acid value is less than 5.0 mgKOH/g. And then evaporating the solvent at the temperature of between 60 and 90 ℃ under the condition of between 13 and 55 KPa.
Example 4
This example provides a method for recycling (meth) acrylic acid in an esterification reaction system, which is specifically as follows.
In a 1000mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter, a water separator (connected with a condenser) and a vacuum system are sequentially added with 300g of tetrahydrofurfuryl alcohol, 286g of methacrylic acid, 180g of toluene, 39g of 1-hydroxyethyl-3-methylimidazole hydrogen sulfate, 5.6g of copper acrylate and 0.3g of hypophosphorous acid, 2.6-3.2 mL/min of air is introduced, the mixture is heated until the esterification reaction is in a reflux state, the water generated by the reaction is taken out of an esterification reaction bottle through the water separator until the water generated per hour is less than 1mL and the temperature of the reaction liquid is stable, and the end point of the esterification reaction is determined.
Cooling the esterification reaction mixture to below 40 ℃, adding 200g of toluene, stirring, standing and filtering; washing the esterification reaction mixture for three times by using 54.5g of acid water (containing 3.7 percent of acid) generated in the esterification reaction, wherein the washing temperature is 40-55 ℃. A reaction mixture (710 g) was obtained, which had an acid value of 29.8 mgKOH/g.
In a 1000ml four-mouth reaction flask, electric stirring, a thermometer, a reflux condenser and a constant temperature oil bath are carried out, 710g of esterification reaction mixture with the acid value of 29.8mgKOH/g, 37.0g of epoxy cyclohexane, 1.7g of triethyl benzyl ammonium chloride, 1.7g of triethylamine and 0.9g of 4-methoxyphenol are added, and the reaction is stopped at the temperature of 90-115 ℃ until the acid value is less than 3.0 mgKOH/g.
And then evaporating the solvent at the temperature of between 60 and 90 ℃ under the condition of between 13 and 55 KPa.
The treatment method provided by the invention firstly utilizes filtering and washing to recover the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain a corresponding reaction product, and the reaction product can be used as an accessory ingredient to exist in an original esterification system, thereby realizing the reutilization of the (methyl) acrylic acid; at the moment, the waste of (methyl) acrylic acid can be avoided, alkali washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.
While the foregoing is directed to particular example embodiments of the present invention, numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present invention. Rather, the scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A method for recycling (meth) acrylic acid in an esterification reaction system, comprising the steps of:
s1: cooling an esterification reaction system containing (methyl) acrylic acid to 40 ℃, then carrying out filtration treatment and washing;
s2: adding epoxide, catalyst b and polymerization inhibitor 2 for reaction;
the esterification reaction system is obtained by the following processes: taking alcohols and (methyl) acrylic acid as raw materials, adding a catalyst a, a polymerization inhibitor 1 and a solvent for esterification reaction to obtain an esterification reaction system; the catalyst a is 2-acrylamide-2-methylpropanesulfonic acid AMPS.
2. The process of claim 1, wherein the epoxide in S2 is one or more of a monomeric epoxy compound or a polymeric epoxide.
3. The process of claim 2, wherein the monomeric epoxy compound is epichlorohydrin, cyclohexene oxide, 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexanecarboxylate, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, 3, 4-epoxycyclohexyl acrylate, 3, 4-epoxycyclohexyl methacrylate, glycidyl versatate, allyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, C8-C10Alkyl glycidyl ethers, C12Alkyl glycidyl ethers, C12-C14One or more of alkyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidyl ether, benzyl glycidyl ether or p-tertiary phenyl glycidyl ether;
the polymeric epoxide is one or more of polymeric aromatic epoxide, polymeric alicyclic epoxide, polymeric aliphatic epoxide or polymeric heterocyclic epoxide.
4. The method according to claim 1, wherein the catalyst b in S2 is a tertiary amine or a salt thereof, a quaternary ammonium salt, a sulfonic acid, a phosphine, a phosphonium salt, a metal halide or a metal organic compound;
the polymerization inhibitor 2 is one or more of 4-methoxyphenol MEHQ, p-tert-butylcatechol, tert-butylhydroquinone, o-methylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-p-cresol, methylhydroquinone or hydroquinone.
5. The method according to claim 1, wherein the temperature of the reaction in S2 is 85-125 ℃.
6. The method according to claim 1, wherein the ratio of the epoxy equivalent of the epoxide in S2 to the equivalent of the (meth) acrylic acid in the esterification reaction system is 1:0.8 to 1.3.
7. The process of claim 1, wherein the alcohol is a monohydric or polyhydric alcohol;
the polymerization inhibitor 1 is hydroquinone HQ, 4-methoxyphenol MEHQ, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2, 6-dimethylphenol and 2, 5-di-tert-butylphenol; one or more of copper chloride, cuprous chloride, copper oxide, cuprous oxide, basic copper carbonate, copper sulfate, copper acetate, acrylic acid ketone, copper methacrylate, copper salicylate, copper naphthenate, copper acetylacetonate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, cobalt acetate, cobalt carbonate, manganese acetate, manganese carbonate, manganese chloride, manganese sulfate, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, dibutyl phosphite, tricyclohexyl phosphite, hypophosphorous acid or phosphorous acid;
the solvent is one or more of toluene, cyclohexane, n-hexane, methylcyclohexane, heptane or petroleum ether.
8. The process according to claim 7, wherein the monohydric alcohol is lauryl alcohol, C8-C10Alcohol, isooctanol, isodecanol, tetrahydrofuryl alcohol, cyclotrimethylolpropane formal, o-phenylphenoxy alcohol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyOne or more of ethoxyethanol and ethoxynonylphenol;
the polyhydric alcohol is ethylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 6-hexanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol (methyl propanediol), dipropylene glycol, tripropylene glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, ethoxylated-1, 6-hexanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, ethoxylated bisphenol A, propoxylated bisphenol A, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol phthalate, polyethylene glycol, polypropylene glycol, polyester diol, polytetrahydrofuran diol, polycaprolactone diol, trimethylolpropane, trimethylolethane, ethoxylated trimethylolpropane, ethylene glycol, propylene glycol, one or more of trimethylolpropane propoxylate, glycerol, ethoxylated glycerol, glycerol propoxylate, tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated isocyanuric acid, propoxylated isocyanuric acid, caprolactone chain-extended ethoxylated isocyanuric acid, polyester triol, ditrimethylolpropane, ethoxylated ditrimethylolpropane, trimethylolpropane propoxylate, caprolactone chain-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, pentaerythritol propoxylate, caprolactone chain-extended pentaerythritol, polyester tetraol, dipentaerythritol, ethoxylated dipentaerythritol, dipentaerythritol propoxylate, caprolactone chain-extended dipentaerythritol, polyester hexaol or hyperbranched polyester polyol.
9. The process according to claim 1, wherein the temperature of the esterification reaction is 70 to 130 ℃.
10. The method according to claim 1, wherein when the alcohol is a monohydric alcohol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to (meth) acrylic acid is 1:1.1 to 1.5; when the alcohol is a polyhydric alcohol, the equivalent ratio of the hydroxyl equivalent in the alcohol to (meth) acrylic acid is 1:0.8 to 1.3.
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