WO2003028888A1 - Procede de recuperation de catalyseur de transesterification - Google Patents

Procede de recuperation de catalyseur de transesterification Download PDF

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WO2003028888A1
WO2003028888A1 PCT/JP2002/009834 JP0209834W WO03028888A1 WO 2003028888 A1 WO2003028888 A1 WO 2003028888A1 JP 0209834 W JP0209834 W JP 0209834W WO 03028888 A1 WO03028888 A1 WO 03028888A1
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reaction
catalyst
transesterification
polystannoxane
alcohol
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PCT/JP2002/009834
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English (en)
Japanese (ja)
Inventor
Jing Yu
Yanxia Xiu
Masayuki Moriwaki
Hidetomo Kai
Sansan Wu
Fengqi Chen
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Dainippon Ink And Chemicals, Inc.
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Publication of WO2003028888A1 publication Critical patent/WO2003028888A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/42—Tin
    • 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

Definitions

  • the present invention relates to a method for recovering an ester exchange catalyst from a crude reaction product when an ester compound such as an unsaturated carboxylic acid ester or a polyether-based polyester is produced by a transesterification reaction.
  • Ester compounds are unsaturated carboxylic esters useful in the technical fields such as paint resins, printing inks, UV curable resins, molding resins, films, adhesives, etc., or poly useful in applications such as polyester plasticizers. It is used industrially as ether-based polyester.
  • Such an ester compound is usually produced by a direct esterification method of a carboxylic acid and a polyol in the presence of an inorganic acid.
  • a direct esterification method of a carboxylic acid and a polyol in the presence of an inorganic acid.
  • side reactions are liable to occur and the product purity is inevitably reduced.
  • excess carboxylic acid and acid catalyst are used, the reaction after completion of the reaction is unavoidable.
  • post-processing became complicated. Therefore, in order to avoid such a problem, production of an ester compound by a transesterification method has been studied.
  • an organotin compound has attracted attention as an ester exchange reaction catalyst having excellent catalytic activity.
  • Japanese Patent Application Laid-Open No. Hei 7-82877 discloses a reaction in which dimethyltin dichloride and dialkyltin oxide are used in combination as catalysts.
  • a technique for preventing the harmful organotin compound from being mixed in the transesterification product by treating the product with an acid or an acid after completion of the transesterification product has been disclosed.
  • the catalyst is completely decomposed to prevent the incorporation of the organotin compound into the reaction product, and the recovery of the catalyst was completely impossible, resulting in an increase in production cost. That is, when a tin-based catalyst having excellent catalytic activity is used in the transesterification reaction, there is no means for recovering the spent catalyst at present. Disclosure of the invention
  • the problem to be solved by the present invention is to provide a method for recovering a transesterification catalyst which can recover the transesterification catalyst without deactivating the catalyst activity while using a transesterification catalyst having excellent catalytic activity. It is in.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, used a polystannoxane compound having a specific structure as a transesterification catalyst in the transesterification reaction, and, after completion of the reaction, It has been found that by extracting the transesterification catalyst with water, the transesterification catalyst can be recovered at a good recovery rate without deactivating the catalytic activity, and the present invention has been completed.
  • R is a methyl group or ethyl group
  • X is each independently an electron-withdrawing group having a lone electron pair on the atom bonded to Sn
  • n represents an integer of 1 to 8.
  • a method for recovering a transesterification catalyst comprising recovering the polystannoxane from the obtained crude reaction product by extracting the polystannoxane with water.
  • the transesterification catalyst used in the present invention has the following general formula (1)
  • R is a methyl group or an ethyl group
  • X is each independently an electron-withdrawing group having a lone pair on the atom bonded to Sn
  • n represents an integer of 1 to 8.
  • the electron-withdrawing group having a lone electron pair on the atom bonded to Sn includes a halogen atom selected from a chlorine atom, a bromine atom or a fluorine atom, a carbon atom number of 1 To 4 alkoxy groups, hydroxyl groups, thiol groups, and thiocyanic acid groups.
  • the polystannoxane used in the present invention includes a disoxanoxane compound or a trisoxane compound in which R in Formula (1) is a methyl group and X is a halogen atom, an acyloxy group, or a thiocyanate group. Noxane is preferred.
  • the tris-noxane compound has better stability in water and is less likely to be hydrolyzed in water than the dis-oxanoxane compound, and can reduce the amount of residual organotin compound in the product. This is preferable in that the recovery rate of the compound increases.
  • tristannoxane compound has the following general formula (2) when performing a transesterification reaction.
  • R represents a methyl group or an ethyl group
  • X independently represents an electron-withdrawing group having a lone pair on the atom bonded to Sn.
  • a tin compound represented by the formula and an alkali compound may be charged and used to form a tristannoxane compound in situ during the transesterification reaction.
  • the alcohol used in the transesterification reaction may be appropriately selected according to the intended use of the ester compound, and examples thereof include aliphatic alcohols, alicyclic alcohols, aromatic alcohols, and polyols. Further, these alcohols may be saturated or unsaturated, and the number of carbon atoms constituting the alcohol is usually 1 to 30.
  • the alcohol can be appropriately selected according to the purpose as described above.
  • a monovalent to tetravalent or hexavalent alcohol can be used.
  • R 2 is an alkylene group having 2 to 8 carbon atoms
  • R 3 is an alkyl group or aryl group having 1 to 18 carbon atoms
  • n is an integer of 1 to 30.
  • dihydric alcohol examples include ethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butanediol, pen diol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, and hexane.
  • Trihydric alcohols include hexanetriol, octanetriol, decanetriol, trimethyl-l-propane, trimethyl-l-propane, and ethyloxyl. Trimethylolpropane, trimethylolbutane, and dariserin.
  • tetrahydric alcohol examples include pen-erythritol, ditrimethylolpropane, hexitol, sorbitol, and mannitol.
  • Hexahydric alcohols include dipentaerythritol.
  • divalent to tetravalent or hexavalent alcohols are particularly useful as polyfunctional monomer raw materials. That is, an ester compound obtained by subjecting such a polyhydric alcohol to a transesterification reaction with an unsaturated carboxylic ester such as (meth) acrylate is extremely useful as a polyfunctional monomer effective for polymer cross-linking. Useful. Further, the polystannoxane has a characteristic of exhibiting excellent activity in such a transesterification reaction, and being capable of obtaining a target product with high yield and purity. It is also noteworthy that in the present invention, even if such a polyhydric alcohol is transesterified with an unsaturated carboxylic acid ester, gelling hardly occurs.
  • the carboxylic acid alkyl ester to be reacted with the alcohol in the transesterification reaction various kinds of saturated or unsaturated carboxylic acid esters can be used.
  • Acrylate is preferred.
  • Such (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate.
  • the transesterification step of the present invention is characterized in that polymerization of (meth) acrylates hardly occurs during the transesterification reaction even when these (meth) acrylates are used.
  • the transesterification in the present invention can be carried out in the presence or absence of a solvent. However, since the transesterification is a reversible reaction, it is desirable to remove the produced alcohol out of the system. It is preferable to use an organic solvent capable of azeotropic distillation with.
  • the amount of the organic solvent used is not particularly limited, but is in a range that does not affect the transesterification reaction product, specifically, about 5 to 50% by mass of the starting material, The range of 0 to 30% by mass is preferable.
  • the organic solvent used here is an aliphatic or alicyclic hydrocarbon having 4 to 10 carbon atoms. Element or a mixture thereof. Specifically, n-pentane, n-hexane, n_heptane, n-octane, cyclohexane, benzene, toluene, 0-xylene, m-xylene, p-xylene, mesitylene, ethylbenzene, cumene And so on. Among these hydrocarbon solvents, n-hexane, n-heptane, cyclohexane, toluene and the like are preferable. These hydrocarbon solvents are recovered by azeotropic distillation, and can be recovered by extracting the alcohol with water.
  • reaction rate can be increased by adding an inert and high-boiling-point solvent.
  • a polymerization inhibitor may be used in combination for suppression.
  • the polymerization inhibitors used herein include, for example, benzoquinone, hydroquinone, force alcohol, diphenyl benzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylphenol -Butylcresol, phenothiazine and the like.
  • the amount of the polymerization inhibitor used depends on the amount of the ester compound as the reaction product and the amount of the raw material components, but is generally 5 to 100 ppm, and especially 20 ppm, based on the weight of the reaction product. It is preferably in the range of ⁇ 700 ppm.
  • the transesterification reaction can be performed at atmospheric pressure.
  • the reaction temperature conditions can be appropriately selected depending on the starting materials and the reaction solvent used, but are preferably from 20 to 150 ° C. That is, the reaction rate in the transesterification reaction is remarkably improved under the temperature condition of 20 ° C. or more, and the side reaction can be suppressed under the temperature condition of 150 ° C. or less.
  • the temperature is preferably from 70 to 120 ° C. from the viewpoint of suppressing the polymerization of unsaturated groups.
  • the transesterification reaction is carried out under an oxygen-containing gas atmosphere or while continuously introducing an oxygen-containing gas into the surface of the reaction solution or into the reaction solution. It is preferable to carry out the polymerization because polymerization of the (meth) acrylate can be favorably suppressed.
  • the oxygen-containing gas is air It may be present, but if the oxygen content is high on a volume basis, there is a risk of fire and explosion, and the product may be colored.Therefore, the gas must have an oxygen content of 5 to 13% by volume. Is preferred.
  • Such a gas having an oxygen content of 5 to 13% by volume can be adjusted, for example, by mixing air or oxygen with an inert gas at a ratio satisfying the above conditions.
  • examples of the inert gas include nitrogen and argon.
  • the flow rate when the oxygen-containing gas is continuously introduced into the surface of the reaction solution or into the reaction solution is 0.1 to 30 mL / Z per 1 mol of the raw material (medium) acrylate.
  • the oxygen-containing gas is continuously introduced into the reaction solution, it is preferable to blow the oxygen-containing gas into the reaction solution so as to form very fine bubbles, since the efficiency of the polymerization preventing effect is enhanced.
  • a coloring inhibitor when (meth) acrylate is used as a raw material, it is desirable to add a coloring inhibitor into the reaction system and perform a transesterification reaction from the viewpoint of preventing coloring of the product.
  • a coloring inhibitor include trialkyl esters such as trimethyl phosphate, triethyl phosphate, and tributyl phosphate; organic phosphonic acids such as dibutyl butyl phosphonate; organic esters of phosphorous acid such as dibutyl hydrogen phosphate; Inorganic phosphorus compounds such as phosphoric acid and polyphosphoric acid, and triphenyl phosphate.
  • phosphorous acid or an organic ester of phosphorous acid is particularly preferred because of its excellent coloring prevention effect.
  • the amount of the coloring inhibitor to be used is desirably 0.01 to 3 parts by mass with respect to 100 parts by mass of the ester compound as the target product of the transesterification reaction.
  • the ratio of the alcohol and the carboxylic acid ester to be used is not particularly limited, but the molar ratio of the carboxylic acid ester to the alcohol is usually 1 or more.
  • the molar ratio of the ester to the hydroxyl group of the alcohol is preferably in the range of 1.1: 1 to 10: 1.
  • the transesterification in the present invention can be specifically performed by the following method.
  • a predetermined amount of alcohol and carboxylic acid ester are mixed with a thermometer, a stirrer,
  • the reactor is equipped with a distilling tube and a line for introducing dry air, and then an appropriate amount of a catalyst, a polymerization inhibitor, and if necessary, a solvent and a color inhibitor are added to the reaction mixture,
  • a method in which the mixture is heated with stirring to the above-mentioned appropriate temperature range, usually to the reflux temperature of the reaction system, may be mentioned.
  • the alcohol generated by the transesterification reaction during the reaction is removed as an azeotrope with an excess of a carboxylic acid ester or an organic solvent by a fractionating tube. It is desirable to do.
  • the content of the target product in the reaction mixture is tracked by gas chromatography analysis or the like, and it is desirable to continue the reaction until the content of the target ester compound becomes 90% by mass or more.
  • the reaction time is not particularly limited, but is usually 6 to 40 hours.
  • the reaction solution may be subjected to a step of extracting it with the following water as a crude reaction product, or an excess of the starting carboxylic acid ester or the reaction solvent is distilled off from the reactor, and the residue is removed. It may be subjected to a step of extracting with a water as a crude reaction product. Alternatively, a crude reaction product may be obtained by distilling excess carboxylic acid ester or the reaction solvent from the reactor and then adding a small amount of an inert solvent such as toluene-heptane.
  • an inert solvent such as toluene-heptane.
  • the method of extracting the polystannoxane with water comprises mixing a predetermined amount of water with the crude reaction product, transferring the polystannoxane into an aqueous layer, Recovering the polystannoxane from the aqueous layer.
  • the water used here is preferably warm water at 30 to 80 ° C. in that the polyoxane can be satisfactorily transferred into the aqueous layer, and the extraction efficiency is improved.
  • the extraction operation of mixing water with the crude reaction product may be performed only once for the reaction product, but may be performed a plurality of times.
  • the amount of water used here is not particularly limited, but the amount used for one extraction may be 40 to 80 times the amount of polyoxane on a mass basis.
  • the recovery rate of the catalyst increases, but in the present invention, Since the catalyst can be satisfactorily transferred from the reaction product to the aqueous layer, for example, a recovery of 70 to 90% by mass is obtained by extracting 3 to 10 times.
  • the extraction operation can be specifically performed using a separation funnel or a reaction vessel equipped with a discharge port.
  • the extraction time varies depending on the scale at which the operation is performed. However, in order to perform the extraction operation efficiently, it is preferable that the mixing is performed for 5 to 30 minutes and then the mixture is allowed to stand for 10 to 40 minutes. Further, in order to enhance the extraction efficiency, it is preferable to maintain the temperature in the system in a temperature range of 30 to 80 ° C.
  • the target transesterification catalyst is recovered by isolating the polystannoxane from the aqueous layer.
  • the separated aqueous layer is concentrated by heating to an aqueous solution having a solid content of 10% by mass or more, and an organic solvent capable of azeotropic distillation with water is added. There is a method of obtaining a target catalyst by removing it.
  • organic solvent examples include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Is received.
  • the amount of the polymerization inhibitor added here is from 1 to L 0 pm on a mass basis with respect to the mass of the aqueous solution having a solid content of 10% by mass or more obtained by heating and concentrating as described above.
  • the temperature conditions and pressure conditions during the dehydration may be appropriately selected depending on the raw material components of the transesterification reaction.
  • (meth) acrylic acid is used as the raw material monomer and the decant dehydration is performed
  • the temperature is preferably 50 to 70 ° C and 1 to 35 kPa.
  • the transesterification catalyst thus recovered retains excellent activity with almost no loss of catalytic activity, and can be used again as a catalyst for transesterification reaction. Even in the case of transesterifying an alcohol and a carboxylic acid ester using such a recovered transesterification catalyst, the desired ester compound can be obtained in good yield.
  • the desired ester when a di- to tetra-hydric alcohol is reacted with (meth) acrylate using the recovered transesterification catalyst, the desired ester can be obtained with excellent yield and selectivity "selectivity". A compound is obtained.
  • the transesterification catalyst since the transesterification catalyst has a good recovery efficiency, even if the transesterification reaction is performed three or more times by collecting and reusing the ester exchange catalyst, the desired ester can be obtained with a good yield and selectivity. A compound is obtained.
  • the organic layer formed when water is mixed with the crude reaction product contains the ester compound as the product.
  • the content of the organotin compound is sufficiently reduced.
  • the organic layer in order to completely remove the organotin compound from the organic layer, it is preferable to treat the organic layer with an alkali.
  • the alkali include hydroxides of alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, sodium methoxide, potassium methoxide, calcium methoxide, and the like.
  • Alkoxides of alkaline metals or alkaline earth metals, and carbonates such as sodium carbonate and calcium carbonate.
  • the method of performing the treatment is not particularly limited, but a 0.5 to 2 times the amount of a 5 to 25% by mass aqueous solution of the organic layer on a mass basis is added to the organic layer, and the aqueous layer is separated after sufficiently stirring. Can be performed.
  • a method of isolating the ester compound as a product from the organic layer for example, a method of distilling off the organic solvent is preferable.
  • (meth) acrylate is used as the carboxylic acid alkyl ester
  • any of the above-mentioned ones can be used, but metoquinone is particularly preferably used in that there is no denaturation coloring.
  • the amount of addition depends on the type of the (meth) acrylate obtained, but is usually based on the solution constituting the organic layer. 5 to 5000 ppm, preferably 50 to 2500 ppm on a mass basis.
  • the ester compound as a reaction product is an aliphatic or alicyclic ester compound having a,] 3-unsaturated bond, particularly when (meth) acrylate is used as the carboxylic acid alkyl ester. .
  • Such an ester compound is useful as a so-called reactive monomer, which is polymerized by an active energy line, heat, a radical polymerization initiator, or the like. Therefore, the present invention is particularly preferably applied to the production of such a reactive monomer.
  • the method for recovering a transesterification catalyst of the present invention is useful not only in the production of reactive monomers but also in the technical fields of paint resins, printing inks, UV curable resins, molding resins, films, adhesives, and the like. It can also be applied to the production of unsaturated carboxylic esters and the production of polyester-based polyesters useful in applications such as polyester-based plasticizers.
  • Injection part temperature 300 ° C
  • Power ram temperature 150-300 ° C (heating rate: 15 ° C / min),
  • This organic layer was returned to the separating funnel again, and the extraction operation was performed in the same manner.
  • the aqueous layers used for extraction were combined, water was removed by distillation under reduced pressure at 80 ° C, a small amount of toluene was added, and dehydration was performed by azeotropic distillation to form a white solid catalyst.
  • a transesterification reaction (second reaction) was performed in the same manner.
  • a white solid catalyst was recovered in the same manner, and a transesterification reaction (third reaction) was performed again using the recovered catalyst.
  • the following table shows the reaction time in each reaction and the content of the target compound in the reaction product.
  • TMP trithiadiaza trimethylolpropane
  • C 1 CH 3
  • S nOS n CH 3
  • 2 C 1 C 1 6
  • 03 g the p- methoxy phenol 2.
  • the reaction was performed at the reaction temperature, and the reaction was followed at intervals of 2 hours.
  • TMPTA trimethylolpropane triacrylate
  • This aqueous solution was transferred to a 3 L reaction vessel equipped with decane, 14.8 mg of p-methoxyphenol was further added, and 1300 g of water was distilled off under reduced pressure at 50 to 55 ° C. Thereafter, 300 g of toluene was added into the flask, and the remaining water and toluene were distilled off under reduced pressure at 55 to 70 ° C. by decant dehydration to recover a white solid catalyst.
  • a transesterification reaction (second reaction) was performed using the recovered catalyst in the same manner as described above, and then a white solid catalyst was recovered in the same manner, and a transesterification reaction (second reaction) was performed using the recovered catalyst.
  • the reaction time and the GC analysis results of the ester compound and the yield of trimethylolpropane triacrylate in each reaction are shown in the following table. Table 2
  • TMPTA tritylolpropane triacrylate
  • TMP tritylolpropane
  • ethyl acrylate ethyl acrylate
  • C 1 S n (CH 3 ) 2 OS n (CH 3 ) 2 OS n (CH 3 ) produced as a catalyst in the same manner as in Example 1.
  • 03 g, p- methoxy off with 7. 4 g of enol, these were added to 3 L flask with dry air inlet tube and a thermometer and equipped fractionating column stirrer, flow rate 6 OmLZ min air
  • the reaction was carried out at a stirring speed of 300 rpm and a reaction temperature of 100 to 110 ° C.
  • the reaction was followed at 2 hour intervals during the reaction.
  • the content of tritylpropane triacrylate (TMPTA) in the system was 91.7% by mass, and the reaction was terminated.
  • TMPTA tritylpropane triacrylate
  • This aqueous solution was transferred to a 3 L reaction vessel equipped with decane, and 14.8 mg of P-methoxyphenol was further added thereto, and 1300 g of the mixture was distilled under reduced pressure at 50 to 55 ° C. Of water was distilled off. Thereafter, 300 g of toluene was added to the flask, and the remaining water and toluene were distilled off under reduced pressure at 55 to 70 O: by decant dehydration to recover a white solid catalyst.
  • the separated aqueous layer was taken out from the bottom of the flask, and 300 g of a 10% aqueous sodium sulfate solution was newly added to the remaining organic layer, and the washing operation was performed in the same manner. 0.08 g of p-methoxyphenol was added to the obtained organic layer, followed by concentration to obtain an ester compound. When the concentration of tin remaining in the ester compound was measured, it was 3.7 ppm.
  • the purity of trimethylolpropane triacrylate in the ester compound and the yield of trimethylolpropane triacrylate based on the mass of the raw material trimethylol are shown in the following table.
  • the present invention it is possible to provide a method for recovering a transesterification catalyst, which can recover the transesterification catalyst without deactivating the catalyst activity while using a transesterification catalyst having excellent catalytic activity.
  • the transesterification catalyst recovered by the recovery method of the present invention has a feature that polymerization of a monomer can be suppressed in the production of an unsaturated carboxylic acid ester. It can be preferably applied to the production of unsaturated carboxylic esters useful in the technical fields of UV curable resins, molding resins, films, adhesives and the like.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé par lequel un composé de polystannoxane ,lequel présente une structure spécifique et est utile en tant que catalyseur de transestérification ayant une excellente activité catalytique, peut être récupéré à un pourcentage de récupération satisfaisant sans désactiver le catalyseur. L'invention concerne également un polystannoxane représenté par la formule générale (1) (dans laquelle R représente méthyle ou éthyle; les X représentent chacun indépendamment un groupe attirant les électrons présentant des électrons par paire célibataires sur l'atome lié à l'atome d'état; et N représente un nombre entier de 1 à 8) lequel est utilisé en tant que catalyseur de transestérification pour faire subir une transestérification à un alcool et un ester carboxylique. Ensuite, le polystannoxane est extrait à l'aide d'eau du produit de réaction brut obtenu afin de récupérer ainsi le polystannoxane.
PCT/JP2002/009834 2001-09-28 2002-09-25 Procede de recuperation de catalyseur de transesterification WO2003028888A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001/301178 2001-09-28
JP2001301178 2001-09-28

Publications (1)

Publication Number Publication Date
WO2003028888A1 true WO2003028888A1 (fr) 2003-04-10

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PCT/JP2002/009834 WO2003028888A1 (fr) 2001-09-28 2002-09-25 Procede de recuperation de catalyseur de transesterification

Country Status (1)

Country Link
WO (1) WO2003028888A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0881209A1 (fr) * 1997-05-30 1998-12-02 Mitsubishi Chemical Corporation Procédé de préparation de l'ester hydroxyalkyle monoacrylate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0881209A1 (fr) * 1997-05-30 1998-12-02 Mitsubishi Chemical Corporation Procédé de préparation de l'ester hydroxyalkyle monoacrylate

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