WO2017135184A1 - Procédé de production de 2-cyanoacrylate - Google Patents

Procédé de production de 2-cyanoacrylate Download PDF

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Publication number
WO2017135184A1
WO2017135184A1 PCT/JP2017/003111 JP2017003111W WO2017135184A1 WO 2017135184 A1 WO2017135184 A1 WO 2017135184A1 JP 2017003111 W JP2017003111 W JP 2017003111W WO 2017135184 A1 WO2017135184 A1 WO 2017135184A1
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WO
WIPO (PCT)
Prior art keywords
cyanoacrylate
producing
depolymerization
polycondensate
acid
Prior art date
Application number
PCT/JP2017/003111
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English (en)
Japanese (ja)
Inventor
加奈子 柴田
安藤　勝
誠 今堀
Original Assignee
東亞合成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東亞合成株式会社 filed Critical 東亞合成株式会社
Priority to JP2017565528A priority Critical patent/JP6729604B2/ja
Publication of WO2017135184A1 publication Critical patent/WO2017135184A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/23—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same unsaturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for producing 2-cyanoacrylate which is widely used as a main component of instant adhesives.
  • 2-Cyanoacrylate starts polymerization quickly with a small amount of moisture present near the surface of the adherend, and adheres almost all of the adherend made of various materials in a very short time of several seconds to several minutes, and Due to its strong adhesive force, it is used as the main component of instant adhesives in a wide range of fields such as electricity, electronics, mechanical parts, precision machinery, household goods and medicine.
  • cyanoacetic acid ester and paraformaldehyde are condensed in an organic solvent in the presence of a basic catalyst such as piperidine, and in the second step, the 2-cyanoacrylate polycondensate obtained in the first step is converted into five.
  • depolymerization is performed under high temperature and reduced pressure conditions, and the crude 2-cyanoacrylate monomer obtained by depolymerization in the third step is distilled to obtain a purified 2-cyanoacrylate monomer. That's it.
  • a polymerization inhibitor such as diphosphorus oxide
  • the problem to be solved by the present invention is to provide a method capable of maintaining the purity and yield of 2-cyanoacrylate monomer at a high level by performing depolymerization at low temperature in a short time in the production of 2-cyanoacrylate monomer.
  • the present inventors diligently studied the depolymerization reaction in the production of 2-cyanoacrylate polycondensate.
  • the depolymerization reaction was performed at room temperature for several minutes. I found it going.
  • the amount of 2-cyanoacrylate monomer produced increases dramatically by adding acid to neutralize the basic substance.
  • the monomer can be stably obtained by removing the salt generated in the neutralization step by a method such as filtration, and the present invention has been completed.
  • the present invention includes a step of adding a basic substance to a polycondensate solution of a cyanoacetate and formaldehyde, and depolymerizing the polycondensate. And a step of neutralizing by adding an acid to the depolymerization reaction solution obtained in the depolymerization step, and a step of removing the salt generated in the neutralization step. It is a manufacturing method of an acrylate.
  • R is a saturated or unsaturated linear hydrocarbon group, branched hydrocarbon group or alicyclic hydrocarbon having 1 to 20 carbon atoms which may have a halogen atom.
  • A is independent Is an alkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group
  • m and n are each 1 or more
  • m + n is 2 to 20 and m is preferably 2 to 4 and n is preferably 1 to 3
  • the group includes an ether bond, and the alkylene group and the hydrocarbon group of Any or all of them are halogen atoms It may have.
  • 2-cyanoacrylate represented by the chemical formula (1) examples include methyl, ethyl, chloroethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, 2-cyanoacrylate, tert-butyl, n-pentyl, 1-methyl-butyl, 1-ethyl-propyl, neopentyl, n-hexyl, 1-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl N-dodecyl, cyclohexyl, benzyl, phenyl, tetrahydrofurfuryl, allyl, propargyl, 2-butenyl, phenethyl, chloropropyl, ethoxyethyl, ethoxypropyl, ethoxy
  • the cyanoacrylate unit of the polycondensate in the present invention is calculated based on the formula (1) on the assumption that a cyanoacrylate ester and a 2,4-dicyanoglutarate diester are generated by a depolymerization reaction.
  • the basic substance in the present invention can be used without particular limitation as long as it is a conventionally known compound showing basicity.
  • a basic substance having a pKb of 6 or less is preferable. More preferably, it is 3 or less. More preferably, it is in the range of 0-3.
  • pKb 14 ⁇ pKa (2)
  • pKa is an acid dissociation constant, and a value described in a known document, for example, “Maruzen Kagaku Handbook”, Basic Edition II (section 10) can be used.
  • the pKb value of a basic substance not described in known literature can be determined by a method using, for example, an acid-base neutralization reaction.
  • the basic substance can be titrated with an appropriate acid standard solution, for example, hydrochloric acid or an aqueous oxalic acid solution, and the titration curve can be analyzed for determination.
  • pKa and pKb are values measured in an aqueous solution at normal pressure (1 atm) and 25 ° C.
  • pKb in the present invention is also a value measured in the same manner.
  • Examples of basic substances include amines, phosphines, thiolates, alkoxides, quaternary ammonium salts, and alkali metal and / or alkaline earth metal oxides, hydroxides, carbonates, phosphates, and silicates. It is preferable to use one or more types. From the viewpoints of solubility in a solvent and salt precipitation during neutralization, amine is more preferable.
  • amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetetramine, aniline, N, N-diisopropylethylamine, tetramethylethylenediamine, 4 -Aminopyridine, N, N-dimethyl-4-aminopyridine, imidazole, 1,4-diazadibicyclo [2,2,2] octane, cyclohexylamine, 2,6-dimethylpyridine, 1,4,7,10-tetra Azacyclododecane, 2,4,6-tris (dimethylaminomethyl) phenol (hereinafter referred to as “DMP-30”), tris (hydroxymethyl) methylamine, 2,4,6-trimethylpi Gin, piperazine, piperidine, pyridine, pyrrolidine, 1,2-propanediamine
  • phosphine examples include methylphosphine, ethylphosphine, dimethylphosphine, diethylphosphine, trimethylphosphine, triethylphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine and the like.
  • thiolate include conjugated bases such as methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, and thiophenol.
  • alkoxide examples include methoxide, ethoxide, 1-propoxide, 2-propoxide, 1-butoxide, 2-methyl-1-propoxide, 2-butoxide, 2-methyl-2-propoxide and the like.
  • quaternary ammonium salts include benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimonium chloride, cetrimonium bromide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxy , Tetrabutylammonium hydroxide, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domifene bromide and the like.
  • oxides, hydroxides, carbonates, phosphates, and silicates of alkali metals and / or alkaline earth metals include sodium oxide, potassium oxide, calcium oxide, sodium hydroxide, potassium hydroxide, Examples include calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, sodium silicate, potassium silicate, and the like.
  • a preferable addition amount of the basic substance is an amount such that the basic group is 0.001 to 5-fold molar equivalent to the cyanoacrylate unit of the 2-cyanoacrylate polycondensate, and more preferably 0.1 to The amount is 3 times the molar equivalent, and more preferably 1 to 2 times the molar equivalent. If it is less than 0.001 molar equivalent, depolymerization may not proceed easily. Depolymerization proceeds at a molar equivalent of 0.001 or more, but when it exceeds 5 molar equivalents, a salt of 5 or higher molar equivalents of the 2-cyanoacrylate monomer to be produced is formed, and the polymerization of the 2-cyanoacrylate monomer is carried out. In order to promote, the monomer yield may decrease.
  • the solvent to be used is preferably an organic solvent having an ether, ketone and / or ester structure, that is, ethers, ketones and / or esters.
  • an organic solvent having high polarity such as tetrahydrofuran (hereinafter referred to as “THF”) or acetone is more preferable because of its high depolymerization rate.
  • THF tetrahydrofuran
  • toluene, xylene, benzene, trichloroethylene, cyclohexane, ethyl acetate, methanol, ethanol, isopropanol, tricresyl phosphate, dioctyl phthalate, diphenylphenyl phosphate, etc. used in the condensation step of 2-cyanoacrylate are one of the organic solvents. It can also be used as a whole or as a whole.
  • the weight average molecular weight (Mw) of the polycondensate of 2-cyanoacrylate is preferably 1,000 to 10,000, and more preferably in the range of 1,500 to 5,000.
  • Mw weight average molecular weight
  • the weight average molecular weight exceeds 10,000, the viscosity of the polycondensate increases, and the efficiency of the depolymerization reaction may deteriorate.
  • the weight average molecular weight is less than 1,000, 2,4-dicyanoglutaric acid diester and the like remaining after depolymerization increase, and the monomer yield may decrease.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) in the present invention are values measured by gel permeation chromatography (hereinafter abbreviated as “GPC”).
  • GPC gel permeation chromatography
  • the temperature in the depolymerization step is preferably 0 to 130 ° C. If it is less than 0 degreeC, a depolymerization speed
  • the acid is not particularly limited as long as it reacts with a basic substance.
  • a substance that shows acidity when dissolved in water or alcohol does not dissolve in water or alcohol, but reacts with a Bronsted base or Lewis base.
  • Specific acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, polyphosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (hereinafter referred to as “PTS”), 10-camphor-sulfonic acid.
  • PTS p-toluenesulfonic acid
  • 10-camphor-sulfonic acid Such as sulfonic acid, acid chloride, acetic acid, and carbonic acid such as inorganic acid, sulfonic acid, and acid chloride.
  • monovalent acids that do not contain moisture are preferable, sulfonic acids are particularly preferable from the viewpoint of salt precipitation and handling, and methanesulfonic acid
  • the neutralization step is not particularly limited and may be a continuous type or a batch type. Since the temperature of the system rises due to the heat of neutralization reaction, it is preferable to carry out the reaction while cooling.
  • the method for removing the produced salt is not particularly limited, such as filtration, centrifugation, decantation and the like, and may be a continuous type or a batch type.
  • the 2-cyanoacrylate in the depolymerized composition is purified by distillation, preferably by heating under reduced pressure of 0.01 to 1.33 kPa.
  • an anionic polymerization inhibitor such as diphosphorus pentoxide, SO 2 , PTS, BF 3 , propane sultone, methanesulfonic acid, etc.
  • radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and pyrogallol.
  • Example 2 Depolymerization was carried out in the same manner as in Example 1 except that the acid added to the depolymerization solution was methanesulfonic acid.
  • Example 5 The amount of piperidine added to the polycondensate solution was the same as in Example 2 except that 0.1, 2, and 5 times the molar equivalent of the monomer calculated from the number average molecular weight of the polycondensate was added. The depolymerization was performed.
  • Example 6 Depolymerization was carried out in the same manner as in Example 2 except that the basic substances shown in Table 1 were used.
  • Example 10 Depolymerization was performed in the same manner as in Example 2 except that the organic solvent for dissolving the polycondensate was changed to ethyl acetate, acetone, and toluene.
  • Example 16 and 17 The amount of piperidine added to the polycondensate solution is the same as that of Example 2 except that 0.001 times and 0.01 times the molar equivalent of the cyanoacrylate unit calculated from the formula (1) are added. In this manner, depolymerization was performed.
  • Example 18 to 20 Depolymerization was performed in the same manner as in Examples 2 to 4 except that no acid was added.
  • Example 21 Depolymerization was performed in the same manner as in Example 2 except that the precipitated salt was not removed with a glass filter.
  • Comparative Example 4 Depolymerization was performed in the same manner as in Comparative Example 3 except that the depolymerization time was 360 minutes.
  • the monomer concentration in Table 1 is based on proton nuclear magnetic resonance spectroscopy (hereinafter referred to as “1H-NMR”) measurement of the depolymerization composition.
  • the integral ratio between the proton bonded to the C double bond and the proton of the ester group was determined, and the ratio of each cyanoacrylate monomer was calculated based on the following formula (3).
  • the ester group in the mathematical formula (3) is the total number of the ethyl ester group, methyl ester group, isobutyl ester group or ethoxyethyl ester group contained in the polycondensate, its decomposition product and the monomer.
  • Yield of fine monomer amount of fine monomer [g] / 2-cyanoacrylate polycondensate amount [g] x 100 (%) (4)
  • Example 23 Except for using the depolymerized composition obtained in Example 2, 59.2 g of a fine monomer was obtained in the same manner as in Example 22.
  • Example 24 Except for using the depolymerized composition obtained in Example 13, 61.7 g of a fine monomer was obtained in the same manner as in Example 22.
  • the present invention makes it possible to produce a high purity 2-cyanoacrylate monomer with few impurity components at a low temperature for a short time, and is an industrially useful method for producing 2-cyanoacrylate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

[Problème] Procédé de dépolymérisation d'un polycondensat de 2-cyanoacrylate à basse température sur une courte durée et de production de 2-cyanoacrylate de haute pureté. [Solution] Procédé de production de 2-cyanoacrylate, ledit procédé étant caractérisé en ce qu'une substance basique est ajoutée à une solution d'un polycondensat d'un ester d'acide cyanoacétique et de formaldéhyde, une dépolymérisation est effectuée, un acide est ajouté à la composition dépolymérisée résultante pour neutralisation, et le sel généré est éliminé.
PCT/JP2017/003111 2016-02-02 2017-01-30 Procédé de production de 2-cyanoacrylate WO2017135184A1 (fr)

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JP2017565528A JP6729604B2 (ja) 2016-02-02 2017-01-30 ２−シアノアクリレートの製造方法

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JP2016-017993 2016-02-02
JP2016017993 2016-02-02

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WO2017135184A1 true WO2017135184A1 (fr) 2017-08-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021025036A1 (fr) 2019-08-08 2021-02-11 東亞合成株式会社 Composé 2-cyanoacrylate et composition adhésive
JPWO2020085334A1 (ja) * 2018-10-23 2021-09-24 東亞合成株式会社 光硬化性接着剤組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58121263A (ja) * 1982-01-11 1983-07-19 Matsumoto Seiyaku Kogyo Kk α−シアノアクリレ−トの製造法
JP2002193907A (ja) * 2000-12-21 2002-07-10 Toagosei Co Ltd ２−シアノアクリレートの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3233007A1 (de) * 1982-09-04 1984-03-08 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von (alpha)-cyanacrylsaeureestern
DE3312427A1 (de) * 1983-04-07 1984-10-11 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von 2-cyanacrylaten aus 2,4-dicyanglutaraten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58121263A (ja) * 1982-01-11 1983-07-19 Matsumoto Seiyaku Kogyo Kk α−シアノアクリレ−トの製造法
JP2002193907A (ja) * 2000-12-21 2002-07-10 Toagosei Co Ltd ２−シアノアクリレートの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ALAN HICKEY ET AL.: "End-Group Identity and Its Effect on the Thermal Degradation of Poly(butyl cyanoacrylate", MACROMOL. RAPID COMMUN., vol. 22, 2001, pages 1158 - 1162, XP001104487, DOI: doi:10.1002/1521-3927(20011001)22:14<1158::AID-MARC1158>3.0.CO;2-B *
BERNARD RYAN ET AL.: "Novel sub-ceiling temperature rapid depolymerization-repolymerization reactions of cyanoacrylate polymers", MACROMOL . R APID COMMUN., vol. 17, 1996, pages 217 - 227, XP055332433 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020085334A1 (ja) * 2018-10-23 2021-09-24 東亞合成株式会社 光硬化性接着剤組成物
WO2021025036A1 (fr) 2019-08-08 2021-02-11 東亞合成株式会社 Composé 2-cyanoacrylate et composition adhésive
KR20220042221A (ko) 2019-08-08 2022-04-04 도아고세이가부시키가이샤 2-시아노아크릴레이트 화합물 및 접착제 조성물

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TWI747877B (zh) 2021-12-01
JP6729604B2 (ja) 2020-07-22
TW201739805A (zh) 2017-11-16
JPWO2017135184A1 (ja) 2018-11-29

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