CN111285764B - Treatment method for reutilization of (methyl) acrylic acid in esterification reaction system - Google Patents

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

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CN111285764B
CN111285764B CN202010092451.8A CN202010092451A CN111285764B CN 111285764 B CN111285764 B CN 111285764B CN 202010092451 A CN202010092451 A CN 202010092451A CN 111285764 B CN111285764 B CN 111285764B
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methyl
esterification reaction
acrylic acid
copper
acid
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CN111285764A (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 reutilizing (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: epoxide is added, and the catalyst b reacts with the polymerization inhibitor 2. The treatment method provided by the invention firstly utilizes filtration and water washing to recycle the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain corresponding reaction products, and the reaction products can be used as accessory components to exist in an original esterification system, thereby realizing the reutilization of (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 low, and the method has a very wide application prospect.

Description

Treatment method for reutilization of (methyl) acrylic acid in esterification reaction system
Technical Field
The invention relates to the technical field of photo-curing materials, in particular to a treatment method for reutilizing (methyl) acrylic acid in an esterification reaction system. The patent application of the invention is a divisional application of patent application No. 201910032567X, and application date 2019-01-14, namely a treatment method for recycling (methyl) acrylic acid in an esterification reaction system.
Technical Field
In the prior reports and actual production, when alcohol and (methyl) acrylic acid react to carry out direct esterification reaction, liquid strong acid or compatible strong acid such as sulfuric acid, methane sulfonic acid, p-toluenesulfonic acid and the like is selected as a catalyst, the (methyl) acrylic acid is excessively added, and the catalyst and unreacted (methyl) acrylic acid are difficult to separate after the esterification reaction is finished. The catalyst and (meth) acrylic acid are generally removed by alkali 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, a large amount of water is needed for washing for many times to remove alkaline substances, the operation is complicated, the reaction procedures 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, so that the treatment cost is high. In other reports, a solid catalyst is selected, the catalyst is filtered and removed after the esterification reaction, and unreacted (methyl) acrylic acid is recovered by reduced pressure distillation, so that the method 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 problems that unreacted (methyl) acrylic acid is treated as waste after esterification reaction in the prior art, so that a large amount of salt-containing waste liquid is caused, the treatment cost is high and the resource is wasted; or purifying, and providing a treatment method for reutilizing (methyl) acrylic acid in an esterification reaction system. The treatment method provided by the invention firstly utilizes filtration and water washing to recycle the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain corresponding reaction products, and the reaction products can be used as accessory components to exist in an original esterification system, thereby realizing the reutilization of (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 low, and the method has a very wide application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a treatment method for reutilizing (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 through the following steps: 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 filtration and water washing to recycle the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain corresponding reaction products, and the reaction products can be used as accessory components to exist in an original esterification system, thereby realizing the reutilization of (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 low, and the method has a very wide application prospect.
Preferably, the epoxide in S2 is one or more of a monomeric epoxide compound or a polymeric epoxide.
Epoxide generally has an average of at least 1 epoxide group per molecule that can react with carboxyl groups, and can be aliphatic, alicyclic, aromatic, or heterocyclic.
More preferably, the monomeric epoxy compound is epichlorohydrin, epoxycyclohexane, 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexane carboxylate, 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, C 8 -C 10 Alkyl glycidyl ether, C 12 Alkyl glycidyl ether, C 12 -C 14 Alkyl glycidyl ethers, phenyl glycidyl ethers, o-tolyl glycidyl ethers, benzyl glycidyl ethers or p-tert-phenyl glycidyl ethersOne or more of glyceryl ethers.
Preferably, the polymeric epoxide is one or more of a polymeric aromatic epoxy compound, a polymeric cycloaliphatic epoxy compound, a polymeric aliphatic epoxy compound, or a polymeric heterocyclic epoxy compound.
More preferably, the polymeric 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 polymerized 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-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate, bis ((3, 4-epoxy cyclohexyl) methyl) adipate, 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester or methyltetrahydrophthalic acid diglycidyl ester;
the polymeric heterocyclic epoxy compound is one or more of hydantoin epoxy resin, triglycidyl isocyanurate or tetraglycidyl glycoluril.
Both monomeric and polymeric epoxides, which are presently disclosed or commercially available, may be used in the present invention.
Specifically, for example, CYD-128, CYD-118 (Baoling petrochemical), DER-331, DER-332, DER-324 (Dow Chemical Co.), NPEL-128, NPEL-127 (Nanya resin), JER828 (Mitsubishi Chemical), araldite GY-240, araldite GY-250 (Hexion Specialty Chemicals, inc.), etc.; trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, and the like, such as XY-636, XY-633, XY-634 (Anhui New technology Co., ltd.), HELOXY MODIFIER 48, HELOXY 68 (Hexion Specialty Chemicals, inc.), and the like.
Preferably, the catalyst b in S2 is a tertiary amine and its salts, quaternary ammonium salts, sulfonic acids, phosphines, phosphonium salts, metal halides or metal organic compounds.
Preferably, the tertiary amine is one or more of N, N-dimethylaniline, benzylamine, 4-dimethylpyridine or triethylamine.
Preferably, the quaternary ammonium salt is one or more of tetramethyl ammonium chloride, tetrabutyl ammonium bromide, triethyl benzyl ammonium chloride and triethyl benzyl ammonium bromide.
Preferably, the sulfonic acid is one or more of methane sulfonic acid, p-toluene sulfonic acid or trifluoro methane sulfonic 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, methyltriphenylantimony, chromium 2-ethylhexanoate, chromium octoate, zinc 2-ethylhexanoate, zinc octoate or zirconium octoate.
Preferably, the polymerization inhibitor 2 is one or more of 4-methoxyphenol MEHQ, p-tert-butylcatechol, tert-butylhydroquinone, o-methyl hydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-p-cresol, methyl hydroquinone or hydroquinone.
Preferably, the temperature of the reaction in S2 is 85 to 125 ℃.
More preferably, the reaction temperature in S2 is 90-110deg.C
Preferably, the process of S1-S2 further comprises a step of recovering the solvent.
The solvent may be recovered prior to 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 (Dow chemical), lewatit series (Lanxess), T-62MP (Thermax), diaion series (MCC), NKC-9 (Jiangyin Nanjing Dada synthetic chemistry), D001 (Jiangsu Su Qing group) or KC101 (Kernel environmental protection technology).
More preferably, the Amberlyst macroporous or gel resin series is one or more of Amberlyst 15, amberlyst 16, 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 or 1-carboxyethyl-3-methylimidazole bisulfate.
Preferably, the sulfonic group functionalized imidazole salt ionic liquid is one or more of 1-butylsulfonic acid-3-methylimidazole chloride salt, 1-butylsulfonic acid-3-methylimidazole bisulfate or 1-propylsulfonic acid-3-methylimidazole bisulfate.
Preferably, the sulfonate functionalized pyridinium ionic liquid is one or more of N-sulfobutyl pyridine p-toluenesulfonate, N-sulfobutyl pyridine bisulfate or N-sulfopropyl pyridine p-toluenesulfonate.
Preferably, the solvent is recovered by distillation.
Distillation is generally carried out under negative pressure.
Preferably, the pressure of the distillation is 2 to 70Kpa.
More preferably, the pressure of the distillation is 3 to 50Kpa.
Most preferably, the pressure of the distillation is from 5 to 15Kpa.
Preferably, the temperature of the distillation is 40-100 ℃.
More preferably, the distillation temperature is 60 to 80 ℃.
Inert gas or oxygen-containing gas may be introduced into the distillation apparatus during distillation.
Preferably, the oxygen-containing gas is air, or a mixture of air and nitrogen (lean air).
The inlet amount of inert gas or oxygen-containing gas is 0.1-1 m 3 /m 3 H, preferably 0.2 to 0.8m 3 /m 3 H and more preferably 0.3 to 0.7m 3 /m 3 H, based on the volume of the reaction mixture.
Preferably, the distillation device is a distillation device, a falling film or a thin film evaporator.
Preferably, when epoxide is added to S2, the equivalent ratio of the epoxide equivalent to (meth) acrylic acid in the esterification reaction system is 1:0.8 to 1.3.
Under these conditions, (meth) acrylic acid and epoxide can be completely reacted.
Preferably, the alcohol is a monohydric or polyhydric alcohol.
More preferably, the monohydric alcohol is lauryl alcohol, C 8 -C 10 Alcohols, isooctanols, isodecanols, tetrahydrofuranols, cyclotrimethylolpropane formal, o-phenylphenoxyethanol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyethoxyOne or more of ethanol and ethoxynonylphenol.
The polyol may be a diol, triol, tetrol, hexahydric alcohol, hyperbranched polyol, etc. conventional in the 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, 10 EO-BPA), propoxylated bisphenol A (e.g., 4 PO-BPA), 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol phthalate, polyethylene glycol (e.g., PEG200, PEG300, PEG400, PEG600, PEG800, PEG 1000), polypropylene glycol (e.g., PPG200, PPG300, PPG400, PPG600, PPG800, PTM 1000), polyester diol, polytetrahydrofuran glycol (e.g., EG1000, EG2000, etc.), polycaprolactone (e.g., PCL205, PCL210, etc., or PLACCEL series products such as Daicel, etc.), trimethylol propane, trimethylol ethane, ethoxylated trimethylol propane (e.g., 3EO-TMP, 9EO-TMP, 15EO-TMP, 30EO-TMP, etc.), propoxylated trimethylol propane (e.g., 3PO-TMP, 4.5PO-TMP, etc.), glycerol, ethoxylated glycerol (e.g., 3EO-GLY, 9 EO-GLY), propoxylated glycerol (e.g., 3PO-GLY, 3.5PO-GLY, 4.5PO-GLY, 6.6PO-GLY, etc.; or, for example, POLYDO GY-700, POLYDO GY-3000, dow Chemical, VORANOLCP450, etc.), tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated cyanuric acid, propoxylated cyanuric acid, caprolactone-extended ethoxylated cyanuric acid, polyester triol, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, caprolactone-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol (e.g., 4EO-PE, 35 EO-PE), propoxylated pentaerythritol (e.g., 5 PO-PE), caprolactone-extended pentaerythritol, polyester tetraol, dipentaerythritol, ethoxylated dipentaerythritol (e.g., 6EO-DP, 12 EO-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 (Dow chemical), lewatit series (Lanxess), T-62MP (Thermax), diaion series (MCC), NKC-9 (Jiangyin Nanjing Dada synthetic chemistry), D001 (Jiangsu Su Qing group) or KC101 (Kernel environmental protection technology).
More preferably, the Amberlyst macroporous or gel resin series is one or more of Amberlyst 15, amberlyst 16, 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 or 1-carboxyethyl-3-methylimidazole bisulfate.
Preferably, the sulfonic group functionalized imidazole salt ionic liquid is one or more of 1-butylsulfonic acid-3-methylimidazole chloride salt, 1-butylsulfonic acid-3-methylimidazole bisulfate or 1-propylsulfonic acid-3-methylimidazole bisulfate.
Preferably, the sulfonate functionalized pyridinium ionic liquid is one or more of N-sulfobutyl pyridine p-toluenesulfonate, N-sulfobutyl pyridine bisulfate or N-sulfopropyl pyridine p-toluenesulfonate.
The polymerization inhibitor 1 in S1 is hydroquinone HQ, 4-methoxyphenol MEHQ, 2-tertiary butyl-4-methylphenol, 6-tertiary butyl-2, 4-dimethylphenol, 2, 6-di-tertiary butyl-4-methylphenol, 2-tertiary butylphenol, 4-tertiary butylphenol, 2, 4-di-tertiary butylphenol, 2-methyl-4-tertiary butylphenol, 4-tertiary butyl-2, 6-dimethylphenol, 2, 5-di-tertiary butylphenol; copper chloride, copper oxide, basic copper carbonate, copper sulfate, copper acetate, copper acrylate, 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-t-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 consistent with those in the prior art.
Preferably, the temperature of the esterification reaction is 70 to 130 ℃.
More preferably, the temperature of the esterification reaction is 80 to 110 ℃.
Preferably, the gas containing oxygen is introduced during the esterification reaction.
The polymerization inhibition effect can be further improved by introducing oxygen-containing gas, the gas can contain inactive gas besides oxygen, and the oxygen content can improve the polymerization inhibition effect and the reaction device is not limited by explosion.
More preferably, the gas further contains 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.
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 carrying out 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 between 1 and 25%, and the concentration of which is generally between 1 and 10% by using a reflux column for washing after the esterification reaction. Therefore, the esterification product can be washed 3-6 times by adopting a small amount of repeated principle and the generated low-concentration acid water.
Preferably, the washing is performed in S1 using the acid water.
Preferably, the temperature of the washing in S1 is 30 to 80 ℃.
The solid strong acid catalyst, the water-soluble ionic strong acid catalyst and the polymerization inhibitor 1 can be removed by washing, and the catalyst is recovered.
More preferably, the washing temperature in S1 is 40 to 60 ℃.
Preferably, the filtration is performed after the temperature is reduced to below 40 ℃ in S1.
More preferably, the filtration is performed after the temperature is reduced to 30 ℃ or lower in S1.
The solid strongly acidic catalyst may be removed completely or mostly by filtration.
The filtering process is as follows: filtering with a closed filter device.
Preferably, when the alcohol is a monohydric alcohol, the equivalent ratio of the hydroxyl group equivalent to (meth) acrylic acid in the alcohol is 1:1.1 to 1.5.
Preferably, when the alcohol is a polyol, the equivalent ratio of hydroxyl group equivalent to (meth) acrylic acid in the alcohol is 1:0.8 to 1.3.
More preferably, when the alcohol is a polyol, the equivalent ratio of hydroxyl group equivalent to (meth) acrylic acid in the alcohol 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 filtration and water washing to recycle the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain corresponding reaction products, and the reaction products can be used as accessory components to exist in an original esterification system, thereby realizing the reutilization of (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 low, and the method has a very wide application prospect.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
Example 1
The present example provides a treatment method for recycling (meth) acrylic acid in an esterification reaction system, concretely as follows.
In a 1000mL four-mouth reaction flask, 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 into the four-mouth reaction flask, an electric stirring, a thermometer, an LZB-2 type glass rotameter and a water separator (connected with a condenser), air of 1.8-2.5 mL/min is introduced, the mixture is heated and warmed to a reflux state in the esterification reaction, and water generated in the reaction is brought out of the esterification reaction bottle through the water separator by the azeotropy of toluene and heptane until water is generated in each hour and the temperature of the reaction liquid is stable, and the mixture is used as the end point of the esterification reaction.
The esterification reaction mixture is cooled to below 40 ℃, 200g of toluene is added, stirred, stood and filtered; 96.2g (acid content 8.9%) of acid water generated by the esterification reaction is used for washing the esterification reaction mixture for three times, and the washing temperature is 55-60 ℃.
Then the solvent is distilled off under the condition of 1340KPa and 60-85 ℃. 531g of a reaction mixture was obtained, which had an acid value of 35.2mgKOH/g.
In a 1000ml four-port reaction flask, 531g of an esterification reaction mixture with an acid value of 35.2mgKOH/g, 63g of CYD-128 epoxy resin (Baling petrochemical) and 2.8g of triphenylphosphine and 1.0g of 4-methoxyphenol are added, and the reaction is stopped at a temperature of 90-110 ℃ until the acid value is less than 3.0mgKOH/g by electric stirring, a thermometer, a reflux condenser and a constant-temperature oil bath.
Example 2
The present example provides a treatment method for recycling (meth) acrylic acid in an esterification reaction system, concretely as follows.
The preparation method is as follows.
In a 1000mL four-mouth reaction flask, 342g of tripropylene glycol, 260g of acrylic acid, 128g of toluene, 22g of 1-sulfopropyl-3-methylimidazole 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 into the four-mouth reaction flask by power stirring, a thermometer and a water separator (connected with a condenser), the mixture is heated and heated until the esterification reaction is in a reflux state, and water generated by the reaction is brought out of the esterification reaction flask through the water separator by azeotropy of toluene and water until water is generated in an hour of less than 1mL and the temperature of the reaction solution is stable, so that the mixture is used as the end point of the esterification reaction.
The esterification reaction mixture is cooled to below 40 ℃, 220g of toluene is added, stirred, stood and filtered; 64.7g (acid content 6.3%) of acid water generated by the esterification reaction is washed for three times to obtain an esterification reaction mixture, and the washing temperature is 40-55 ℃.
Then evaporating the solvent under the conditions of 13-40 KPa and 60-85 ℃. 526g of a reaction mixture was obtained, and the acid value was 12.2mgKOH/g.
In a 1000ml four-port reaction flask, 526g of an esterification reaction mixture with an acid value of 12.2mgKOH/g, 10.9g of epichlorohydrin, 1.5g of 4-lutidine and 1.0g of 4-methoxyphenol are added, and the mixture is stirred, a thermometer, a reflux condenser and a constant-temperature oil bath pot are added, and reacted at a temperature of 85-100 ℃ until the acid value is less than 5.0mgKOH/g, and the reaction is terminated.
Example 3
The present example provides a treatment method for recycling (meth) acrylic acid in an esterification reaction system, concretely as follows.
In a 1000mL four-mouth reaction flask, 320g of pentaerythritol propoxide (5 PO), 230g of acrylic acid, 140g of cyclohexane, 36g of sodium bisulfate monohydrate, 1.5g of cuprous oxide, 0.9g of copper dibutyl dithiocarbamate, 1.6g of 4-methoxyphenol and 5.2g of phosphorous acid are sequentially added into the four-mouth reaction flask by power stirring, a thermometer, an LZB-2 glass rotameter and a water separator (connected with a condenser), the mixture is heated and warmed to a reflux state by the esterification reaction, and water generated by the reaction is brought out of the esterification reaction flask by the water separator by azeotropy of the cyclohexane and the water until the water is less than 1mL per hour and the temperature of the reaction solution is stable and is used as the end point of the esterification reaction.
The esterification reaction mixture is cooled to below 40 ℃, 300g of toluene is added, stirred, stood and filtered; 59.3g (acid containing 10.3%) of acid water generated by the esterification reaction was washed three times to wash the esterification reaction mixture at 40-55 ℃. 886g of a reaction mixture was obtained, which had an acid value of 16.7mgKOH/g.
In a 1000ml four-port reaction flask, 600g of an esterification reaction mixture (containing a 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 mixture is stirred, a thermometer, a reflux condenser and a constant temperature oil bath pot, reacted at 90-115 ℃ until the acid value is less than 5.0mgKOH/g, and the reaction is terminated. Then the solvent is distilled off under the conditions of 13 KPa-55 KPa and 60-90 ℃.
Example 4
The present example provides a treatment method for recycling (meth) acrylic acid in an esterification reaction system, concretely as follows.
In a 1000mL four-mouth reaction flask, 300g tetrahydrofurfuryl alcohol, 286g methacrylic acid, 180g toluene, 39g 1-hydroxyethyl-3-methylimidazole bisulfate, 5.6g copper acrylate and 0.3g hypophosphorous acid are sequentially added into the flask by a power stirring, thermometer, LZB-2 glass rotameter, water knockout drum (connected with a condenser) and a vacuum system, 2.6-3.2 mL/min of air is introduced, the temperature is raised until the esterification reaction is in a reflux state, and water generated by the reaction is brought out of the esterification reaction flask through the water knockout drum until the water is less than 1mL per hour and the temperature of the reaction liquid is stable and is used as the end point of the esterification reaction.
The esterification reaction mixture is cooled to below 40 ℃, 200g of toluene is added, stirred, stood and filtered; the esterification reaction mixture was washed three times with 54.5g (acid containing 3.7%) of acid water at 40-55 ℃. 710g of a reaction mixture was obtained, which had an acid value of 29.8mgKOH/g.
In a 1000ml four-port reaction flask, 710g of an esterification reaction mixture having an acid value of 29.8mgKOH/g, 37.0g of cyclohexene oxide, 1.7g of triethylbenzyl ammonium chloride, 1.7g of triethylamine and 0.9g of 4-methoxyphenol were added and reacted at 90 to 115℃until the acid value was less than 3.0mgKOH/g, followed by termination of the reaction, followed by stirring, a thermometer, a reflux condenser and a constant temperature oil bath.
Then the solvent is distilled off under the conditions of 13 KPa-55 KPa and 60-90 ℃.
The treatment method provided by the invention firstly utilizes filtration and water washing to recycle the catalyst a and the polymerization inhibitor 1 in the esterification reaction, then utilizes the reaction of epoxide and (methyl) acrylic acid to obtain corresponding reaction products, and the reaction products can be used as accessory components to exist in an original esterification system, thereby realizing the reutilization of (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 low, and the method has a very wide application prospect.
While the foregoing is directed to particular illustrative embodiments of the present invention, several modifications and variations may be made by those skilled in the art without departing from the principles of the present invention. Indeed, the scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A treatment method for reutilizing (methyl) acrylic acid in an esterification reaction system is characterized by comprising 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 through the following steps: 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 1-sulfopropyl-3-methylimidazole chloride; and the temperature of the water washing in the step S1 is 40-60 ℃.
2. The process of claim 1 wherein the epoxide in S2 is one or more of a monomeric epoxide or a polymeric epoxide.
3. The method according to claim 2, wherein the monomeric epoxy compound is epichlorohydrin, epoxycyclohexane, 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexane carboxylate, 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, C 8 -C 10 Alkyl glycidyl ether, C 12 Alkyl glycidyl ether, C 12 -C 14 One 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 a polymeric aromatic epoxy compound, a polymeric alicyclic epoxy compound, a polymeric aliphatic epoxy compound or a polymeric heterocyclic epoxy compound.
4. The process according to claim 1, wherein in S2 the catalyst b is a tertiary amine and its salts, quaternary ammonium salts, sulphonic acids, phosphines, phosphonium salts, metal halides or metal-organic compounds;
the polymerization inhibitor 2 is one or more of 4-methoxyphenol MEHQ, p-tert-butylcatechol, tert-butylhydroquinone, o-methyl hydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-p-cresol, methyl hydroquinone or hydroquinone.
5. The process according to claim 1, wherein the reaction temperature in S2 is 85 to 125 ℃.
6. The method according to claim 1, wherein the ratio of the epoxide equivalent of S2 to the equivalent of (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-tertiary butyl-4-methylphenol, 6-tertiary butyl-2, 4-dimethylphenol, 2, 6-di-tertiary butyl-4-methylphenol, 2-tertiary butylphenol, 4-tertiary butylphenol, 2, 4-di-tertiary butylphenol, 2-methyl-4-tertiary butylphenol, 4-tertiary butyl-2, 6-dimethylphenol and 2, 5-di-tertiary butylphenol; copper chloride, copper oxide, basic copper carbonate, copper sulfate, copper acetate, copper acrylate, 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-t-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 method according to claim 7, wherein the monohydric alcohol is lauryl alcohol or C 8 -C 10 One or more of alcohol, isooctanol, isodecyl alcohol, tetrahydrofuranyl alcohol, cyclotrimethylolpropane formal, o-phenylphenoxyethanol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyethoxyethanol and ethoxynonylphenol;
the polyalcohol is ethylene glycol, neopentyl glycol, 1, 3-propylene glycol, 1, 6-hexanediol, 2-ethyl-1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol (methyl propylene glycol), dipropylene glycol, tripropylene glycol, neopentyl glycol ethoxylate, 1, 6-hexanediol ethoxylate, 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 glycol, polycaprolactone diol, trimethylolpropane, trimethylolethane, trimethylolpropane ethoxylate, trimethylolpropane propoxylate, trimethylolpropane, and glycerol, ethoxylated glycerol, propoxylated glycerol, tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated cyanuric acid, propoxylated cyanuric acid, caprolactone-extended ethoxylated cyanuric acid, polyester triol, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, caprolactone-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, caprolactone-extended pentaerythritol, polyester tetraol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, caprolactone-extended dipentaerythritol, polyester hexaol or hyperbranched polyester polyol.
9. The process according to claim 1, wherein the esterification reaction temperature is 70 to 130 ℃.
10. The method according to claim 1, wherein when the alcohol is a monohydric alcohol, the equivalent ratio of hydroxyl group equivalent to (meth) acrylic acid in the alcohol is 1:1.1 to 1.5; when the alcohol is a polyhydric alcohol, the equivalent ratio of hydroxyl equivalent in the alcohol to (methyl) acrylic acid is 1:0.8-1.3.
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