Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C263/00—Preparation of derivatives of isocyanic acid
  • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
  • C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C263/00—Preparation of derivatives of isocyanic acid
  • C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups

Definitions

• the present invention relates to a (meth) acrylic acid ester compound having an isocyanato group and a method for producing the same.
• the (meth) acrylic acid ester compound having an isocyanato group represented by acryloyloxyethyl isocyanate and methacryloyloxyethyl isocyanate has a highly reactive isocyanato group and an ethylenic double bond in one molecule.
• Paint (coating material), adhesive, isocyanate, dental material, magnetic recording material, etc. and is an extremely useful compound in industry.
• the (meth) acrylic acid ester compound having an isocyanato group can be produced, for example, using a (meth) acrylic acid compound, phosgene, or the like in the presence of a catalyst (see Patent Document 1).
• N, N-dimethylformamide (hereinafter referred to as N, N-dimethylformamide) (hereinafter referred to as When (also referred to as "DMF") is used, phosgene reacts with DMF to generate dimethylcarbamoyl chloride (DMCC), which is one of the dialkylcarbamoyl chlorides, as an impurity.
• DMCC dimethylcarbamoyl chloride
• dialkylcarbamoyl chloride hydrogen chloride and dialkylamine are generated, which promote metal corrosion and the like.
• Purification treatment such as distillation is performed to remove dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound having an isocyanato group.
• Purification treatment such as distillation is performed to remove dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound having an isocyanato group.
• the present invention aims to reduce the content of dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound.
• the present inventors have an isocyanato group by using a predetermined catalyst when reacting a compound having an ethylenically unsaturated group, which is one of the raw materials, with phosgene. They have found that the content of dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound can be reduced, and have completed the present invention. That is, the present invention includes, for example, the matters described in the following [1] to [18].
• R 3 is an ethylenically unsaturated group having 2 or 3 carbon atoms) (R 3 -COO) n -R 4 - (NCO) m ⁇ (1)
• R 4 is a hydrocarbon group of m + n valent which may contain carbon atoms 1-7 ether groups, m and n Are independently integers of 1 or 2)
• the dialkylcarbamoyl chloride is at least one compound selected from the group consisting of N, N-dimethylcarbamoyl chloride, dihexylcarbamoyl chloride, dibenzylcarbamoyl chloride, dicyclohexylcarbamoyl chloride and di- (2-ethylhexyl) carbamoyl chloride.
• the (meth) acrylic acid ester compound having an isocyanato group is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 2- (isocyanatoethyloxy).
• the method for producing a (meth) acrylic acid ester compound having an isocyanato group according to any one of [1] to [3], which is ethyl methacrylate or 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
• R 1 and R 2 are independently alkyl groups having 5 to 10 carbon atoms which may have substituents, cycloalkyl groups having 5 to 10 carbon atoms which may have substituents, or An aryl group having 6 to 10 carbon atoms which may have a substituent)
• R 3 is an ethylenically unsaturated group having 2 or 3 carbon atoms
• R 4 is an m + n-valent hydrocarbon group having 1 to 7 carbon atoms which may contain an ether group.
• the dialkylcarbamoyl chloride is at least one compound selected from the group consisting of N, N-dimethylcarbamoyl chloride, dihexyl carbamoyl chloride, dibenzyl carbamoyl chloride, dicyclohexyl carbamoyl chloride and di- (2-ethylhexyl) carbamoyl chloride.
• the (meth) acrylic acid ester compound having an isocyanato group according to [8].
• the (meth) acrylic acid ester compound having an isocyanato group is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 2- (isocyanatoethyloxy).
• the (meth) acrylic acid ester compound having an isocyanato group according to [8] or [9], which is ethyl methacrylate or 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
• R 3 is an ethylenically unsaturated group having 2 or 3 carbon atoms
• R 3 -COO n -R 4 - (NCO) m ⁇
• R 4 is a hydrocarbon group of m + n valent which may contain carbon atoms 1-7 ether groups, m and n Are independently integers of 1 or 2)
• the dialkylcarbamoyl chloride is at least one compound selected from the group consisting of N, N-dimethylcarbamoyl chloride, dihexylcarbamoyl chloride, dibenzylcarbamoyl chloride, dicyclohexylcarbamoyl chloride and di- (2-ethylhexyl) carbamoyl chloride.
• the (meth) acrylic acid ester compound having an isocyanato group is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 2- (isocyanatoethyloxy).
• the (meth) acrylic acid ester compound having an isocyanato group of the present invention contains a small amount of the impurity dialkylcarbamoyl chloride, it is used in fields such as paints (coating materials), adhesives, phosphates, dental materials, and magnetic recording materials. It is useful.
• the present invention includes a (meth) acrylic acid ester compound having an isocyanato group having a dialkylcarbamoyl chloride content of 0.1% by mass or less, and a method for producing the same.
• (meth) acrylic acid means methacrylic acid or acrylic acid.
• the (meth) acrylic acid ester compound having an isocyanato group (-NCO) is a compound represented by the following formula (1).
• R 3 is an ethylenically unsaturated group having 2 or 3 carbon atoms. When the number of carbon atoms of R 3 is 4 or more, the reactivity of the ethylenically unsaturated group may decrease.
• R 4 is an m + n-valent hydrocarbon group having 1 to 7, preferably 2 to 6, more preferably 3 to 5, and even more preferably 2 carbon atoms, even if it is linear. It may be branched or may be branched. Further, R 4 may contain an ether bond. From R 4 is view of easy availability of raw materials, -CH 2 -, - CH 2 CH 2 -, or -CH 2 CH 2 OCH 2 CH 2 - is preferably, more preferably -CH 2 CH 2 - Is.
• n and n are independently integers of 1 or 2, and it is preferable that both are 1 from the viewpoint of ease of manufacture.
• Examples of the (meth) acrylic acid ester compound having an isocyanato group represented by the formula (1) include 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxy-n-propyl isocyanate, 2-methacryloyloxyisopropylisocyanate, and 4-methacryloyl.
• Oxy-n-butylisocyanate 2-methacryloyloxy-tert-butylisocyanate, 2-methacryloyloxybutyl-4-isocyanate, 2-methacryloyloxybutyl-3-isocyanate, 2-methacryloyloxybutyl-2-isocyanate, 2-methacryloyl Oxybutyl-1-isocyanate, 5-methacryloyloxy-n-pentylisocyanate, 6-methacryloyloxy-n-hexylisocyanate, 7-methacryloyloxy-n-heptylisocyanate, 2- (isocyanatoethyloxy) ethylmethacrylate, 3- Methacryloyloxyphenyl isocyanate, 4-methacryloyloxyphenyl isocyanate, 2-acryloyloxyethyl isocyanate, 3-acryloyloxy-n-propyl isocyanate, 2-
• 2-acryloyloxyethyl isocyanate 2-methacryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 2- (isocyanatoethyloxy) from the viewpoint of ease of production and / or availability of raw materials.
• Ethyl methacrylate or 1,1-bis (acryloyloxymethyl) ethyl isocyanate more preferably 2-acryloyloxyethyl isocyanate or 2-methacryloyloxyethyl isocyanate, still more preferably 2-acryloyloxyethyl isocyanate.
• dialkylcarbamoyl chloride (also referred to as dialkylcarbamoyl chloride) is a compound having a carbamoyl group generated by the reaction of compound (A) described later with phosgene.
• dialkyl carbamoyl chloride at least one compound selected from the group consisting of N, N-dimethylcarbamoyl chloride, dihexyl carbamoyl chloride, dibenzyl carbamoyl chloride, dicyclohexyl carbamoyl chloride and di- (2-ethylhexyl) carbamoyl chloride is preferable.
• the content of dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound having an isocyanato group is 0.1% by mass or less, preferably 0.01% by mass or less, and 0.005% by mass or less. Is more preferable.
• the lower limit of the content of dialkylcarbamoyl chloride is not particularly limited and may be 0 mass ppm. Since over-purification is not practical from the viewpoint of yield, the lower limit of the content of dialkylcarbamoyl chloride is, for example, 1 mass ppm and may be 10 mass ppm.
• the dialkylcarbamoyl chloride content is measured by gas chromatography according to an internal standard method, for example, using a (meth) acrylic acid ester compound having an isocyanato group obtained through a purification step performed after the step (3) described later. be able to.
• the (meth) acrylic acid ester compound having an isocyanato group after purification is used. It may be determined that the content of the dialkylcarbamoyl chloride contained in the above range is also within the above range.
• N-disubstituted formamide compound (A) The content of N-disubstituted formamide (A) contained in the (meth) acrylic acid ester compound having an isocyanato group of the present invention is the stability and easiness of polymerization of the (meth) acrylic acid ester compound having an isocyanato group. From this point of view, 100 mass ppm or less is preferable, 50 mass ppm or less is more preferable, and 20 mass ppm or less is further preferable.
• the lower limit of the content of the N-disubstituted formamide compound (A) is not particularly limited and may be 0 mass ppm. Since over-purification is not practical from the viewpoint of yield, the lower limit of the content of the N-disubstituted formamide compound (A) is, for example, 1 mass ppm and may be 10 mass ppm.
• N-disubstituted formamide compound (A) is synonymous with the compound (A) described in ⁇ Method for producing (meth) acrylic acid ester compound having an isocyanato group> described later.
• the (meth) acrylic acid ester compound having an isocyanato group having a dialkylcarbamoyl chloride content of 0.1% by mass or less can be obtained, for example, by a production method described later.
• the manufacturing method includes a step (2) and a step (3), preferably a step (1).
• the step (3) is performed after the step (2), and when the step (1) is performed, the step (1) is performed before the step (2).
• each step will be described.
• Step (2) is a step of bringing the compound (B) into contact with phosgene in the presence of the compound (A) to obtain a phosgene reaction product.
• Compound (A) is a catalyst used during the acid chloride reaction between compound (B) and phosgene.
• the compound (A) is an N-disubstituted formamide, and is preferably a compound represented by the following formula (4).
• R 1 and R 2 are independently an alkyl group having 5 to 10 carbon atoms which may have a substituent and a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent.
• an aryl group having 6 to 10 carbon atoms which may have a substituent has catalytic activity presumed to be derived from an electronic effect, and is easily separated from a (meth) acrylic acid ester compound having an isocyanato group. From this point, an alkyl group having 6 to 9 carbon atoms which may have a substituent, a cycloalkyl group having 6 to 9 carbon atoms which may have a substituent, or a carbon number which may have a substituent.
• dialkylcarbamoyl chloride contained in the (meth) acrylic acid ester compound having an isocyanato group can be reduced to 0.1% by mass or less.
• dialkylcarbamoyl chloride remains as a high boiling point component when the (meth) acrylic acid ester compound having an isocyanato group is distilled and purified because the boiling point of dialkylcarbamoyl chloride is high.
• substituent include an ether group and an aryl group.
• the boiling point of compound (A) under atmospheric pressure is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, and more preferably 300 ° C. or higher.
• Examples of the compound (A) include dihexylformamide (hereinafter, also referred to as “DHF”), dibenzylformamide (hereinafter, also referred to as “DBNF”), dicyclohexylformamide (hereinafter, also referred to as “DCHF”), and di (2-ethylhexyl) formamide. (Hereinafter also referred to as "DEHF”) can be suitably used for the present invention.
• the boiling points at these atmospheric pressures are DHF: 326 ° C., DBNF: 380 ° C., DCHF: 329 ° C., and DEHF: 378 ° C., respectively.
• Compound (A) can be obtained by the step (1) described later.
• Compound (B) is one of the raw materials for a (meth) acrylic acid ester compound having an isocyanato group, and is a compound represented by the following formula (2).
• R 3 has the same meaning as R 3 in the formula (1) also applies to the preferred embodiment.
• (meth) acrylic acid can be preferably used in the present invention.
• the reaction between compound (B) and phosgene is not particularly limited as long as a phosgene reactant is obtained by acid chloride formation of compound (B), but it can be carried out under the following conditions, for example.
• the compound (A) and the compound (B) are mixed so that the ratio of the compound (A) to the compound (B) is 0.1 to 5.0 mol% per 1 mol of the compound (B), and the mixed solution is 50 to 70. Heat to ° C. Then, 100 to 150 mol% of phosgene is added per 1 mol of compound (B), and the mixture is reacted at 50 to 70 ° C. for 1.5 to 3.0 hours to obtain a phosgene reaction product.
• phosgene may be removed and the phosgene reaction product may be purified by distillation or the like.
• Step (3) the phosgene reaction product obtained in the above step (2) is brought into contact with the hydroxyamine hydrochloride compound to obtain a (meth) acrylic acid ester compound having an isocyanato group represented by the above formula (1). This is the process of obtaining.
• the hydroxyamine hydrochloride compound is not particularly limited as long as it can produce a (meth) acrylic acid ester compound having an isocyanato group represented by the above formula (1) by reaction with a phosgene reactant.
• Examples of the hydroxyamine hydrochloride compound include the compound of the following formula (5).
• R 4, m and n are each and R 4, m and n in the formula (1) synonymous a preferred embodiment as well.
• Examples of the hydroxyamine in the hydroxyamine hydrochloride compound include ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, and 2-amino-.
• 1-butanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 6-amino-2-methyl-2-heptanol, 2- (2) -Aminoethoxy) ethanol can be mentioned.
• ethanolamine and 2- (2-aminoethoxy) ethanol can be preferably used in the present invention.
• the reaction between the phosgene reactant and the hydroxyamine hydrochloride compound is not particularly limited as long as the (meth) acrylic acid ester compound having an isocyanato group of the present invention is obtained, and can be carried out by a known method, for example. Specifically, hydroxyamine and 0.5 to 2.0 mol equivalent hydrochloric acid per 1 mol of hydroxyamine are mixed and reacted at 80 to 100 ° C. for 0.5 to 2.0 hours to obtain a hydrochloride of hydroxyamine.
• a phosgene reactant is added to 100 parts by mass of the hydrochloride salt of hydroxyamine and reacted for 0.1 to 1.0 hours to obtain an aminoalkyl acrylate hydrochloride.
• This can be brought into contact with phosgene and reacted at 80 to 90 ° C. for 7 to 10 hours to introduce an isocyanato group into aminoalkylacrylate hydrochloride to obtain a (meth) acrylic acid ester compound having an isocyanato group.
• the (meth) acrylic acid ester compound having an isocyanato group obtained by distillation or the like may be purified.
• the content of the N-disubstituted formamide compound (A) in the (meth) acrylic acid ester compound having an isocyanato group obtained in step (3) is the stability of the (meth) acrylic acid ester compound having an isocyanato group. From the viewpoint of ease of polymerization and polymerization, 100 mass ppm or less is preferable, 50 mass ppm or less is more preferable, and 20 mass ppm is further preferable.
• the lower limit of the content of the N-disubstituted formamide compound (A) is not particularly limited and may be 0 mass ppm. Since over-purification is not practical from the viewpoint of yield, the lower limit of the content of the N-disubstituted formamide compound (A) is, for example, 1 mass ppm and may be 10 mass ppm.
• the content of the N-disubstituted formamide compound (A) can be determined by gas chromatography using, for example, a (meth) acrylic acid ester compound having an isocyanato group obtained through a purification step performed after the step (3) described later. Can be measured according to the internal standard method. At this time, for example, if the content of the N-disubstituted formamide compound (A) contained in the (meth) acrylic acid ester compound having an isocyanato group before purification is within the above range, it has an isocyanato group after purification ( It may be determined that the content of the N-disubstituted formamide compound (A) contained in the meta) acrylic acid ester compound is also within the above range.
• the step (1) is a step of bringing the amine compound of the compound (E) represented by the following formula (3) into contact with formic acid to obtain the compound (A).
• R 1 and R 2 have the same meanings as R 1 and R 2 in the formula (4), preferred embodiments are also the same.
• Compound (E) As the compound (E), for example, dihexylamine, dibenzylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine and the like can be preferably used in the present invention.
• the reaction between the compound (E) and formic acid is not particularly limited as long as the compound (A) that can be used in the present invention is obtained, but for example, it can be carried out by a known method. Specifically, the compound (E) and an organic solvent are mixed, 1.0 to 1.5 mol equivalents of formic acid is added to the obtained mixed solution, and 3 to 125 ° C. at 100 to 125 ° C. React for 6 hours. The reaction solution after the reaction is filtered, and the obtained filtrate and an organic solvent are mixed to obtain crystals of compound (A).
• the compound (B) represented by the above formula (2) is brought into contact with phosgene to obtain a phosgene reactant, and the obtained phosgene reactant and hydroxy are obtained.
• the (meth) acrylic acid ester compound having an isocyanato group having a dialkylcarbamoyl chloride content of 0.1% by mass or less which is obtained by contacting with an amine hydrochloride compound, the meaning of the term is as described above ⁇ having an isocyanato group ( It has the same meaning as each term described in ⁇ meth) acrylic acid ester compound> and ⁇ method for producing (meth) acrylic acid ester compound having an isocyanato group>.
• the measurement method and the calculation method in the examples are as follows. [Contents of 2-acryloyloxyethyl isocyanate, dialkylcarbamoyl chloride and catalyst (formamide compound)] The contents of 2-acryloyloxyethyl isocyanate, dialkylcarbamoyl chloride and catalyst (formamide compound) were measured by gas chromatography (GC) analysis by separating each component under the conditions described below and measuring by an internal standard method.
• GC gas chromatography
• Hazen Colors (APHA)
• JIS K0071-1 The number of Hazen colors was measured in accordance with JIS K0071-1: 2017 by comparison with the APHA standard solution using a colorimetric tube.
• the hydrolyzable chlorine was measured as follows according to JIS K1603: 2007. 5 g of the sample was weighed into a 100 mL Erlenmeyer flask, and 35 mL of methanol and 15 mL of water were added to prepare a reaction solution. A reflux condenser was attached to this Erlenmeyer flask, and the reaction solution was heated under reflux in a water bath at 80 ° C. for 30 minutes and then cooled to room temperature. After cooling, the obtained solution was subjected to potentiometric titration using a 1/100 mol / L silver nitrate solution to determine the concentration of hydrolyzable chlorine.
• step (2) The incidence of dialkylcarbamoyl chloride (hereinafter also referred to as "dicarbamoyl chloride form") in step (2) is the content of dicarbamoyl chloride form measured by gas chromatography and the mass of the solution obtained in step (2).
• the number of moles of the dicarbamoyl chloride compound was calculated from the above, and the value was divided by the number of moles of the N-disubstituted formamide used in the step (2).
• DHF (Compound (A)
• DHF (Compound (A)
• dihexylamine Compound (E)
• 43.6 g (0.47 mol) of toluene were charged into a 100 mL three-necked flask equipped with a dropping funnel and Dean-Stark.
• 11.2 g (0.24 mol) of formic acid was added dropwise thereto via a dropping funnel over 5 minutes.
• the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside. After the addition of formic acid was completed, the internal temperature was raised to 125 ° C.
• DBNF (Compound (A)) was produced as follows. 39.4 g (0.2 mol) of dibenzylamine (Compound (E)) and 43.6 (0.47 mol) of toluene were charged into a 100 mL three-necked flask equipped with a dropping funnel and Dean-Stark. 11.2 g (0.24 mol) of formic acid was added dropwise thereto via a dropping funnel over 5 minutes. At this time, since heat is generated by the neutralization reaction, the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside. After the addition of formic acid was completed, the internal temperature was raised to 125 ° C.
• the reaction solution was filtered using a filter paper of type 5 A specified in JIS P3801: 1995, and insoluble matter was removed from the reaction solution. 50 mL of hexane was added to the filtrate, and the mixture was cooled to 5 ° C. to precipitate crystals. The precipitated crystals were collected by filtration, and the recovered crystals were washed twice with 50 mL of hexane. After washing, the crystals were dried at 40 ° C. for 6 hours to obtain the desired DBNF. The yield of DBNF relative to dibenzylamine was 67%.
• DCHF (Compound (A)
• DCHF (Compound (A)
• 37.1 g (0.2 mol) of dicyclohexylamine (Compound (E)) and 43.6 (0.38 mol) of -n-butyl acetate were placed in a 100 mL three-necked flask equipped with a dropping funnel and Dean-Stark.
• 11.2 g (0.24 mol) of formic acid was added dropwise thereto via a dropping funnel over 5 minutes.
• the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside.
• the internal temperature was raised to 125 ° C. by an oil bath, and the reaction was carried out for 10 days while removing the water generated by the neutralization reaction from the reaction system by azeotropic boiling with -n-butyl acetate. ..
• the reaction solution was filtered using a filter paper of type 5 A specified in JIS P3801: 1995, insoluble matter was removed from the reaction solution, and then -n-butyl acetate was distilled off under reduced pressure to obtain crystals.
• the obtained crystals were dissolved in 50 mL of hexane and cooled to 5 ° C. to precipitate crystals.
• the precipitated crystals were collected by filtration and washed twice with 10 mL of hexane cooled to 5 ° C. After washing, the crystals were dried at 40 ° C. for 6 hours to obtain the desired DCHF.
• the yield of DCHF relative to dicyclohexylamine was 36.7%.
• DEHF (Compound (A)
• DEHF di (2-ethylhexyl) amine
• Compound (E) di (2-ethylhexyl) amine
• 538 g 5.84 mol
• toluene a 2 L three-necked flask equipped with a dropping funnel and Dean Stark.
• 137.3 g (2.98 mol) of formic acid was added dropwise thereto via a dropping funnel over 2 hours.
• the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside.
• di-n-butylformamide (hereinafter referred to as "DBF") was produced as follows. 25.85 g (0.2 mol) of di-n-butylamine and 43.6 g (0.47 mol) of toluene were placed in a 100 mL three-necked flask equipped with a dropping funnel and Dean Stark. 11.2 g (0.24 mol) of formic acid was added dropwise thereto via a dropping funnel over 5 minutes. At this time, since heat is generated by the neutralization reaction, the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside.
• 4-formylmorpholine (hereinafter referred to as "4-FM") was produced as follows. 17.42 g (0.2 mol) of morpholine and 43.6 g (0.47 mol) of toluene were placed in a 100 mL three-necked flask equipped with a dropping funnel and Dean-Stark. 11.2 g (0.24 mol) of formic acid was added dropwise thereto via a dropping funnel over 5 minutes. At this time, since heat is generated by the neutralization reaction, the internal temperature is maintained at 100 ° C. or lower by a water jacket installed outside.
• Step (2) Production Example of 70 g (0.97 mol) of acrylic acid (Compound (B)), 0.01 g (0.07 mol) of phenothiazine, and 2.73 g (1 mol% with respect to acrylic acid) in a 200 mL four-necked flask.
• DEHF Compound (A)
• phosgene was introduced therein over 8 hours. After reacting at 60 ° C.
• Step (3) 70 g (1.15 mol) of 2-aminoethanol was placed in a 300 mL four-necked flask equipped with a stirrer, a condenser, a thermometer and an inner tube, and the temperature was raised to 85 ° C. 40.5 g (1.11 mol) of hydrogen chloride was blown into this at 200 mL / min to prepare a hydrochloride of ethanolamine.
• Examples 2 to 4 and Comparative Examples 1 to 3 As shown in Table 1, the catalyst of Example 1 and the amount used thereof were changed to the catalysts produced in Production Examples 1 to 3, 5 and 6, respectively, and the amount used thereof, in the same manner as in Example 1. AOI was manufactured. The results are shown in Table 1. The lower limit of detection of the catalyst and the dialkylcarbamoyl chloride compound in AOI using gas chromatography was 10 mass ppm, respectively. Further, in Comparative Example 1, the content of the dicarbamoyl chloride compound in the crude AOI was 0.4% by mass.
• Example 5> AOI was produced in the same manner as in Example 1 except that the purification method of Example 1 was changed from thin film distillation to simple distillation. The results are shown in Table 1.

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