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

Definitions

• the present disclosure relates to a method for producing ⁇ -cyanoacrylate. More specifically, the present disclosure relates to a method for producing ⁇ -cyanoacrylate, characterized in that ⁇ -cyanoacrylate is obtained by reacting a cyanoacetate with a dialkoxymethane in the presence of a cyclic carboxylic acid anhydride, a specific amine catalyst, and a specific acid catalyst.
• the present disclosure also relates to a method for producing ⁇ -cyanoacrylate, characterized in that ⁇ -cyanoacrylate is obtained by reacting a cyanoacetate with a compound having an oxymethylene skeleton, such as a dialkoxymethane, in the presence of boron oxide, a specific amine catalyst, and a specific acid catalyst.
• a compound having an oxymethylene skeleton such as a dialkoxymethane
• ⁇ -Cyanoacrylate undergoes anionic polymerization in the presence of trace amounts of moisture or basic components on the surface of the substrate, and has the property of hardening in a short time at room temperature. For this reason, ⁇ -cyanoacrylate is used as the main component of cyanoacrylate-based instant adhesives. Cyanoacrylate-based instant adhesives are widely used in various industries, the medical field, and even in home repair and craft applications.
• ⁇ -cyanoacrylates include methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, isopropyl cyanoacrylate, butyl cyanoacrylate, octyl cyanoacrylate, 2-octyl cyanoacrylate, methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and hexanediol biscyanoacrylate.
• ⁇ -cyanoacrylates In many of the industrial production methods of these ⁇ -cyanoacrylates, a corresponding ⁇ -cyanoacetic acid ester is subjected to a Knoevenagel reaction with a substance that generates formaldehyde, such as paraformaldehyde or trioxane, to produce a prepolymer, and then the prepolymer is depolymerized under high temperature and reduced pressure while the ⁇ -cyanoacrylate is distilled and recovered as a monomer (e.g., Patent Document 1).
• a substance that generates formaldehyde such as paraformaldehyde or trioxane
• a known manufacturing method that avoids the above problems is to obtain ⁇ -cyanoacrylate by esterifying cyanoacrylic acid chloride with the corresponding alcohol (Patent Document 6).
• This manufacturing method does not include a step of generating a prepolymer, so there is no need for a depolymerization step at high temperatures, and has the advantage of being able to produce ⁇ -cyanoacrylate with a relatively large molecular weight or ⁇ -cyanoacrylate with reactive functional groups.
• the disadvantage is that cyanoacrylic acid chloride and the by-product hydrogen chloride are highly corrosive and irritating, and corrosion countermeasures for the manufacturing equipment and safety measures for workers are expensive.
• Patent Document 7 As a method for producing ⁇ -cyanoacrylate that improves corrosiveness and irritation and does not produce prepolymers, a method of reacting ⁇ -cyanoacetic acid ester with a compound having electron-withdrawing ester groups at both ends of the methylene and polyoxymethylene groups has been disclosed (Patent Document 7). This production method does not use highly corrosive and irritating chlorine-based compounds, and does not include a process for producing prepolymers. Therefore, there is an advantage in that a depolymerization process at high temperatures is not required, and ⁇ -cyanoacrylates with relatively large molecular weights and ⁇ -cyanoacrylates with reactive functional groups can be produced.
• this production method requires a relatively high reaction temperature to activate the compound having electron-withdrawing ester groups at both ends of the methylene and polyoxymethylene groups described above.
• a high reaction temperature causes polymerization of the produced ⁇ -cyanoacrylate and other side reactions, so there is a problem in that the yield of the desired ⁇ -cyanoacrylate is difficult to increase.
• this manufacturing method requires the preparation of a compound having an electron-withdrawing ester group at both ends of a methylene group and a polyoxymethylene group in advance using a highly reactive acid anhydride as a raw material, making the manufacturing process complicated.
• the unreacted acid anhydride remaining after the reaction and the compound having an electron-withdrawing ester group at both ends of a methylene group and a polyoxymethylene group are highly reactive, so it may be necessary to inactivate and dispose of these unreacted materials, resulting in the problem that the manufacturing and disposal processes take a long time.
• Patent No. 5311272 Japanese Patent Application Publication No. 06-192202 European Patent No. 0127855 European Patent No. 0459617 Special Publication No. 58-053676 Japanese Patent Publication No. 08-505383 Patent No. 6452262
• the objective of one embodiment of the present disclosure which has been made in light of the above-mentioned current situation, is to provide a method for producing ⁇ -cyanoacrylate that does not use chlorine-based compounds, does not include a step of producing a prepolymer or a step of depolymerizing at high temperature, does not require a step of preparing a reaction intermediate in advance, allows for simple purification treatment after completion of the reaction, and is capable of producing ⁇ -cyanoacrylate in good yield.
• the present disclosure includes the following aspects. ⁇ 1>
• the method includes a reaction step of reacting a cyanoacetic acid ester with a dialkoxymethane in the presence of a cyclic carboxylic acid anhydride, a catalyst A, and a catalyst B
• the catalyst A is at least one compound selected from the group consisting of a cyclic diamine, a salt of a cyclic diamine, and a complex containing a cyclic diamine
• the catalyst B is at least one compound selected from the group consisting of a compound B1 group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid, a salt of the compound B1 group, a complex containing the compound B1 group, an ester of the compound B1 group, and an anhydride of the compound B1 group.
• the method includes a reaction step of reacting a cyanoacetic acid ester with a compound represented by the following formula (1) in the presence of boron oxide, catalyst A and catalyst B,
• the catalyst A is at least one compound selected from the group consisting of a cyclic diamine, a salt of a cyclic diamine, and a complex containing a cyclic diamine
• the catalyst B is at least one compound selected from the group consisting of a compound B1 group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid, a salt of the compound B1 group, a complex containing the compound B1 group, an ester of the compound B1 group, and an anhydride of the compound B1 group.
• R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent including a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, or an aryl group, R 1 and R 2 may be bonded to each other to form a ring, and m is 1 to 100.
• the dialkoxymethane is a dialkoxymethane represented by the following formula (1A):
• the cyclic carboxylic acid anhydride is a cyclic carboxylic acid anhydride represented by the following formula (2):
• the catalyst A is at least one compound selected from the group consisting of a cyclic diamine represented by the following formula (3), a salt of the cyclic diamine represented by the following formula (3), and a complex containing the cyclic diamine represented by the following formula (3),
• R 1 and R 2 are each independently a linear or branched alkyl group having 1 to
• R 1 and R 2 may be bonded to each other to form a ring.
• R3 is a linear or branched divalent group having 1 to 10 carbon atoms, and may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 4 and R 6 are each independently a linear or branched divalent group having 1 to 10 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 5 is a hydrogen atom, or a linear or branched monovalent group having 1 to 20 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 4 and R 5 , R 5 and R 6 , R 6 and R 4 , and R 4 , R 5 , and R 6 may each be linked to each other to form a ring.
• n is 0 to 20
• X 1 and X 2 are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 5 to 24 carbon atoms, a carbon atom chemically bonded to silica gel, or a carbon atom in a copolymer skeleton containing at least one structural unit derived from styrene, ethylstyrene, and diviny
• X 1 and X 2 may be bonded to each other to form a ring.
• r is 1 to 20
• X3 and X4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X5 is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom , a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X3 and X4 , X4 and X5 , X5 and X3 , and X3, X4 , and X5 may each be linked to each other to form a ring.
• the dialkoxymethane is at least one selected from the group consisting of methylal, ethylal, dibutoxymethane, 1,3-dioxolane, and 1,3-dioxane.
• ⁇ 5> The method for producing an ⁇ -cyanoacrylate according to ⁇ 1>, ⁇ 3> or ⁇ 4>, wherein the cyclic carboxylic acid anhydride is at least one selected from the group consisting of succinic anhydride, phthalic anhydride, and maleic anhydride.
• the catalyst A is at least one compound selected from the group consisting of a cyclic diamine represented by the following formula (3), a salt of the cyclic diamine represented by the following formula (3), and a complex containing the cyclic diamine represented by the following formula (3),
• the method for producing an ⁇ -cyanoacrylate according to ⁇ 2> wherein the catalyst B is at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound B2 group represented by the following formula (5), a salt of the compound B2 group, a complex of the compound B2 group, an ester of the compound B2 group, and an anhydride of the compound B2 group:
• R 4 and R 6 are each independently a linear or branched divalent group having 1 to 10 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an al
• R 5 is a hydrogen atom, or a linear or branched monovalent group having 1 to 20 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 4 and R 5 , R 5 and R 6 , R 6 and R 4 , and R 4 , R 5 , and R 6 may each be linked to each other to form a ring.
• n is 0 to 20
• X 1 and X 2 are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, a carbon atom chemically bonded to silica gel, or a carbon atom in a copolymer skeleton containing at least one structural unit derived from styrene, ethylstyrene, and divinylbenzene, and may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom,
• X 1 and X 2 may be bonded to each other to form a ring.
• r is 1 to 20
• X3 and X4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X5 is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom , a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X3 and X4 , X4 and X5 , X5 and X3 , and X3, X4 , and X5 may each be linked to each other to form a ring.
• ⁇ 7> The method for producing an ⁇ -cyanoacrylate according to ⁇ 2> or ⁇ 6>, wherein the compound represented by formula (1) is at least one selected from the group consisting of methylal, ethylal, 1,3-dioxolane, 1,3-dioxane, trioxane, and paraformaldehyde.
• ⁇ 8> The method for producing an ⁇ -cyanoacrylate according to any one of ⁇ 1> to ⁇ 7>, wherein the catalyst A is at least one selected from the group consisting of piperazine, homopiperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine.
• the catalyst B is selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to silica gel, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, monoisotridecyl phosphate, monohexadecyl phosphate, monooleyl phosphate, and monooc
• ⁇ 10> The method for producing an ⁇ -cyanoacrylate according to any one of ⁇ 1> to ⁇ 9>, wherein the cyanoacetate ester has one or two cyanoacetyl groups.
• ⁇ 11> ⁇ 1> ⁇ 2> is a method for producing an ⁇ -cyanoacrylate according to any one of ⁇ 1> to ⁇ 10>, wherein the reaction temperature in the reaction step is 55° C. to 105° C.
• the disclosed method for producing ⁇ -cyanoacrylate does not use chlorine-based compounds, does not include a step of producing a prepolymer or a step of depolymerizing at high temperature, does not require a step of preparing a reaction intermediate in advance, and provides a method for producing ⁇ -cyanoacrylate that is easy to purify after the reaction is completed and can produce ⁇ -cyanoacrylate in good yield.
• a numerical range indicated using “to” means a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
• the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure.
• the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
• a combination of two or more preferred aspects is a more preferred aspect.
• the amount of each component means the total amount of multiple substances, unless otherwise specified.
• the method for producing an ⁇ -cyanoacrylate according to the first embodiment of the present disclosure includes a reaction step of reacting a cyanoacetic acid ester with a dialkoxymethane in the presence of a cyclic carboxylic acid anhydride, a catalyst A, and a catalyst B.
• Catalyst A is at least one compound selected from the group consisting of cyclic diamines, salts of cyclic diamines, and complexes containing cyclic diamines.
• the catalyst B is at least one compound selected from the group consisting of the compounds B1 group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid, salts of the compounds B1 group, complexes containing the compounds B1 group, esters of the compounds B1 group, and anhydrides of the compounds B1 group.
• the method for producing ⁇ -cyanoacrylate according to the first embodiment of the present disclosure does not use chlorine-based compounds, and therefore corrosion of the production equipment is suppressed.
• the method for producing ⁇ -cyanoacrylate according to the first embodiment of the present disclosure does not include a step of generating a prepolymer or a step of depolymerization at high temperature, and therefore can produce ⁇ -cyanoacrylate with a relatively large molecular weight or ⁇ -cyanoacrylate with a reactive functional group.
• the method for producing ⁇ -cyanoacrylate according to the present disclosure can produce ⁇ -cyanoacrylate in good yield at a low reaction temperature by reacting cyanoacetic ester with dialkoxymethane in the presence of a cyclic carboxylic acid anhydride, catalyst A, and catalyst B.
• the method for producing ⁇ -cyanoacrylate according to the second embodiment of the present disclosure includes a reaction step in which a cyanoacetic ester is reacted with a compound represented by formula (1) in the presence of boron oxide, catalyst A, and catalyst B.
• Catalyst A is at least one compound selected from the group consisting of cyclic diamines, salts of cyclic diamines, and complexes containing cyclic diamines.
• the catalyst B is at least one compound selected from the group consisting of the compounds B1 group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid, salts of the compounds B1 group, complexes containing the compounds B1 group, esters of the compounds B1 group, and anhydrides of the compounds B1 group.
• R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent including a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, or an aryl group, R 1 and R 2 may be bonded to each other to form a ring, and m is 1 to 100.
• the method for producing ⁇ -cyanoacrylate according to the second embodiment of the present disclosure does not use chlorine-based compounds, and therefore corrosion of the production equipment is suppressed.
• the method for producing ⁇ -cyanoacrylate according to the present disclosure does not include a step of generating a prepolymer or a step of depolymerization at high temperature, and therefore can produce ⁇ -cyanoacrylate with a relatively large molecular weight or ⁇ -cyanoacrylate with a reactive functional group.
• the method for producing ⁇ -cyanoacrylate according to the second embodiment of the present disclosure can produce ⁇ -cyanoacrylate with good yield by reacting a cyanoacetic ester with a compound represented by the following formula (1) in the presence of boron oxide, catalyst A, and catalyst B.
• Cyanoacetates are compounds that have at least one cyanoacetyl group in the molecule.
• Examples of compounds having one cyanoacetyl group include methyl cyanoacetate, ethyl cyanoacetate, propyl cyanoacetate, isopropyl cyanoacetate, amyl cyanoacetate, butyl cyanoacetate, isobutyl cyanoacetate, hexyl cyanoacetate, cyclohexyl cyanoacetate, octyl cyanoacetate, 2-octyl cyanoacetate, 2-ethylhexyl cyanoacetate, allyl cyanoacetate, octadecyl cyanoacetate, methoxyethyl cyanoacetate, ethoxyethyl cyanoacetate, methoxyethoxyethyl cyanoacetate, methoxyethoxyethyl cyanoacetate, methoxyethoxyethyl cyanoacetate, methoxyethoxyethyl
• Examples of compounds having two cyanoacetyl groups include hexanediol biscyanoacetate, ethylene glycol dicyanoacetate, diethylene glycol dicyanoacetate, triethylene glycol dicyanoacetate, tetraethylene glycol dicyanoacetate, polyethylene glycol dicyanoacetate, propylene glycol dicyanoacetate, dipropylene glycol dicyanoacetate, tripropylene glycol dicyanoacetate, tetrapropylene glycol dicyanoacetate, and polypropylene glycol dicyanoacetate.
• Examples of compounds having three cyanoacetyl groups include trimethylolethane tricyanoacetate, trimethylolpropane tricyanoacetate, glycerin tricyanoacetate, tris(2-cyanoacetoxyethyl)isocyanurate, hexanetriol tricyanoacetate, octanetriol tricyanoacetate, decanetriol tricyanoacetate, and alkylene oxide adducts of these.
• Examples of compounds having four cyanoacetyl groups include ditrimethylolethane tetracyanoacetate, ditrimethylolpropane tetracyanoacetate, diglycerol tetracyanoacetate, pentaerythritol tetracyanoacetate, erythritol tetracyanoacetate, and alkylene oxide adducts of these.
• Examples of compounds having five cyanoacetyl groups include tritrimethylolethane pentacyanoacetate, tritrimethylolpropane pentacyanoacetate, triglycerin pentacyanoacetate, xylitol pentacyanoacetate, and alkylene oxide adducts of these.
• Examples of compounds having six or more cyanoacetyl groups include polytrimethylolethane polycyanoacetate, polytrimethylolpropane polycyanoacetate, polyglycerin polycyanoacetate, dipentaerythritol hexanecyanoacetate, sorbitol hexacyanoacetate, tripentaerythritol octacyanoacetate, polypentaerythritol polycyanoacetate, and alkylene oxide adducts of these.
• Cyanoacetic acid esters may be used alone or in combination of two or more.
• the cyanoacetate ester is preferably a cyanoacetate ester having one or two cyanoacetyl groups, such as octyl cyanoacetate, 2-octyl cyanoacetate, octadecyl cyanoacetate, methoxyethyl cyanoacetate, ethoxyethyl cyanoacetate, methoxyethoxyethyl cyanoacetate, methoxyethoxyethoxyethyl cyanoacetate, methoxyethoxyethoxyethyl cyanoacetate, ethoxyethoxyethyl cyanoacetate, ethoxyethoxyethoxyethyl cyanoacetate, methoxypropyl cyanoacetate, ethoxypropyl cyanoacetate, methoxypropoxypropyl cyanoacetate, ethoxypropoxypropyl cyanoacetate, methoxypropoxypropyl
• R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent including a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, or an aryl group, R 1 and R 2 may be bonded to each other to form a ring, and m is 1 to 100.
• R 1 and R 2 in formula (1) include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a t-butyl group, an n-, s-amyl group, a t-amyl group, a neopentyl group, an n-hexyl group, an s-hexyl group, a t-hexyl group, an n-heptyl group, an s-heptyl group, a t-heptyl group, an n-octyl group, an s-octyl group, a t-octyl group, a 2-ethylhexyl group, a capryl group, a nonyl group, a decyl group, an undecyl group, a lauryl group,
• stearyl group nonadecyl group, arachyl group, seryl group, myricyl group, melissyl group, vinyl group, allyl group, methallyl group, crotyl group, 1,1-dimethyl-2-propenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 2-methyl-3-butenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group , oleyl group, linole group, linolene group, cyclopentyl group, vinyl
• R1 and R2 are bonded to each other, it is preferred that R1 and R2 are bonded to each other to form an ethylene group or a propylene group.
• m is preferably 1 to 50, more preferably 1 to 30, even more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 3.
• the compound represented by formula (1) may be used alone or in combination of two or more.
• the compound represented by formula (1) is preferably at least one selected from the group consisting of methylal, ethylal, 1,3-dioxolane, 1,3-dioxane, trioxane, and paraformaldehyde.
• the compound represented by formula (1) is preferably at least one selected from the group consisting of methylal, 1,3-dioxolane, trioxane, and paraformaldehyde.
• the ratio of the cyanoacetate ester to the compound represented by formula (1) is not particularly limited, but the amount of the compound represented by formula (1) used is preferably 0.5 mol to 15.0 mol, and more preferably 0.9 mol to 5.0 mol, per 1 mol of cyanoacetyl group in the cyanoacetate ester.
• the amount of the compound represented by formula (1) used is 0.5 mol or more, the conversion rate of the cyanoacetate ester tends to be high.
• the amount of the compound represented by formula (1) used is 15.0 mol or less, the amount of ⁇ -cyanoacrylate produced per unit volume is large, resulting in excellent productivity.
• the dialkoxymethane includes a compound represented by the following formula (1A).
• R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• R 1 and R 2 may be bonded to each other to form a ring.
• R 1 and R 2 in formula (1A) include a methyl group, an ethyl group, an n- or i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-amyl group, an s-amyl group, a t-amyl group, a neopentyl group, an n-hexyl group, an s-hexyl group, a t-hexyl group, an n-heptyl group, an s-heptyl group, a t-heptyl group, an n-octyl group, an s-octyl group, a t-octyl group, a 2-ethylhexyl group, a capryl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, a tride
• R1 and R2 are bonded to each other, it is preferred that R1 and R2 are bonded to each other to form an ethylene group or a propylene group.
• the dialkoxymethane may be used alone or in combination of two or more types.
• the dialkoxymethane is preferably at least one selected from the group consisting of methylal, ethylal, dibutoxymethane, 1,3-dioxolane, and 1,3-dioxane.
• the dialkoxymethane is preferably at least one selected from the group consisting of methylal, ethylal, and 1,3-dioxolane.
• the ratio of cyanoacetate to dialkoxymethane is not particularly limited, but it is preferable to use 0.5 to 15.0 moles of dialkoxymethane per mole of cyanoacetyl group in cyanoacetate, and more preferably 0.9 to 5.0 moles.
• the amount of dialkoxymethane used is 0.5 moles or more, the conversion rate of cyanoacetate tends to be high.
• the amount of dialkoxymethane used is 15.0 moles or less, the amount of ⁇ -cyanoacrylate produced per unit volume is high, resulting in excellent productivity.
• a cyanoacetic acid ester is reacted with a dialkoxymethane in the presence of a cyclic carboxylic acid anhydride.
• the cyclic carboxylic acid anhydride is preferably a cyclic carboxylic acid anhydride represented by the following formula (2):
• R3 is a linear or branched divalent group having 1 to 10 carbon atoms, and may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• Examples of cyclic carboxylic acid anhydrides represented by formula (2) include itaconic anhydride, succinic anhydride, citraconic anhydride, maleic anhydride, phthalic anhydride, octyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, dodecyl succinic anhydride, octadecyl succinic anhydride, isooctadecyl succinic anhydride, decenyl succinic anhydride, hexadecen ...
• octenylsuccinic anhydride isooctadecenylsuccinic anhydride, tetradecenylsuccinic anhydride, 2-octenylsuccinic anhydride, 2,3-anthracenedicarboxylic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 1,8-naphthalic anhydride phthalic anhydride, 1,2-naphthalic anhydride, tetrabromophthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, 3-bromophthalic anhydr
• the cyclic carboxylic acid anhydrides may be used alone or in combination of two or more.
• the cyclic carboxylic acid anhydride is preferably at least one selected from the group consisting of succinic anhydride, phthalic anhydride, and maleic anhydride.
• the cyclic carboxylic acid anhydride is preferably maleic anhydride.
• the amount of cyclic carboxylic anhydride used is not particularly limited, but it is preferable to use 0.3 to 20.0 moles of cyclic carboxylic anhydride per mole of cyanoacetyl group of cyanoacetic ester, and more preferably 0.5 to 5.0 moles.
• the amount of cyclic carboxylic anhydride used is 0.3 moles or more, polymerization of ⁇ -cyanoacrylate due to alcohol by-produced in the conversion of dialkoxymethane or polyoxymethylene dialkyl ether is less likely to occur, and the amount of ⁇ -cyanoacrylate produced is improved.
• the amount of cyclic carboxylic anhydride used is 20.0 moles or less, the amount of ⁇ -cyanoacrylate produced per unit volume is large, resulting in excellent productivity.
• ⁇ Boron oxide> In the method for producing an ⁇ -cyanoacrylate according to the second embodiment of the present disclosure, a cyanoacetic ester is reacted with a compound represented by formula (1) in the presence of boron oxide.
• the amount of boron oxide used is not particularly limited, but it is preferable to use 0.15 to 10.0 moles of boron oxide (with one mole of B 2 O 3 counted as one mole) per mole of cyanoacetyl group of the cyanoacetic acid ester, and more preferably 0.25 to 2.5 moles.
• the amount of boron oxide used is 0.15 moles or more, polymerization of ⁇ -cyanoacrylate due to alcohol, phenol or water produced as a by-product in the conversion of the compound represented by formula (1) is unlikely to occur, and the amount of ⁇ -cyanoacrylate produced is improved.
• the amount of boron oxide used is 10.0 moles or less, the amount of ⁇ -cyanoacrylate produced per unit volume is large, resulting in excellent productivity.
• Catalyst A is at least one compound selected from the group consisting of cyclic diamines, salts of cyclic diamines, and complexes containing cyclic diamines.
• the catalyst A is preferably at least one compound selected from the group consisting of a cyclic diamine represented by the following formula (3), a salt of a cyclic diamine represented by the following formula (3), and a complex containing a cyclic diamine represented by the following formula (3).
• R 4 and R 6 are each independently a linear or branched divalent group having 1 to 10 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 5 is a hydrogen atom, or a linear or branched monovalent group having 1 to 20 carbon atoms, and may have at least one substituent selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
• R 4 and R 5 , R 5 and R 6 , R 6 and R 4 , and R 4 , R 5 , and R 6 may each be linked to each other to form a ring.
• the cyclic diamine shown in formula (3) may form a salt or a complex with a compound that exhibits acidity.
• Catalyst A may be, for example, piperazine, piperazine dihydrochloride, homopiperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-butylpiperazine, 2-(piperazin-1-yl)pyrazine, 1-(tert-butoxycarbonyl)piperazine, 1-tert-butoxycarbonyl-2-methylpiperazine, 1-tert-butoxycarbonyl-3-methylpiperazine, 1-(tert-butoxycarbonyl)homopiperazine, 1-benzyl-3-(3-pyridinyl)piperazine, 1-benzyl-3-[2-(trifluoromethyl)phenyl]piperazine, 1-benzyl-3-(4-fluorophenyl)piperazine, 1-(2-chlorophenyl)piperazine, 1-methyl-3-phenylpiperazine, 1-cyclopentylpiperazine, 1-(3-fluorobenzyl)piperazine, 1-(4-fluorobenzyl
• Catalyst A may be used alone or in combination of two or more types.
• catalyst A is preferably at least one selected from the group consisting of piperazine, homopiperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine. From the viewpoints of good reactivity with cyanoacetic ester and ease of availability, catalyst A is preferably at least one selected from the group consisting of piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine.
• the amount of catalyst A used is not particularly limited, but it is preferable to use 0.0001 to 0.3 moles, and more preferably 0.001 to 0.1 moles, of catalyst A per mole of cyanoacetyl groups in the cyanoacetic acid ester. If the amount of catalyst A used is 0.0001 moles or more, a large amount of ⁇ -cyanoacrylate will be produced. If the amount of catalyst A used is 0.3 moles or less, the purification process after completion of the reaction will be simple.
• the catalyst B is at least one compound selected from the group consisting of the compounds B1 group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid, salts of the compounds B1 group, complexes containing the compounds B1 group, esters of the compounds B1 group, and anhydrides of the compounds B1 group.
• catalyst B is at least one compound selected from the group consisting of sulfuric acid, sulfates, complexes containing sulfuric acid, sulfate esters, anhydrides of sulfuric acid, sulfonic acids, salts of sulfonic acids, complexes containing sulfonic acids, sulfonic acid esters, anhydrides of sulfonic acids, phosphoric acids, phosphates, complexes containing phosphoric acid, phosphoric acid esters, anhydrides of phosphoric acid, phosphorous acids, phosphites, complexes containing phosphorous acids, phosphorous esters, and anhydrides of phosphorous acids.
• the catalyst B is preferably at least one compound selected from the group consisting of the compounds represented by the following formula (4) and the compounds of group B2 represented by the following formula (5), salts of group B2, complexes of group B2, esters of group B2, and anhydrides of group B2.
• n is 0 to 20
• X 1 and X 2 are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 5 to 24 carbon atoms, a carbon atom chemically bonded to silica gel, or a carbon atom in a copolymer skeleton containing at least one structural unit derived from styrene, ethylstyrene, and divinylbenzene, and may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a
• r is 1 to 20, and X3 and X4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom, a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X5 is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 24 carbon atoms, which may have a substituent containing at least one selected from the group consisting of a double bond, a triple bond, an oxygen atom, a nitrogen atom, a hydrogen atom , a halogen atom, a silicon atom, an alkyl group, and an aryl group.
• X3 and X4 , X4 and X5 , X5 and X3 , and X3, X4 , and X5 may each be linked
• the compound represented by formula (4) and the compound represented by formula (5) may form a salt or a complex with a basic compound, water, or a solvent.
• Catalyst B may be, for example, sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-iodobenzenesulfonic acid, long-chain alkylsulfonic acids such as decanesulfonic acid, long-chain alkylbenzenesulfonic acids such as laurylbenzenesulfonic acid, p-phenolsulfonic acid, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, 2-morpholinoethanesulfonic acid, 4,4'-biphenyldisulfonic acid, 2,5-dichlorobenzenesulfonic acid dihydrate, sulisobenzone,
• Catalyst B may be used alone or in combination of two or more types.
• catalyst B is sulfuric acid, alkylsulfonic acids such as methanesulfonic acid, arylsulfonic acids such as p-toluenesulfonic acid and laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to silica gel, inorganic phosphoric acids such as phosphoric acid, pyrophosphoric acid, and polyphosphoric acid and dehydration condensates thereof, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, monoisotride
• catalyst B is preferably at least one selected from the group consisting of methanesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to silica gel, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoisotridecyl phosphate, monooleyl phosphate, monooctadecyl phosphate, monotetracosyl phosphate, dimethyl phosphate, diethyl phosphate, diisopropyl phosphate, dibutyl phosphate, diisotridecyl phosphate, dioleyl phosphate, dioctadecyl phosphate, and ditetracosyl phosphate.
• the amount of catalyst B used is not particularly limited, but it is preferable that the amount of sulfur or phosphorus atoms contained in catalyst B is 0.0003 to 0.9 moles, and more preferably 0.003 to 0.3 moles, per mole of cyanoacetyl groups in the cyanoacetic ester. If the amount of sulfur or phosphorus atoms contained in catalyst B is 0.0003 moles or more, a large amount of ⁇ -cyanoacrylate is produced. If the amount of sulfur or phosphorus atoms contained in catalyst B is 0.9 moles or less, the purification process after completion of the reaction is simple.
• the ratio of catalyst A to catalyst B is not particularly limited, but it is preferable that the sulfur or phosphorus atoms contained in catalyst B be 1.2 moles or more, and more preferably 1.5 moles or more, per mole of catalyst A. If the sulfur or phosphorus atoms contained in catalyst B are 1.2 moles or more, the amount of ⁇ -cyanoacrylate produced will increase.
• the cyclic carboxylic acid anhydride, the catalyst A, and the catalyst B may be added from the beginning or midway of the reaction in the reaction step. In addition, each component may be added all at once or in portions.
• boron oxide, catalyst A, and catalyst B may be added in the reaction step from the beginning or during the reaction. In addition, each component may be added all at once or in portions.
• the preferred combinations of dialkoxymethane, cyclic carboxylic acid anhydride, catalyst A, and catalyst B are as follows:
• the dialkoxymethane is represented by the formula (1A):
• the cyclic carboxylic acid anhydride is a cyclic carboxylic acid anhydride represented by formula (2):
• Catalyst A is at least one compound selected from the group consisting of a cyclic diamine represented by formula (3), a salt of the cyclic diamine represented by formula (3), and a complex containing the cyclic diamine represented by formula (3), [0023]
• catalyst B is at least one compound selected from the group consisting of a compound represented by formula (4) and a compound of group B2 represented by formula (5), a salt of the compound of group B2, a complex of the compound of group B2, an ester of the compound of group B2, and an anhydride of the compound of group B2.
• the dialkoxymethane is at least one selected from the group consisting of methylal, ethylal, dibutoxymethane, 1,3-dioxolane, and 1,3-dioxane;
• the cyclic carboxylic acid anhydride is at least one selected from the group consisting of succinic anhydride, phthalic anhydride, and maleic anhydride;
• Catalyst A is at least one selected from the group consisting of piperazine, homopiperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine;
• Catalyst B is sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resin, a solid catalyst in which a sulfonic acid group is chemically bonded to silica gel, phosphoric acid, pyrophosphoric acid, polyphospho
• the dialkoxymethane is at least one selected from the group consisting of methylal, ethylal, and 1,3-dioxolane;
• the cyclic carboxylic acid anhydride is maleic anhydride,
• Catalyst A is at least one selected from the group consisting of piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine;
• Catalyst B is at least one selected from the group consisting of methanesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to silica gel, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoisotridecyl phosphate, monooleyl phosphate, monooctadecyl phosphate, monotetracosy
• Catalyst A is at least one compound selected from the group consisting of a cyclic diamine represented by formula (3), a salt of the cyclic diamine represented by formula (3), and a complex containing the cyclic diamine represented by formula (3)
• catalyst B is at least one compound selected from the group consisting of a compound represented by formula (4) and a compound of group B2 represented by formula (5), a salt of the compound of group B2, a complex of the compound of group B2, an ester of the compound of group B2, and an anhydride of the compound of group B2.
• the compound represented by formula (1) is at least one selected from the group consisting of methylal, ethylal, 1,3-dioxolane, 1,3-dioxane, trioxane, and paraformaldehyde;
• Catalyst A is at least one selected from the group consisting of piperazine, homopiperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine;
• Catalyst B is sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resin, a solid catalyst in which a sulfonic acid group is chemically bonded to silica gel, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobuty
• the compound represented by formula (1) is at least one selected from the group consisting of methylal, 1,3-dioxolane, trioxane, and paraformaldehyde;
• Catalyst A is at least one selected from the group consisting of piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine;
• Catalyst B is at least one selected from the group consisting of methanesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to silica gel, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoisotridecyl phosphate, monooleyl phosphate, monooctadecyl phosphate, monotetracosyl phosphate, dimethyl phosphate, diethy
• a solvent may not be used, but a solvent may be used if necessary.
• the solvent include hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin, and tetralin; acetals such as diethyl acetal and dihexyl acetal, diethyl ether, dipropyl
• the solvent is preferably a hydrocarbon, an ether, a carboxylate, an alkyl phosphate, or an aryl phosphate.
• the solvent may be used alone or in combination of two or more kinds.
• the reaction temperature is preferably 40° C. to 120° C., and more preferably 55° C. to 105° C. If the reaction temperature is 40° C. or higher, the reaction proceeds easily, whereas if the reaction temperature is 120° C. or lower, the polymerization of the cyanoacryloyl group does not proceed easily, the amount of ⁇ -cyanoacrylate produced increases, the color tone of the reaction liquid is good, and the purification step after completion of the reaction is simple.
• the reaction pressure is not particularly limited as long as the specified reaction temperature can be maintained.
• the reaction may be carried out under reduced pressure or under increased pressure.
• the reaction pressure is usually 0.000001 MPa to 1 MPa (absolute pressure).
• alcohol or phenol derived from dialkoxymethane is by-produced along with the production of ⁇ -cyanoacrylate.
• the by-produced alcohol or phenol may be left coexisting in the reaction system, or may be discharged outside the reaction system during the reaction.
• an inert gas such as argon, helium, nitrogen, or carbon dioxide, or an acidic gas may be introduced into the reaction system for the purpose of maintaining a good color tone of the reaction liquid or preventing polymerization of the cyanoacryloyl group.
• Methods for introducing gas include dissolving the gas in the reaction liquid, flowing the gas into the gas phase in the reaction system, or blowing the gas into the reaction liquid (so-called bubbling). These gases may be used alone or in combination of two or more.
• a polymerization inhibitor to the reaction system for the purpose of preventing polymerization of the cyanoacryloyl group.
• the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, catechol, pyrogallol, tert-butylcatechol, gallic acid, 3,9-bis ⁇ 1,1-dimethyl-2-[ ⁇ -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl ⁇ -2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 2- ⁇ 1-[2-hydroxy
• the polymerization inhibitor may be used alone or in combination of two or more kinds.
• the amount of the polymerization inhibitor added in the reaction solution is preferably 5 ppm by mass to 30,000 ppm by mass, more preferably 25 ppm by mass to 10,000 ppm by mass. When the amount of the polymerization inhibitor added is 5 ppm by mass or more, the polymerization inhibition effect is sufficiently exhibited. When the amount of the polymerization inhibitor added is 30,000 ppm by mass or less, the color tone of the reaction solution is good, and separation and purification from the obtained ⁇ -cyanoacrylate is easy.
• reaction time in the disclosed method for producing ⁇ -cyanoacrylate varies depending on the type and amount of catalyst used, reaction temperature, reaction pressure, etc., but is usually 0.1 to 100 hours, and preferably 1 to 50 hours.
• the method for producing an ⁇ -cyanoacrylate according to the first embodiment of the present disclosure can be carried out by any of a batch method, a semi-batch method, and a continuous method.
• a batch method a cyanoacetic acid ester, a dialkoxymethane, a cyclic carboxylic acid anhydride, a catalyst A, a catalyst B, and a polymerization inhibitor are charged into a reactor, and the mixture is stirred at a predetermined temperature while flowing an inert gas into the gas phase of the reaction system, thereby producing the target ⁇ -cyanoacrylate.
• the method for producing an ⁇ -cyanoacrylate according to the second embodiment of the present disclosure can be carried out by any of a batch method, a semi-batch method, and a continuous method.
• a cyanoacetic acid ester, a compound represented by formula (1), boron oxide, catalyst A, catalyst B, and a polymerization inhibitor are charged into a reactor, and the mixture is stirred at a predetermined temperature while flowing an inert gas into the gas phase of the reaction system, thereby producing the target ⁇ -cyanoacrylate.
• the reaction product obtained by the method for producing ⁇ -cyanoacrylate of the present disclosure can be subjected to a separation and purification operation that combines crystallization operations such as cooling crystallization and concentration crystallization, filtration operations such as pressure filtration, suction filtration, centrifugal filtration, and squeeze filtration, distillation operations such as simple distillation, fractional distillation, continuous distillation, thin film evaporation, and molecular distillation, and extraction operations such as solid-liquid extraction and liquid-liquid extraction, to obtain the desired ⁇ -cyanoacrylate with high purity.
• a solvent may be used in the separation and purification operation.
• a neutralizing agent for neutralizing the catalyst A, catalyst B, and/or polymerization inhibitor used in the method for producing ⁇ -cyanoacrylate of the present disclosure an adsorbent for adsorption and removal, an acid and/or alkali for decomposing or removing by-products, activated carbon for improving color tone, an antifoaming agent for suppressing foaming of the process liquid, and an auxiliary agent (e.g., diatomaceous earth) for improving filtration efficiency and filtration speed may be used.
• an auxiliary agent e.g., diatomaceous earth
• the reaction yield in the examples and comparative examples was calculated from the peak area of the target ⁇ -cyanoacrylate by sampling a small amount of the reaction solution in the reaction system and performing proton nuclear magnetic resonance (hereinafter referred to as 1 H-NMR) analysis (400 MHz, 24° C., deuterated chloroform solvent).
• 1 H-NMR proton nuclear magnetic resonance
• the purification yield was calculated using the parts by mass of ⁇ -cyanoacrylate obtained after subjecting the reaction-terminated liquid containing ⁇ -cyanoacrylate to separation and purification procedures such as distillation, crystallization, and filtration.
• Purification yield (%) (parts by mass of target ⁇ -cyanoacrylate contained in the purified product)/(parts by mass when all of the cyanoacryloyl groups of the cyanoacetic ester used as the raw material have reacted and been converted to ⁇ -cyanoacrylate) ⁇ 100
• Example 1 In a 110-mL test tube equipped with a rotor, a thermometer, a gas inlet tube, and a Dimroth condenser, 7.200 parts (0.0335 mol) of methoxypropoxypropyl cyanoacetate, 6.968 parts (0.0669 mol) of ethylal, 13.121 parts (0.1338 mol) of maleic anhydride as a cyclic carboxylic acid anhydride, 0.153 parts (0.0013 mol) of 2,6-dimethylpiperazine as catalyst A, and 0.153 parts (0.0013 mol) of catalyst B were added.
• the catalyst B As the catalyst B, 0.351 parts (0.0017 moles) of dibutyl phosphate, 0.386 parts (0.0040 moles) of methanesulfonic acid, and 0.113 parts (4000 wtppm relative to the total weight of the raw materials charged) of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) were charged as a polymerization inhibitor, and the test tube was placed in a metal bath and stirred while flowing nitrogen gas at a flow rate of 4 ml/min into the gas phase of the reaction system. The temperature of the metal bath was raised to 95°C over 1 hour, and then the mixture was heated and stirred at 95°C for 7 hours.
• Examples 2 to 16 and Comparative Examples 1 to 12 The types and contents (in the tables, the unit is "parts") of cyanoacetic ester, dialkoxymethane, cyclic carboxylic anhydride, catalyst A, and catalyst B, as well as the temperature and time of heating and stirring, were changed, and the reaction to produce ⁇ -cyanoacrylate was carried out in the same manner as in Example 1, and the reaction yield was calculated.
• the results are shown in Tables 1 to 6. In the tables, the following abbreviations were used, and the reaction yield was calculated from the following formula.
• MP2CAc methoxypropoxypropyl cyanoacetate
• MP2CA methoxypropoxypropyl cyanoacrylate
• HDBisCAc hexanediol bis cyanoacetate
• HDBisCA hexanediol bis cyanoacrylate
• 2-OctCAc 2-octyl cyanoacetate
• 2-OctCA 2-octyl cyanoacrylate
• EECAc ethoxyethyl cyanoacetate
• EECA ethoxyethyl cyanoacrylate
• ME3CAc methoxyethoxyethyl cyanoacetate
• ME3CA methoxyethoxyethoxyethyl cyanoacrylate
• MDA methylene diacetate
• Example 13 the mixture was stirred at 60° C. for 16 hours, followed by stirring at 90° C. for 4 hours.
• Example 15 the mixture was stirred at 55° C. for 24 hours, and then at 90° C. for 9 hours.
• Example 17 A 1-liter flask equipped with a stirrer, a thermometer, a gas inlet tube, and a Dimroth condenser was charged with 120.000 parts (0.5575 mol) of MP2CAc, 79.540 parts (1.0453 mol) of methylal, 205.013 parts (2.0907 mol) of maleic anhydride as a cyclic carboxylic acid anhydride, 2.234 parts (0.0223 mol) of 2-methylpiperazine as catalyst A, 7.810 parts of isotridecyl phosphate (JP-513 (product name) manufactured by Johoku Chemical Industry Co., Ltd.) as catalyst B, 20.472 parts (0.0627 mol) of LAS as catalyst B, and 1.747 parts (4000 wtppm relative to the total weight of the raw materials charged) of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) as a polymerization inhibitor, and the flask was placed in an oil bath
• the temperature of the oil bath was raised to 100°C over 2 hours, and then the mixture was heated and stirred at 100°C for 3 hours.
• a small amount of the reaction liquid was collected and subjected to 1 H-NMR analysis, and the production of the target ⁇ -cyanoacrylate, MP2CA, was confirmed.
• the reaction yield was 79%.
• the Dimroth condenser was removed and a Liebig condenser was installed, and reduced-pressure distillation was started.
• the pressure in the system was gradually reduced to 0.4 kPa to distill and remove low-boiling components such as unreacted methylal and maleic anhydride.
• the kettle liquid was cooled to 40°C or less, the pressure was returned to normal pressure, and 0.201 parts of boron trifluoride diethyl ether complex was added to the kettle liquid, after which the pressure in the system was reduced to 24 Pa, and the oil bath temperature was raised to 105°C to distill and recover the target purified product containing MP2CA.
• the purification yield was 67%.
• the desired ⁇ -cyanoacrylate could be obtained in a higher yield than in the comparative examples in which a cyclic carboxylic anhydride, catalyst A or catalyst B was not used, and in the comparative examples in which MDA, a compound having electron-withdrawing ester groups at both ends of a methylene group, which is a conventional technology, was used.
• Example 5 in which a strongly acidic ion exchange resin was used
• Example 6 in which a cyanoacetate having two cyanoacetyl groups in the molecule was used
• the effects of the present disclosure are remarkable when an immobilized catalyst or a cyanoacetate having multiple cyanoacetyl groups in the molecule is used.
• Example 101 In a 110-mL test tube equipped with a rotor, a thermometer, a gas inlet tube, and a Dimroth condenser, 7.200 parts (0.0335 mol) of methoxypropoxypropyl cyanoacetate, 5.091 parts (0.0669 mol) of methylal, 5.240 parts (0.0753 mol) of boron oxide, 0.201 parts (0.0020 mol) of 2-methylpiperazine as catalyst A, and isotridecyl phosphate (Johoku Chemical Industry Co., Ltd.) as catalyst B were added.
• Example 109 Into a 1-liter flask equipped with a stirrer, a thermometer, a gas inlet tube, and a Dimroth condenser, 144.000 parts (0.6690 mol) of MP2CAc, 101.812 parts (1.3380 mol) of methylal, 104.796 parts (1.5053 mol) of boron oxide, 4.021 parts (0.0401 mol) of 2-methylpiperazine as catalyst A, and isotridecyl phosphate (Johoku Chemical Industry Co., Ltd.) as catalyst B were added.
• reaction liquid was collected and subjected to 1 H-NMR analysis, and the production of MP2CA, the target ⁇ -cyanoacrylate, was confirmed.
• the reaction yield was 81%.
• the kettle liquid was cooled to 40°C or less, the pressure was returned to normal pressure, and 0.260 parts of boron trifluoride diethyl ether complex and 1.620 parts of silicone oil as an antifoaming agent were added to the kettle liquid, and the liquid was then fed to a thin-film evaporator with a jacket temperature of 110°C and a system pressure reduced to 300 Pa, where the target purified product containing MP2CA was distilled and recovered.
• the purification yield was 56%.
• the method for producing ⁇ -cyanoacrylate disclosed herein can produce ⁇ -cyanoacrylate with a relatively large monomer molecular weight and ⁇ -cyanoacrylate with reactive functional groups in good yield.
• the ⁇ -cyanoacrylate obtained by the method for producing ⁇ -cyanoacrylate disclosed herein can be used as the main component of various adhesives and is suitable for use in various industrial and medical fields, as well as for repair and construction applications in the home.

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