WO2007129606A1 - (メタ)アクリル酸エステルの製造方法 - Google Patents
(メタ)アクリル酸エステルの製造方法 Download PDFInfo
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- WO2007129606A1 WO2007129606A1 PCT/JP2007/059164 JP2007059164W WO2007129606A1 WO 2007129606 A1 WO2007129606 A1 WO 2007129606A1 JP 2007059164 W JP2007059164 W JP 2007059164W WO 2007129606 A1 WO2007129606 A1 WO 2007129606A1
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- meth
- acrylic acid
- semicarbazide
- acid ester
- organic solvent
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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
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Definitions
- the present invention relates to a method for producing a (meth) acrylic acid ester.
- (meth) acrylic acid esters are cured by ultraviolet irradiation or electron beam irradiation, they are used in various industrial applications such as optical lenses, printing inks, coating agents, and adhesives as a component of photocurable compositions. Used.
- the (meth) acrylic acid ester composition containing a polymer component causes uneven curing and turbidity, and therefore cannot be suitably used in applications such as optical lenses where uniformity and light transmission are important.
- (meth) acrylic acid esters deteriorate the water resistance in addition to problems of odor and equipment corrosion, so the cured product absorbs water when used for coatings and adhesives. As a result, the coating surface may be peeled off or the adhesive strength may be reduced.
- (meth) acrylic acid ester may be heated and stirred for homogenization at the time of blending, or may be exposed to a heat resistance test after photocuring. In addition to the generation of such polymer and acid components, it cannot be used in optical lens applications where transparency is essential in order to produce coloration.
- acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”.
- (Meth) acrylic acid esters are usually produced by reacting (meth) acrylic acid and alcohols in the presence of an acid catalyst in the presence of a dehydrating ester, but various impurities are by-produced during the esterification reaction. In order to remove such impurities, it is usually not always sufficient to remove force impurities that are washed with water or an aqueous alkaline solution for the reaction solution after dehydration esterification.
- Patent Document 1 discloses a method in which a reaction product after dehydration esterification is neutralized and then treated with amines! Speak.
- Patent Document 2 discloses a method of adding a cationic surfactant when neutralizing or washing the reaction solution after the production of (meth) acrylic acid ester. Therefore, it is disclosed that emulsification in the vicinity of the interface between the organic layer and the aqueous layer can be prevented, the separation time of the organic layer and the aqueous layer can be shortened, and as a result, impurities can be efficiently removed. ing.
- Patent Document 2 Although the method described in Patent Document 2 is excellent in shortening the separation time of the organic layer and the aqueous layer, the storage stability and thermal stability of the resulting (meth) acrylic acid ester are insufficient. It was.
- Patent Document 1 Japanese Patent Laid-Open No. 6-219991 (Claims)
- Patent Document 2 Japanese Patent Laid-Open No. 2001-048831 (Claims) Disclosure of the invention
- An object of the present invention is to provide a method for producing a (meth) acrylic acid ester having excellent storage stability and thermal stability.
- a method for producing a (meth) acrylic acid ester
- the step of adding semicarbazide to the reaction solution after step (2) and the reaction solution force of adding semicarbazide also includes the step of removing the organic solvent.
- a process for producing (meth) acrylic acid ester characterized by comprising a step (2) of carrying out the treatment and a step of adding semicarbazide;
- the (meth) acrylic acid ester obtained by the production method of the present invention is excellent in storage stability and thermal stability, and more specifically, can suppress an increase in acid value. For this reason, the obtained (meth) acrylic acid ester can be suitably used for various industrial uses such as optical lenses, printing inks, coating agents and adhesives as a compounding component of the photocurable composition.
- (meth) acrylic acid and alcohol are subjected to dehydration ester reaction in the presence of an acid catalyst, and the resulting reaction solution is subjected to neutralization treatment and washing treatment with a semi-strength reaction solution.
- the present invention relates to a method for producing a (meth) acrylic acid ester to which rubazide is added.
- the present invention can be preferably applied to the production of (meth) acrylic acid esters in which many impurities are generated and the alcohol is a polyhydric alcohol.
- the alcohol is a polyhydric alcohol
- a method of adding and mixing the treating agent at 30 to 100 ° C. in the reaction solution is preferable.
- the dehydration esterification reaction is preferably performed in an organic solvent. In this case, it is preferable to remove the solvent after adding the treatment agent to the reaction solution.
- step (1) first, (meth) acrylic acid and alcohol are heated and stirred in an organic solvent in the presence of an acid catalyst to cause dehydration esterification to obtain a reaction solution containing (meth) acrylic acid ester (1) [Hereinafter also simply referred to as step (1)] is performed.
- Glycols such as ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and their alkylene oxide adducts.
- Glycerin such as glycerin, diglycerin, triglycerin, polyglycerin and their alkylene oxide adducts.
- alkylene oxide examples include ethylene oxide and propylene oxide.
- the present invention can be preferably applied to polyhydric alcohols among the above-mentioned alcohols, in which many impurities are easily generated in the obtained (meth) acrylic acid ester.
- the alcohol that can be used in the present invention is preferably an alcohol having no alkylene oxide group among the above-mentioned alcohols! /.
- the proportion of (meth) acrylic acid and alcohol used in the dehydration esterification reaction is more preferably 0.8 to 2.0 moles of (meth) acrylic acid per mole of hydroxyl groups of the alcohol. 1. 0 to 1.5 moles.
- this ratio is 0.8 mol or more, the reaction time for dehydration esterification can be shortened, and side reactions such as Michael addition of alcoholic hydroxyl groups to (meth) acryloyl groups of (meth) acrylic acid esters can be achieved. Since it can be suppressed, it excels in product purity.
- Examples of the acid catalyst used in the dehydration esterification reaction include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, and the like. One kind can be used alone, or two or more kinds can be arbitrarily combined. Can be used. It is preferable to use sulfuric acid as the acid catalyst.
- the use ratio of the acid catalyst is preferably 0.05 to 10 mol%, more preferably 0.5 to 5 mol%, based on the number of moles of the alcoholic hydroxyl group provided to the dehydrated ester cake.
- this ratio is 0.05 mol% or more, a practical reaction rate can be sufficiently obtained.
- it is 10 mol% or less, side reactions can be suppressed, the product purity is excellent, and coloring can be suppressed.
- the catalyst removal operation and the product decolorization operation are simple.
- organic solvents include, for example, aromatic hydrocarbons such as toluene, benzene and xylene, hexane and cyclohexane. Aliphatic hydrocarbons such as xane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone.
- the organic solvent may be used alone or in combination of two or more.
- the proportion of the organic solvent is preferably 30 to 70% by weight in the reaction solution.
- the esterification reaction temperature is preferably 70 to 140 ° C.
- the reaction temperature is 70 ° C or higher, the reaction rate is excellent, and when it is 140 ° C or lower, the amount of impurities by-product during esterification can be suppressed, and no gelling occurs.
- a polymerization inhibitor for the purpose of preventing polymerization of the (meth) atalyloyl group, and an oxygen-containing gas may be introduced into the reaction solution.
- the polymerization inhibitor include organic polymerization inhibitors such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6 tri-tert-butylphenol, benzoquinone, and phenothiazine.
- Examples thereof include inorganic polymerization inhibitors such as copper chloride and copper sulfate, and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate.
- a polymerization inhibitor may be used individually by 1 type, or may be used in combination of 2 or more types arbitrarily.
- the proportion of the polymerization inhibitor is preferably 5 to 20, OOOwtppm in the reaction solution, more preferably 25 to 3, OOOwtppm.
- oxygen-containing gas examples include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium.
- step (2) of carrying out the neutralization treatment and the water washing treatment on the reaction solution after the step (1) [hereinafter sometimes simply referred to as step (2)] is carried out.
- step (2) each method is described below.
- the neutralization treatment is performed for the purpose of removing acidic components such as unreacted (meth) acrylic acid and acidic catalyst in the reaction product liquid, and is usually performed by bringing the reaction liquid into contact with an alkaline aqueous solution.
- Neutralization treatment can be performed according to a conventional method. Examples of the method include stirring and mixing.
- the alkali component examples include alkali metal salts such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and ammonia.
- the alkali component one kind may be used alone, or two or more kinds may be used in any combination. Of these, sodium hydroxide is preferred because of its excellent effect, low cost and easy availability.
- the amount of the alkali component is usually 1 time or more, preferably 1.1 to 2.0 times in molar ratio with respect to the acid content of the reaction solution. When the molar ratio of the additive is 1 or more, the acid content can be sufficiently neutralized.
- the concentration of the alkaline aqueous solution is preferably 1 to 25% by weight, more preferably 10 to 25% by weight. If this concentration is 1% by weight or more, the amount of waste water after neutralization can be suppressed, and if it is 25% by weight or less, (meth) acrylic acid ester will not polymerize!
- the stirring and mixing time may be appropriately set according to the amount of the reaction solution, the amount of the acidic component contained therein, the purpose, and the like, but is preferably about 5 to 120 minutes.
- the above-mentioned esterification reaction solution or neutralization treatment solution is washed with water.
- the point at which the water washing treatment is performed can be appropriately selected according to the components used and the purpose. Moreover, you may perform the water washing process in multiple times.
- water is usually used.
- an inorganic aqueous solution Specifically, an aqueous solution of ammonium sulfate and a salty ammonium solution are preferred.
- Ammonium salt aqueous solution such as aqueous solution, sodium salt aqueous solution such as sodium chloride, and acidic water such as hydrochloric acid aqueous solution.
- heating can be performed as necessary.
- the heating temperature is preferably 30 to 80 ° C, and the heating time is preferably 5 minutes to 5 hours.
- Distilled water is preferably used as the water used in the neutralization treatment or Z and washing treatment.
- a polymerization inhibitor for the purpose of preventing the polymerization of the (meth) attalyloyl group, and an oxygen-containing gas may be introduced into the reaction solution.
- the polymerization inhibitor include the same ones as described above, and the ratio thereof includes the same ratio as described above.
- Examples of the oxygen-containing gas include the same as described above.
- semicarbazide is added to the reaction solution obtained after the neutralization treatment and the water washing treatment.
- the present invention includes a step of adding semicarbazide to the reaction solution after the step (2) and a step of removing the organic solvent from the reaction solution added with semicarbazide, or
- the reaction solution force after the step (2) also includes a step of removing the organic solvent, a step of adding semicarbazide to the product excluding the organic solvent, and a step of heating the product to which the semicarbazide has been added.
- the production method is preferred.
- Semicarbazide is a compound having at least one semicarbazide group.
- the semicarbazide that can be used in the present invention is preferably a compound represented by the following formula (1).
- R 1 and R represent monovalent organic groups, which may be the same or different. Also good. R 1 and R 2 are preferably a substituted or unsubstituted alkyl group or a phenyl group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a stearyl group, a benzyl group, and a hydroxyethyl group. Of these, lower alkyl groups having 1 to 4 carbon atoms are more preferred! /.
- R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
- A represents a hydrogen atom or an n-valent organic group.
- A is preferably an n-valent organic group, more preferably a divalent or trivalent organic group.
- n is an integer of 1 or more, preferably an integer of 1 to 3, more preferably 2 or 3.
- the n-valent organic group is not particularly limited, but is preferably an aliphatic group or an alicyclic group that is preferably a hydrogen atom, a carbon atom, a nitrogen atom, and a group composed of Z or oxygen nuclear power. It is more preferable.
- Semicarbazide can be used alone or in combination of two or more.
- Various compounds can be used as the semicarbazide (hereinafter sometimes referred to as a treating agent), and examples thereof include compounds obtained by reacting isocyanate compounds with N, N disubstituted hydrazines.
- Examples of the isocyanate compound include 1,4-tetramethylene diisocyanate, 1,5 pentamethylene diisocyanate, 1,6 hexamethylene diisocyanate, 2, 2, 4 (or 2, 4, 4) Trimethyl-1, 6 hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1, 3 bis (isocyanate methyl) monocyclohexane, 4, 4'-dicyclohexyl Aliphatic or cycloaliphatic diisocyanates such as methane diisocyanate, xylylene diisocyanate and tetramethylxylene diisocyanate; 4, 4, — Diphenylmethane diisocyanate, 1, 4 Aromatic diisocyanates such as cyanate, 2,4 tolylene diisocyanate and naphthalene diisocyanate; derived from these diisocyanates Riisoshianeto; and n- buty
- N, N disubstituted hydrazine examples include N, N dimethyl hydrazine, N, N jet hydrazine, N, N dipropyl hydrazine, N, N diisopropyl hydrazine, N, N-distearyl hydrazine, N-methyl- N-ethylhydrazine, N-methyl-N-propyl hydrazine, N-methylN benzylhydrazine, N, N di (j8-hydrochichechinole) hydrazine and the like.
- the reaction of the isocyanate compound and the N, N-disubstituted hydrazine can be performed with or without a solvent.
- a solvent it is necessary to use a solvent inert to isocyanate.
- the reaction is preferably performed at a temperature of ⁇ 20 to 150 ° C., more preferably 0 to 100 ° C.
- isocyanate and the N, N-disubstituted hydrazine are reacted in approximately equivalent amounts.
- R 1 and R 2 in the above formula (1) are lower alkyl groups having 1 to 4 carbon atoms in that they have an excellent acid value increase suppressing function and are easily available, and R 3 and A semicarbazide having a semicarbazide group in which R 4 is a hydrogen atom is preferred. Furthermore, because of these advantages, R 1 and R 2 in the above formula (1) are lower alkyl groups having 1 to 4 carbon atoms because the treating agent is difficult to evaporate in the solvent removal step described later. A compound having a semicarbazide group in which R 3 and R 4 are hydrogen atoms and having a molecular weight of 200 or more is more preferable.
- the compounds include 1,4-tetramethylene bis-N, N dimethyl semicarbazide, 1, 6 hexamethylene bis-N, N dimethyl semicarbazide, 1, 1, 1 ', 1, monotetramethyl 4, 4' ( Methylenedi-p-phenylene) disemicarbazide and the following compounds are preferred.
- the timing of adding the treatment agent is arbitrary as long as it is after the step (2), and specifically includes before the solvent removal step or during the solvent removal step.
- the desolvation step and the treatment agent addition step can be performed in one step, and the treatment agent addition step is performed. Is preferable because it can be omitted.
- the final (meth) acrylic acid ester strength is high. If the viscosity of semicarbazide is insufficient if it is highly viscous, adding semicarbazide to the final product will result in insufficient dissolution and dispersion of semicarbazide. It may become. According to this method, even when the finally obtained (meth) acrylic acid ester has a high viscosity, the semicarbazide is added in a low-viscosity state containing an organic solvent, so that the semicarbazide has excellent solubility or dispersibility. This is preferable.
- Examples of the method of adding the treating agent include a method of adding to the (meth) acrylic acid ester with stirring and mixing.
- Semicarbazide is difficult to dissolve in (meth) acrylic acid esters and organic solvents, so it is preferable to disperse it in water and add it.
- the addition ratio of the treatment agent 2 to: L0,000 wtppm is preferable to 5 to 3, and OOOwtppm is more preferable to (meth) acrylic acid ester 50 to L, OOOwtppm force S is more preferable. . If this value is 2 wtppm or more, the effect of semicarbazide can be effectively exhibited. On the other hand, if it is 10, OOOwtppm or less, the resulting (meth) acrylic acid ester has excellent solubility, and as a composition. When used, it has excellent compatibility with other ingredients. It becomes.
- heating is preferable. This is because when the polyhydric alcohol is used as the alcohol, the resulting (meth) acrylic acid ester has a high viscosity, and the treatment agent can be blended uniformly in a short time.
- the heating temperature and heating time may be appropriately set according to the (meth) acrylic acid ester to be obtained and the purpose, but the heating temperature is preferably 30 to 100 ° C, more preferably 30 to 80 ° C.
- the heating time is preferably 5 minutes to 5 hours, more preferably 30 minutes to 3 hours.
- a polymerization inhibitor for the purpose of preventing the polymerization of the (meth) attalyloyl group, and an oxygen-containing gas may be introduced into the reaction solution.
- the polymerization inhibitor include the same ones as described above, and the ratio thereof includes the same ratio as described above.
- Examples of the oxygen-containing gas include the same as described above.
- the solvent removal process will be described.
- the neutralization treatment liquid or the water washing treatment liquid is transferred to the solvent removal tank, and the organic solvent in the organic layer after the water layer is separated by the neutralization treatment or the water washing treatment is removed. It is.
- the solvent removal treatment may be carried out according to a conventional method, for example, a method of removing the organic solvent by heating the solvent removal tank under reduced pressure.
- the depressurization degree of the solvent removal tank may be appropriately set according to the raw material to be used and the purpose, and is preferably 0.5 to 50 kPa. A method of gradually increasing the depressurization degree depending on the degree of removal of the organic solvent is preferable.
- the heating temperature may be appropriately set according to the (meth) acrylic acid ester to be obtained, the degree of reduced pressure, and the purpose, but is preferably 40 to 100 ° C, more preferably 60 to 80 ° C.
- the polymerization inhibitor include the same ones as described above, and the ratio thereof is the same ratio as described above.
- the reaction solution force after step (2) also includes a step of removing the organic solvent, a step of adding semicarbazide to the product excluding the organic solvent, and a step of heating the product to which the semicarbazide has been added.
- the method for producing the (meth) acrylic acid ester will be described.
- the viscosity can be reduced by heating to improve the mixing property of semicarbazide.
- a treating agent is added to the product excluding the organic solvent, which can be obtained by the same method as the desolvation step described above.
- the process to be performed may follow the same method as described above.
- the heating temperature is 40 to
- 100 ° C force S is preferable, more preferably 40 to 80 ° C.
- the filtration step it is preferable to perform pressure filtration in accordance with a conventional method.
- Examples of the pressure filtration method include a method in which the reaction liquid after solvent removal is put into a filter equipped with filter paper and filtration is performed while pressure is applied to the filter.
- the method of adding a filter aid to the reaction solution after the desolubilizer, the method of pre-coating the filter aid on the surface of the excess filter paper, and the method of using these in combination are preferred because the filtration efficiency can be improved.
- the gas used for pressurization include nitrogen, oxygen-containing gas (for example, oxygen 5% by volume, nitrogen 95% by volume), and air.
- the water concentration contained in the acrylate ester was adjusted to 1,000-3, OOOwtppm.
- the glass container containing the acrylate was sealed and heated in a heating block maintained at 80 ° C. for 144 hours. After cooling, the acid value was measured by the method described above.
- reaction solution After completion of the reaction, the reaction solution is cooled to 40 ° C or lower, and after toluene and water are added and washed by washing, a 20 wt% sodium hydroxide aqueous solution is added and neutralized. Extraction washing was performed by adding water.
- the obtained organic layer is in a state in which the target acrylic ester is diluted with toluene and a small amount of water, and the washing operation is substantially completed.
- 0.0g of MQ and 1, 6-hexamethylenebis-N, N-dimethylsemicarbazide (hereinafter referred to as HMSC) were added to acrylic acid ester at 562wtppm, and added to the oxygen-containing gas.
- HMSC 6-hexamethylenebis-N, N-dimethylsemicarbazide
- Example 1 the solvent removal treatment without adding HMSC was performed.
- the reaction solution after removal of the solvent was filtered under pressure to obtain an acrylate ester.
- the obtained acrylic acid ester was measured for the acid value, and the acid value was measured after the forced deterioration test. The results are shown in Table 1.
- Example 1 the solvent removal treatment without adding HMSC was performed.
- the mixture was stirred for 1 hour at 70 ° C. and uniformly mixed. Thereafter, after filtration under pressure, an acrylate was obtained.
- the obtained acrylic acid ester had a low acid value after the forced deterioration test, as in Example 1 above.
- Example 1 atorylate was produced in the same manner as in Example 1 except that HMSC was replaced in the solvent removal step and a predetermined amount of the treatment agent described in Table 2 below was added.
- Example 2 Into the same flask as in Example 1, 133 g of ditrimethylolpropane, 175 g of acrylic acid, 169 g of toluene, 5.3 g of sulfuric acid, 51 g of MQO. And 51 g of HQO. The mixture was heated and stirred within a range of ⁇ 110 ° C. and a reaction system pressure of 400 to 760 mmHg. The dehydrated esterification reaction was carried out for 5 hours while the generated water was removed from the system using a Dean-Stark tube.
- reaction solution was neutralized by the same method as in Example 1, and further added with water for extraction and washing.
- MQ was 0.06 g
- the treatment agent HMSC was Then, 186 wtppm was added, and toluene was distilled off by heating to 60-80 ° C under reduced pressure while blowing oxygen-containing gas.
- Example 5 atallate was produced in the same manner as in Example 1 except that a predetermined amount of the treatment agent described in Table 3 was added instead of HMSC.
- Example 5 the solvent removal treatment without adding HMSC was performed.
- Example 5 the solvent removal treatment without adding HMSC was performed.
- the mixture was stirred for 1 hour at 70 ° C. and uniformly mixed. Thereafter, after filtration under pressure, an acrylate was obtained.
- the obtained acrylic ester has a low acid value after forced deterioration, as in Example 5 above. It was a thing.
- Example 5 the solvent removal treatment without adding HMSC was performed.
- Compound A was added to the crude product obtained after distillation of toluene at the same rate as in Example 6.
- the mixture was stirred for 1 hour at 70 ° C. and uniformly mixed. Thereafter, after filtration under pressure, an acrylate was obtained.
- the obtained acrylic acid ester had a low acid value after forced deterioration, as in Example 6 above.
- the production method of the present invention can be used for a production method of (meth) acrylic acid ester.
- the obtained (meth) acrylic acid ester can be suitably used for various industrial uses such as optical lenses, printing inks, coating agents, and adhesives as a component of the photocurable composition.
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JP2008514449A JP5003676B2 (ja) | 2006-05-10 | 2007-04-27 | (メタ)アクリル酸エステルの製造方法 |
CN2007800167559A CN101443305B (zh) | 2006-05-10 | 2007-04-27 | (甲基)丙烯酸酯的制造方法 |
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Cited By (3)
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JP2008308466A (ja) * | 2007-06-18 | 2008-12-25 | Toagosei Co Ltd | (メタ)アクリル酸エステルの製造方法 |
JP5003676B2 (ja) * | 2006-05-10 | 2012-08-15 | 東亞合成株式会社 | (メタ)アクリル酸エステルの製造方法 |
JP2015224254A (ja) * | 2014-05-26 | 2015-12-14 | 東亞合成株式会社 | 硬化型組成物 |
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JPH06219991A (ja) * | 1993-01-25 | 1994-08-09 | Arakawa Chem Ind Co Ltd | 多官能性(メタ)アクリレートの製造方法 |
JP2001122820A (ja) * | 1999-10-26 | 2001-05-08 | Hitachi Chem Co Ltd | (メタ)アクリル酸エステルの製造法 |
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GB950622A (en) * | 1959-10-08 | 1964-02-26 | Celanese Corp | Purifying esters of ª‡,ª‰ olefinically unsaturated carboxylic acids |
DE10026644A1 (de) * | 2000-05-29 | 2001-12-06 | Basf Ag | Verfahren zur Herstellung von Estern ungesättigter Carbonsäuren |
CN101443305B (zh) * | 2006-05-10 | 2012-07-18 | 东亚合成株式会社 | (甲基)丙烯酸酯的制造方法 |
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JPH06219991A (ja) * | 1993-01-25 | 1994-08-09 | Arakawa Chem Ind Co Ltd | 多官能性(メタ)アクリレートの製造方法 |
JP2001122820A (ja) * | 1999-10-26 | 2001-05-08 | Hitachi Chem Co Ltd | (メタ)アクリル酸エステルの製造法 |
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JP5003676B2 (ja) * | 2006-05-10 | 2012-08-15 | 東亞合成株式会社 | (メタ)アクリル酸エステルの製造方法 |
JP2008308466A (ja) * | 2007-06-18 | 2008-12-25 | Toagosei Co Ltd | (メタ)アクリル酸エステルの製造方法 |
JP2015224254A (ja) * | 2014-05-26 | 2015-12-14 | 東亞合成株式会社 | 硬化型組成物 |
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CN101443305A (zh) | 2009-05-27 |
CN101443305B (zh) | 2012-07-18 |
JP5003676B2 (ja) | 2012-08-15 |
TWI402254B (zh) | 2013-07-21 |
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