WO2012157456A1 - Procédé de fabrication d'acide 2-cyanoacrylique - Google Patents

Procédé de fabrication d'acide 2-cyanoacrylique Download PDF

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Publication number
WO2012157456A1
WO2012157456A1 PCT/JP2012/061649 JP2012061649W WO2012157456A1 WO 2012157456 A1 WO2012157456 A1 WO 2012157456A1 JP 2012061649 W JP2012061649 W JP 2012061649W WO 2012157456 A1 WO2012157456 A1 WO 2012157456A1
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cyanoacrylic acid
pyrolysis
temperature
raw material
pyrolysis reactor
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PCT/JP2012/061649
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English (en)
Japanese (ja)
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田中　稔
裕史 安藤
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東亞合成株式会社
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Publication of WO2012157456A1 publication Critical patent/WO2012157456A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to a method for producing 2-cyanoacrylic acid.
  • the cyanoacrylate adhesive mainly composed of 2-cyanoacrylate has the property that 2-cyanoacrylate is easily anionically polymerized and rapidly cured in the presence of a small amount of water or a basic substance. Therefore, it is widely used as an instant adhesive in various industries, medical fields, leisure fields, and even general households.
  • the conventional cyanoacrylate adhesives are excellent in tensile adhesive strength at room temperature, but the peel adhesive strength and impact adhesive strength are not always sufficient, and more advanced performance in terms of heat resistance and water resistance. There is a need for further improvements.
  • a conventional cyanoacrylate-based adhesive uses a polymer obtained by anionic polymerization of 2-cyanoacrylate ester for adhesion, and the polymer obtained by anionic polymerization has a linear shape without a cross-linked structure. Since it is a polymer, it is presumed that the above-mentioned characteristics are caused by it.
  • 2-cyanoacrylic acid can be used in the production of these 2-cyanoacrylic acid esters or higher alkyl esters of 2-cyanoacrylic acid
  • 2-cyanoacrylic acid and alcohol can be used in the same manner as in the production of ordinary acrylic acid esters.
  • Various 2-cyanoacrylic acid esters can be easily obtained by producing 2-cyanoacrylic acid chloride from 2-cyanoacrylic acid and reacting it with an alcohol.
  • Patent Document 3 describes a production method other than the thermal decomposition reaction, but there is a problem in productivity due to a long transesterification time.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing 2-cyanoacrylic acid, which can obtain 2-cyanoacrylic acid in a high yield.
  • a method for producing 2-cyanoacrylic acid capable of obtaining 2-cyanoacrylic acid in high yield could be provided.
  • the method for producing 2-cyanoacrylic acid according to the present invention comprises a gasification step of gasifying 2-cyanoacrylate in a raw material tank, and introducing the gas of 2-cyanoacrylate into a thermal decomposition reactor.
  • a pyrolysis step for decomposing and a recovery step for recovering 2-cyanoacrylic acid produced in the pyrolysis step wherein the gas introduction rate in the pyrolysis step is 0 per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor. 0.1 g / min or more and 80 g / min or less, and the pyrolysis temperature in the pyrolysis step is 550 to 850 ° C.
  • the 2-cyanoacrylic acid obtained by the production method of the present invention is a 2-cyanoacrylic acid ester, particularly a polyfunctional 2-cyanoacrylic acid ester or a 2-cyanoacrylic acid higher alkyl ester, which is the main component of the cyanoacrylate adhesive. It is useful as a production raw material.
  • X to Y representing a numerical range means “X or more and Y or less” unless otherwise specified. That is, it means a numerical range including X and Y as end points.
  • the gasification step is a step of gasifying 2-cyanoacrylate in a raw material tank.
  • the 2-cyanoacrylic acid ester used in the gasification step is a compound represented by the following formula (1).
  • R is a saturated or unsaturated, straight chain hydrocarbon group, branched chain hydrocarbon group, or cyclic hydrocarbon having 1 to 20 carbon atoms which may have a halogen atom. Group or an aromatic hydrocarbon group.
  • 2-cyanoacrylic acid ester examples include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n-pentyl, n- Hexyl, amyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 2-pentenyl, n-hexyl, 6-chlorohexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, 2-hexenyl, 4-methyl-pentenyl , 3-methyl-2-cyclohexenyl, norbornyl, heptyl, cyclohexanemethyl, cycloheptyl, 1-methyl-cyclohexyl, 2-methyl-cyclohexyl, 3-methyl-cyclohexyl, 2-ethylhexyl, n-octyl,
  • 2-cyanoacrylic acid alkyl ester is preferable from the viewpoint of raw material cost, and 2-cyanoacrylic acid lower alkyl ester (having 1 to 6, preferably 2 to 6, more preferably 2 to 4 carbon atoms). More preferably, it has 2 or 3 carbon atoms, more preferably ethyl 2-cyanoacrylate.
  • a polymerization inhibitor is preferably added to the 2-cyanoacrylic acid ester.
  • a polymerization inhibitor an anionic polymerization inhibitor generally used for a cyanoacrylate adhesive or a radical polymerization inhibitor can be used.
  • the anionic polymerization inhibitor include sulfur dioxide, acidic gas such as boron trifluoride, sulfonic acid compound such as methanesulfonic acid, hydroxypropanesulfonic acid, p-toluenesulfonic acid, boron trifluoride ethyl ether.
  • radical polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, pyrogallol, di-t-butylphenol, and t-butylpyrocatechol.
  • the addition amount of the polymerization inhibitor is not particularly limited, but is preferably 100 to 3,000 ppm, more preferably 200 to 2,500 ppm, and more preferably 300 to 2,000 ppm with respect to 2-cyanoacrylate. More preferably it is. The addition amount within the above range is preferable because the polymerization of 2-cyanoacrylate is sufficiently suppressed and economical.
  • the 2-cyanoacrylate ester and, if necessary, a polymerization inhibitor are placed in a raw material tank and heated under reduced pressure to gasify the 2-cyanoacrylate ester.
  • the degree of vacuum is preferably 10 to 1,000 Pa, more preferably 50 to 850 Pa, and still more preferably 100 to 700 Pa.
  • the temperature of the raw material tank is preferably 40 to 80 ° C., more preferably 45 to 75 ° C., and further preferably 50 to 70 ° C. If the degree of vacuum and the temperature of the raw material tank are within the above ranges, polymerization of the raw material 2-cyanoacrylate can be suppressed, and gasification of the 2-cyanoacrylate can be performed efficiently. Further, by changing the degree of vacuum and the temperature of the raw material tank, the gas speed of 2-cyanoacrylate gas introduced into the thermal decomposition reactor can be adjusted.
  • the thermal decomposition step is a step of introducing the 2-cyanoacrylic acid ester gas obtained in the above gasification step into a thermal decomposition reactor to obtain the desired 2-cyanoacrylic acid by thermal decomposition.
  • the pyrolysis reactor used in the pyrolysis step is not particularly limited as long as it is a reactor that can withstand a reaction at a high temperature, but is preferably a reaction tube made of quartz, metal, or ceramics. Moreover, when enlarging a thermal decomposition reactor, it is preferable that it is a metal or ceramics reaction tube, and it is more preferable that it is stainless steel.
  • the reason is that it is difficult to increase the size of the pyrolysis reactor made of quartz, and it is difficult to control the internal temperature because the thermal conductivity is low and the heat capacity is large compared to stainless steel. If the internal temperature control is insufficient, excessive decomposition and poor decomposition tend to occur, and the selectivity tends to be low. Furthermore, the pyrolysis reactor made of quartz has a large amount of incinerated 2-cyanoacrylate ester (ash content), and there is a concern that heat transfer may deteriorate due to a long-time reaction. On the other hand, the thermal decomposition reactor made of stainless steel is easy to increase in size and has a high thermal conductivity and a small heat capacity, so that the internal temperature can be easily controlled.
  • the incinerated 2-cyanoacrylic acid ester hardly adheres, and even if it is reacted for a long time, the heat transfer is hardly lowered.
  • the protrusion may be a convex shape, a cross shape, or the like, but a reactor with many protrusions such as a Vigreux column is difficult to increase in size and ash remains easily.
  • the value obtained by dividing the amount of crude 2-cyanoacrylic acid produced by the pyrolysis reaction by the amount of 2-cyanoacrylic acid ester introduced into the pyrolysis reactor is called the conversion rate.
  • the value obtained by dividing the amount of purified 2-cyanoacrylic acid by the amount of crude 2-cyanoacrylic acid before recrystallization is called selectivity.
  • the value obtained by multiplying the conversion rate and the selectivity is defined as the yield. Details of the calculation method will be described later.
  • the gas introduction rate of 2-cyanoacrylate needs to be 80 g / min or less per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor. Moreover, it is preferable that it is 0.1 g / or more.
  • the gas introduction rate is more preferably 3 to 65 g / min, and further preferably 5 to 50 g / min.
  • the introduction speed can be adjusted by the degree of vacuum and the temperature of the raw material tank.
  • a minimum is not specifically limited, From a viewpoint of productivity, it is preferable that it is 0.1 g / or more.
  • the temperature of the pyrolysis reactor needs to be 550 to 850 ° C., preferably 600 to 800 ° C., and more preferably 650 to 800 ° C. If the temperature is less than 550 ° C., the thermal decomposition reaction does not proceed sufficiently. On the other hand, when the temperature exceeds 850 ° C., excessive decomposition tends to occur, and the yield of 2-cyanoacrylic acid is lowered.
  • Pyrolysis reactors are SUS304 [Ni (8 to 10.5%), Cr (18 to 20%)], SUS316 [Ni (10 to 14%), Cr (16 to 18%), Mo (2 to 3%) )], Martensite such as SUS403 [Cr (11.5 to 13%)], SUS405 [Cr (11.5 to 14.5%), Al (0.1 to 0.3) %)], SUS630 [Ni (3-5%), Cr (15-17.5%), Cu (3-5%), Nb (0.15-0.45%)] Both precipitation hardening systems such as those described above, as well as Hastelloy (registered trademark of Haynes International Inc.) and Inconel (registered trademark of Special Matels Corporation) with Mo added to impart heat resistance can be used.
  • those containing Ni are preferable.
  • SUS304 and SUS316 which are relatively inexpensive and easy to process, are preferable, and when Ni removal occurs due to use at a high temperature for a long time, deterioration can be easily determined from the outside by magnetic measurement.
  • the recovery process is a process of recovering 2-cyanoacrylic acid produced in the above thermal decomposition process.
  • the temperature of the 2-cyanoacrylic acid receiver is preferably equal to or higher than the temperature of the raw material tank.
  • the difference between the temperature of the receiver and the temperature of the raw material tank in the recovery process is preferably ⁇ (receiver temperature) ⁇ (temperature of the raw material tank) ⁇ is 0 ° C. or higher, and is 0 to 90 ° C. Is more preferable, 0 to 50 ° C.
  • the crude 2-cyanoacrylic acid obtained in the above recovery step can be converted to purified 2-cyanoacrylic acid by recrystallization according to a conventional method. Specifically, the crude 2-cyanoacrylic acid is dissolved in toluene or the like and then filtered to remove the polymer of 2-cyanoacrylic acid, which is a byproduct of thermal decomposition. Thereafter, the filtrate is cooled to precipitate 2-cyanoacrylic acid crystals, which are washed with toluene or the like to obtain purified 2-cyanoacrylic acid.
  • FIG. 1 schematically shows an example of a manufacturing apparatus suitably used in the present invention.
  • the 2-cyanoacrylic acid production apparatus 100 shown in FIG. 1 includes at least a raw material tank 1, a pyrolysis reactor 5, and a receiver 8.
  • the raw material tank 1 is heated to a desired temperature by the raw material tank heater 2.
  • the receiver 8 is heated to a desired temperature by the receiver heater 9.
  • the pyrolysis reactor 5 is heated to a desired temperature by a pyrolysis furnace (electric heater) 6.
  • the raw material tank 1 and the pyrolysis reactor 5 are connected by a raw material tank-pyrolysis reactor connecting pipe 3.
  • the pyrolysis reactor 5 and the receiver 8 are connected to the pyrolysis reactor-receiver connecting pipe 7.
  • the pyrolysis reactor 5 is provided with a thermometer 4 for measuring the internal temperature, and the temperature in the pyrolysis reactor 5 can be measured.
  • a trap 1 10 is connected to the receiver 8, and a trap 2 11 is further connected.
  • the trap 1 10 and the trap 2 11 are cooled to a desired temperature.
  • the temperature of the trap 1 10 is set to ⁇ 30 ° C.
  • the trap 2 11 is cooled with liquid nitrogen.
  • a vacuum pump 12 is connected to the trap 211, and by operating the vacuum pump 12, the whole of the raw material tank 1 to the trap 211 is decompressed.
  • the raw material tank 1 is charged with 2-cyanoacrylic acid ester as a raw material. At this time, it is preferable to add a polymerization inhibitor to the raw material tank 1 simultaneously.
  • the pyrolysis furnace 6 is heated to a desired temperature, and the raw material tank heater 2 and the receiver heater 9 are heated to a desired temperature.
  • the 2-cyanoacrylic acid ester (compound represented by the above formula (1)) introduced into the thermal decomposition reactor 5 is thermally decomposed into 2-cyanoacrylic acid and alkene. Crude 2-cyanoacrylic acid is recovered in the receiver 8. Since 2-cyanoacrylic acid has a boiling point higher than that of 2-cyanoacrylic acid ester, 2-cyanoacrylic acid can be deposited even when the temperature of the receiver 8 is higher than the temperature of the raw material tank 1. On the other hand, the by-produced alkene and the raw material 2-cyanoacrylate are cooled in trap 1 10 and trap 2 11, and 2-cyanoacrylate is recovered in trap 1 10 and the alkene is recovered in trap 2 11. .
  • Example 1 A raw material tank 1 shown in FIG. 1 was charged with 1,000 g of ethyl 2-cyanoacrylate and 1,000 ppm of p-toluenesulfonic acid as a polymerization inhibitor.
  • a 300 mm long pyrolysis furnace (electric heater) 6 is loaded with a SUS316 pyrolysis reactor 5 (inner surface area 0.0202 m 2 ) having an inner diameter of 21.4 mm and heated to an internal temperature of 700 ° C. did.
  • the temperature of the raw material tank 1 and the receiver 8 is set to 55 ° C.
  • the vacuum pump 12 is started so that the internal pressure becomes 400 to 467 Pa. The degree of vacuum was adjusted. After a while, light yellow crude 2-cyanoacrylic acid was deposited on the inner wall of the receiver 8. After 5 hours of production, heating of the vacuum pump 12 and the pyrolysis reactor 5 was stopped, and the crude 2-cyanoacrylic acid produced in the receiver 8 was recovered.
  • the rate of the gas led to the pyrolysis reactor 5 is 0.955 g / min. Asked.
  • the gas introduction rate per 1 m 2 of the inner surface area was 47.3 g / min.
  • the yield of crude 2-cyanoacrylic acid was 113.8 g.
  • the pyrolysis reactor 5 was increased in weight by 0.13 g due to adhesion of polymer or ash. Using the amount of ethyl 2-cyanoacrylate introduced and the amount of crude 2-cyanoacrylic acid produced, the conversion rate was determined as follows.
  • Example 2 The inner diameter of the pyrolysis reactor was 38.9 mm (inner surface area 0.0366 m 2 ), the temperature of the raw material tank 1 and the receiver 8 was 60 ° C., the inner pressure was 533 to 600 Pa, and the temperature of the pyrolysis reactor 5 was 800 ° C.
  • the other operations were the same as in Example 1.
  • the velocity of the gas led to the pyrolysis reactor was 0.814 g / min, and 22.2 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of manufacture was 109.7 g and the pyrolysis reactor was increased by 1.24 g.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 78.6 g. Conversion: 44.9%, selectivity: 71.7%, yield: 32.2%.
  • Example 3 The same SUS316 pyrolysis reactor 5 having an inner diameter of 38.9 mm as in Example 2 was used, in which a SUS316 partition having a thickness of 2 mm was put in a cross (inner surface area 0.0833 m 2 ), and the internal pressure was 333 to 400 Pa. The same operation as in Example 1 was carried out except that.
  • the velocity of the gas introduced into the pyrolysis reactor was 0.804 g / min, and 9.65 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of manufacture was 123.9 g and the pyrolysis reactor was increased by 0.09 g.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 95.4 g. Conversion: 51.4%, selectivity: 77.0% Yield: 39.6%.
  • Example 4 The same operation as in Example 3 was performed except that the internal pressure was 267 to 333 Pa, and the production time was 20 hours.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 1.06 g / min, and 12.7 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced after 20 hours of production was 644.8 g, and pyrolysis reactor 5 was increased by 0.29 g.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 440.5 g. Conversion: 50.7%, selectivity: 68.3%, yield: 34.6%.
  • Example 5 The pyrolysis reactor 5 of Example 1 was changed to a Vigreux column having an inner surface area of 0.0427 m 2 by providing protrusions inside a quartz reaction tube having an inner diameter of 33.6 mm. The same operation as in Example 1 was performed except that the raw material ethyl 2-cyanoacrylate was 1,000 g, the temperature of the raw material tank 1 and the receiver 8 was 60 ° C., and the internal pressure was 200 to 267 Pa. The velocity of the gas introduced into the pyrolysis reactor 5 was 0.980 g / min, and 23.0 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of manufacture was 134.9 g, and pyrolysis reactor 5 was increased by 1.35 g.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 99.0 g. Conversion: 45.9%, selectivity: 73.4%, yield: 33.7%.
  • Example 6 The pyrolysis reactor 5 of Example 1 was changed to a mullite reaction tube having an inner diameter of 20.0 mm (inner surface area 0.0188 m 2 ), and the same operation as in Example 1 was performed except that the internal pressure was 533 to 600 Pa.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 0.516 g / min, and 27.4 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of manufacture was 55.0 g, and pyrolysis reactor 5 was increased by 0.23 g.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 30.3 g. Conversion: 35.5%, selectivity: 55.0%, yield: 19.5%.
  • Example 7 The same operation as in Example 1 was performed, except that the temperature of the raw material tank 1 of Example 1 was 55 ° C., the temperature of the receiver 6 was 45 ° C., and the internal pressure was 267 to 333 Pa.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 0.94 g / min, and 46.5 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of manufacture was 164.0 g, and pyrolysis reactor 5 was increased by 0.13 g.
  • the crude 2-cyanoacrylic acid was generally wet.
  • the amount of purified 2-cyanoacrylic acid obtained by recrystallization was 47.7 g. Conversion: 58.2%, selectivity: 29.1%, yield: 16.9%.
  • Comparative Example 1 The same operation as in Example 1 was performed except that the thermal decomposition temperature was 500 ° C.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 0.139 g / min, and 3.3 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the reaction was carried out for 5 hours, but no crude 2-cyanoacrylic acid was produced (conversion rate: 0%).
  • Comparative Example 2 The same operation as in Example 1 was performed except that the temperature of the raw material tank 1 and the receiver 8 was 60 ° C., the internal pressure was 200 to 267 Pa, and the temperature of the pyrolysis reactor 5 was 550 ° C.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 1.81 g / min, and 89.6 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor.
  • the amount of crude 2-cyanoacrylic acid produced after 5 hours of production was 1.6 g (conversion: 0.29%).
  • Comparative Example 3 1,000 g of p-toluenesulfonic acid was mixed with 1,000 g of ethyl 2-cyanoacrylate and put in the dropping funnel 22 shown in FIG. The introduction of the raw material was adjusted by slightly opening the lower cock 23 of the dropping funnel 22. In addition, argon was introduced as a carrier gas 21 for the transfer of 2-cyanoacrylic acid gas generated by thermal decomposition.
  • the pyrolysis reactor 24 was made of the same quartz as in Example 5, and was heated by the pyrolysis furnace 25 so that the internal temperature became 700 ° C. The inside of the reaction apparatus was depressurized by the vacuum pump 28.
  • 2-Cyanoacrylic acid generated by thermal decomposition was collected in a receiver 26, and raw materials and by-products were collected in a trap 27 cooled with liquid nitrogen. After the production for 8 hours, heating of the vacuum pump 28 and the pyrolysis reactor 24 was stopped, and the crude 2-cyanoacrylic acid produced in the receiver 26 was recovered.
  • the introduction rate of ethyl 2-cyanoacrylate introduced into the thermal decomposition reactor 24 was determined to be 0.09 g / min by subtracting the weight of the dropping funnel 22 whose tare was measured in advance from the weight after the test. Therefore, the introduction rate per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 24 was 2.1 g / min.
  • Comparative Example 4 The same operation as in Example 1 was performed except that the thermal decomposition temperature was 870 ° C.
  • the velocity of the gas introduced into the pyrolysis reactor 5 was 0.454 g / min, and 12.4 g / min per 1 m 2 of the surface area of the inner surface of the pyrolysis reactor 5.
  • the amount of crude 2-cyanoacrylic acid produced was 14.8 g, and the brown coloration was very strong.
  • the weight of the pyrolysis reactor 5 was increased by 0.24 g.
  • the obtained crude product was recrystallized in the same manner as in Example 1. However, purified 2-cyanoacrylic acid was not obtained. That is, the product obtained in the pyrolysis step is judged to be a polymer of 2-cyanoacrylic acid and 2-cyanoacrylate. Conversion: 10.8%, selectivity: 0.0%, yield: 0.0%.
  • Examples 1 to 5 the production methods of 2-cyanoacrylic acid shown in Examples 1 to 5 can obtain the target product in a relatively high yield and are excellent in productivity. Moreover, when the pyrolysis reactor is a reaction tube made of metal or ceramics, it can be seen that there are few incinerated residues and it is suitable for industrialization. Although the yield of Example 6 using the mullite pyrolysis reactor was low, the internal surface area was small, and it is possible to increase the yield by increasing the internal surface area. In Example 7, since the temperature of the 2-cyanoacrylic acid receiver is lower than the temperature of the raw material tank, undecomposed ethyl 2-cyanoacrylate is condensed in the receiver.
  • the present invention is a method that can efficiently produce 2-cyanoacrylic acid and is also suitable for industrialization.
  • the obtained 2-cyanoacrylic acid is particularly useful as a raw material for producing polyfunctional 2-cyanoacrylic acid esters or higher alkyl esters of 2-cyanoacrylic acid.

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Abstract

L'invention porte sur un procédé de fabrication d'acide 2-cyanoacrylique qui permet d'obtenir de l'acide 2-cyanoacrylique avec un rendement élevé. Le procédé de fabrication d'acide 2-cyanoacrylique est caractérisé en ce qu'il comporte les étapes suivantes : la gazéification d'un ester de type 2-cyanoacrylate dans une cuve de matière première ; la pyrolyse comprenant l'introduction de l'ester de type 2-cyanoacrylate gazeux dans un réacteur de pyrolyse et l'exécution d'une pyrolyse ; la récupération de l'acide 2-cyanoacrylique produit dans l'étape de pyrolyse, les étapes étant effectuées dans l'ordre indiqué. Le débit d'introduction de gaz dans l'étape de pyrolyse est supérieur ou égal à 0,1 g/min et inférieur ou égal à 80 g/min par mètre carré de la surface interne du réacteur de pyrolyse, et la température de pyrolyse de l'étape de pyrolyse est de 550 à 850°C.
PCT/JP2012/061649 2011-05-19 2012-05-07 Procédé de fabrication d'acide 2-cyanoacrylique WO2012157456A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3415181A1 (de) * 1984-04-21 1985-10-31 Henkel KGaA, 4000 Düsseldorf (alpha)-cyanacrylsaeure
WO1995023131A1 (fr) * 1994-02-23 1995-08-31 Saldane Limited Procede de preparation d'acide 2-cyanoacrylique
WO1996014292A1 (fr) * 1994-11-04 1996-05-17 Saldane Limited Procede de purification d'un ester non enolisable a l'aide d'un reactif metallique choisi parmi un metal, un oxyde metallique et un hydrure metallique
JPH08325219A (ja) * 1995-03-27 1996-12-10 Toagosei Co Ltd ２−シアノアクリル酸の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3415181A1 (de) * 1984-04-21 1985-10-31 Henkel KGaA, 4000 Düsseldorf (alpha)-cyanacrylsaeure
WO1995023131A1 (fr) * 1994-02-23 1995-08-31 Saldane Limited Procede de preparation d'acide 2-cyanoacrylique
WO1996014292A1 (fr) * 1994-11-04 1996-05-17 Saldane Limited Procede de purification d'un ester non enolisable a l'aide d'un reactif metallique choisi parmi un metal, un oxyde metallique et un hydrure metallique
JPH08325219A (ja) * 1995-03-27 1996-12-10 Toagosei Co Ltd ２−シアノアクリル酸の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W.P.RATCHFORD ET AL.: "Preparation of Acrylic and Methacrylic Acid by Pyrolysis of Their Alkyl Esters", JOURNAL OF AMERICAN CHEMICAL SOCIETY, vol. 66, 1944, pages 1864 - 1866 *

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