JP2001213844A - Apparatus and method for producing acrylic acid ester or methacrylic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for efficiently producing a (meth)acrylic acid ester, especially a poly(meth)acrylate by using a metal material not being corroded with a reaction solution containing various kinds of compounds, a catalyst, an additive, etc., to become raw materials for producing a (meth)acrylic acid ester, having excellent heat transfer and excellent processability. SOLUTION: A nickel alloy having 6-20 mass % molybdenum, 14-20 mass % chromium and 0.5-5.5 mass % of cobalt is used as a raw material for the apparatus for producing an acrylic acid ester or methacrylic acid ester and an acrylic acid ester or a methacrylic acid ester is produced by using the apparatus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylate or methacrylate (hereinafter referred to as (meth)) which is used in a wide range of fields such as paints, inks, adhesives, potting agents, sealing agents, molding materials and the like. Acrylic acid ester), especially polyethylene glycol di
Poly (meth) acrylates such as (meth) acrylate, trimethylolpropane tri (meth) acrylate and polyester poly (meth) acrylate (hereinafter poly (meth) acrylate)
The present invention also relates to an apparatus capable of efficiently producing acrylates) and a method for efficiently producing such acrylates using the apparatus, and belongs to the chemical production technology.

[0002]

2. Description of the Related Art (Meth) acrylic acid esters, especially polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and polyester poly (meth) acrylate, furthermore, epoxy poly (meth) acrylate, urethane poly (meth) ) Acrylates and other poly (meth) acrylates are mainly produced by transesterification and dehydration esterification reactions, but in order to produce them efficiently, highly corrosive reaction catalysts and polymerization inhibitors must be used. Currently required. Therefore, the apparatus for producing them, specifically, the inner walls of an esterification reaction vessel, a rectification tower, a condensation reaction vessel and the like are usually provided with a glass lining to avoid corrosion.
As described above, poly (meth) acrylate has a wide application field, and the demand is steadily expanding.However, since the inner wall of the reaction vessel must be glass-lined, the heat transfer property of the glass lining It is difficult to increase the reaction speed based on defects, and it is difficult to increase the size of equipment due to the heat transfer and workability of glass lining. For this purpose, the use of metal materials is being studied, and the following proposals have been made. In other words, in a device for producing a (meth) acrylic acid ester by reacting (meth) acrylic acid and an alcohol in the presence of sulfuric acid, a surface in which a solution containing (meth) acrylic acid and sulfuric acid contacts is made of zirconium or an alloy thereof. Formed to enable polymer removal cleaning and miniaturization with alkali (meta)
Acrylic ester manufacturing equipment has been proposed (Japanese Patent Laid-Open No.
00-7615).

[0003]

[Problems to be solved by the present invention]
An object of the present invention is to provide an apparatus and a method for producing (meth) acrylic acid ester, particularly poly (meth) acrylate, which can be produced more efficiently.

[0004]

Means for Solving the Problems The present inventors have developed various kinds of (meth) acrylic acid esters, particularly poly (meth) acrylates, which are suitable for use in a production apparatus, that is, are used as raw materials for producing (meth) acrylic acid esters. The present invention was completed by searching for a metal material that was not corroded by a reaction solution containing a compound, a catalyst, an additive, etc., had good heat conductivity, and had good workability, and examined various materials. That is, in the present invention, the content of molybdenum, chromium and cobalt is 6 to 20% by mass,
(Meth) acrylic acid ester manufacturing apparatus characterized by using a nickel alloy of ２４24 mass% and 0.5-5.5 mass% as a material, and being manufactured using the manufacturing apparatus ( The present invention relates to a method for producing a (meth) acrylic acid ester, and further relates to a method for producing a method comprising using a strong acid as a catalyst and a metal salt as a polymerization inhibitor, particularly a metal chloride. is there.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The first invention of the present invention relates to a (meth) acrylic acid ester production apparatus,
In the present invention, the method for producing a (meth) acrylic ester is a method for producing a (meth) acrylic ester by a dehydration esterification reaction or a transesterification reaction of reacting (meth) acrylic acid with an alcohol in the presence of general sulfuric acid. In particular, the (meth) acrylic acid ester production apparatus of the present invention is a curable resin or polyethylene glycol di (meth) acrylate widely used as a raw material thereof,
For the production of poly (meth) acrylates such as poly (meth) acrylate of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, polyester poly (meth) acrylate, epoxy poly (meth) acrylate or urethane poly (meth) acrylate It is suitable. The following is a description of an example of a method for producing a polyhydric alcohol poly (meth) acrylate or a polyester poly (meth) acrylate as an example of a method for producing such a curable resin. That is, a polybasic acid or its anhydride (in the case of polyester poly (meth) acrylate), polyhydric alcohol, (meth) acrylic acid, esterification is placed in a reactor equipped with a stirrer, thermometer, air blowing tube and water separator. A catalyst, a polymerization inhibitor, and a reaction solvent also serving as a dehydrating azeotropic agent are charged, and water generated in the reaction is removed from the system as an azeotropic mixture with the reaction solvent while esterification is performed.
The end point of the esterification reaction is determined by the amount of water produced as a by-product, the reaction solution is washed with an aqueous alkali solution and water, the aqueous layer is separated, and the reaction solvent is distilled off under reduced pressure. This is a method of producing (meth) acrylate or polyester poly (meth) acrylate. In this method, the reaction can also be carried out by a sequential reaction method in which a part or all of the raw materials are sequentially added. The reaction temperature is preferably about 50 to 220 ° C., under reduced pressure and normal pressure.
The reaction can be carried out under any pressure. As the solvent in the reaction, n-hexane, cyclohexane,
Benzene, toluene, xylene, trichloroethane, tetrachloroethylene, methyl chloroform, diisopropyl ether and the like are preferably used. As the esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, benzenesulfonic acid, p-toluenesulfonic acid, cation An exchange resin or the like is used. Further, it is desirable that the esterification reaction is performed in the presence of a polymerization inhibitor.
Hydroquinone, methoxyhydroquinone, p-benzoquinone, t-butylcatechol, phenothiazine, naphthoquinone and cupric chloride are used. Polybasic acids or anhydrides used in the production of polyester poly (meth) acrylate include succinic acid, adipic acid, sebacic acid, 1,12-dodecane diacid, fumaric acid, maleic acid, itaconic acid, citraconic acid, Mesaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hymic acid, endo acid, het acid and anhydrides thereof. In addition, polyhydric alcohols used for producing polyhydric alcohol poly (meth) acrylates and polyester poly (meth) acrylates include ethylene glycol,
Propylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexenediol, cyclohexanedimethanol,
Glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, dipentaerythritol, ditrimethylolpropane, pentaerythritol, aliphatic polyhydric alcohols to which polyalkylene oxide is added, bisphenol A, bisphenol F, bisphenol And aromatic polyhydric alcohols in which the above-mentioned alkylene oxide is polyadded to S and hydroquinone.

[0006] The production apparatus used in the above-mentioned production method generally comprises a reaction vessel as a main apparatus and, as ancillary equipment, a heat exchange apparatus, a heating apparatus, a distillation column, a rectification column and the like. As described above, since the raw material, the catalyst and the polymerization inhibitor are used as the reaction solution, a compound having strong acidity or corrosiveness is used as the reaction solution, and therefore, the inside of which is glass-lined is used. In the present invention, a nickel alloy is used as the material of those devices, and the content of molybdenum, chromium and cobalt is 6 to 20% by mass, 14 to 24% by mass, and 0.5 to 0.5%, respectively, as the nickel alloy. A nickel alloy of 5% by mass is used, and a commercially available alloy can be used as the alloy. The nickel alloy does not need to be used in all of the (meth) acrylic acid ester production equipment, but may be used only in equipment and auxiliary equipment that comes into contact with corrosive reaction liquids, including pumps and piping, and only in the contact surface. It may be adopted. By using the nickel alloy in the (meth) acrylate manufacturing apparatus, in the combination of the catalyst and the polymerization inhibitor, it has a corrosive property such as a combination of sulfuric acid and a metal salt, particularly a metal chloride such as copper chloride. Even when using compounds, corrosion of the reactor can be prevented,
In addition, it is possible to prevent the adhesion of scale due to the generation of an undesirable polymer, and to increase the size of the equipment in addition to the heat transfer.

[0007]

EXAMPLES In the following, a corrosion test was performed on various stainless steels and nickel alloys in a reaction solution used for producing (meth) acrylic acid ester, and a material suitable as an apparatus for producing (meth) acrylic acid ester was selected. did. ○ Test materials 4 kinds of tested stainless steel materials and 6 nickel alloys
The composition of the species is summarized in Table 1.

[0008]

[Table 1]

○ Corrosion test method 12.7 mol of acrylic acid, 1.8 mol of dipentaerythritol and toluene were charged into a 3000 ml three-neck separable flask so as to be 35% by mass, sulfuric acid 2% by mass, and second chloride The mixture was heated to a concentration of 2000 ppm of copper, 1000 ppm of phenothiazine, and 1000 ppm of methylhydroxyquinone, heated, and reacted at a temperature of 100 to 120 ° C. The reaction is continued by removing water until the condensed water reaches 70% of the theoretical value,
Thereafter, the mixture was brought to a total reflux, and the reaction was brought into an equilibrium state. A test piece made of each material in the reaction solution in the equilibrium state and in the upper part (gas phase part) was set, and an exposure test was performed. The exposure period was 4 to 10 weeks, and the reaction solution was changed every week. The same reaction was carried out intermittently, and a poly (meth) acrylate was also installed in a gas phase portion of a reactor having a capacity of 15 m ² and subjected to an exposure test in the same manner. The state of corrosion was determined by observing the surface state with an optical microscope and the corrosion rate calculated from the weight loss of the test piece, and the scale adhesion amount and scale removability were evaluated. Scale removability was determined based on the following criteria. ◎ It can be removed with running water when the amount of deposits is 10 g or less per 1 m ² . ○ When the amount of deposits is 10 g or more per 1 m ² , it can be removed with running water. × The amount of the deposits is 10 g or more per 1 m ^{2 and} cannot be removed by running water. ××× The amount of attached matter is 10 g or more per 1 m ² and is firmly attached and can be removed only with a metal spatula.

[0010] Corrosion test results Tables 2 and 3 show the corrosion test results for the test pieces made of the above ten materials. As is evident from these results, the nickel alloy of the present invention has little corrosion due to the reaction solution for producing the (meth) acrylic ester, and has good adhesion of the scale and good removability of the formed scale.

[0011]

[Table 2]

[0012]

[Table 3]

[0013]

According to the apparatus for producing (meth) acrylic ester produced by using the nickel alloy according to the present invention, the scale caused by the corrosion due to the reaction solution is small and the amount of the scale deposited due to the undesirable polymer formation is also generated. The removability is good, and the size of the equipment can be increased due to the metal material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C07C 67/62 C07C 67/62 69/54 69/54 Z F term (reference) 4H006 AA02 AA04 BA28 BA35 BA36 BA39 BA52 BA66 BA94 BB11 BB12 BC10 BC11 BD83

Claims (4)

[Claims] 1. An acrylic material comprising a nickel alloy having molybdenum, chromium and cobalt contents of 6 to 20% by mass, 14 to 24% by mass and 0.5 to 5.5% by mass, respectively. Acid or methacrylate production equipment. 2. A method for producing an acrylic ester or a methacrylic ester, which is produced using the apparatus according to claim 1. 3. The method for producing an acrylate or methacrylate according to claim 2, wherein a strong acid as a catalyst and a metal salt as a polymerization inhibitor are used. 4. The method for producing an acrylate or methacrylate according to claim 3, wherein the metal salt is a metal chloride.