JP6869542B2 - Method for Producing N-Substituted (Meta) Acrylamide - Google Patents

Description

The present invention relates to a simple industrial method for producing N-substituted (meth) acrylamide.

N-substituted (meth) acrylamides include monofunctional (meth) acrylamides with one (meth) acrylamide group and polyfunctional (meth) acrylamides with two or more (meth) acrylamide groups. The structure varies depending on the type and number of substituents, and it can cover a wide range of physical properties and functions from liquid to solid, hydrophilic to hydrophobic, paints, adhesives, adhesives, various coating agents, etc. It is used in an extremely diverse field such as synthetic raw materials such as papermaking agents, polymer flocculants, and contact lenses, reactive diluents for UV curable resins, and cross-linking agents for thermal polymerization or photopolymerization. Has been actively examined since.

One of the industrial methods for producing N-substituted (meth) acrylamide is a method using a (meth) acrylic acid ester as a starting material. Specifically, (1) (meth) acrylic acid ester and an amine are used. Method of performing direct amidation reaction in the presence of a strongly basic catalyst; (2) After carrying out a Michael addition reaction between a (meth) acrylic acid ester and an amine, an amidation reaction with an amine is further carried out, and then the formation thereof. This is a method for synthesizing N-substituted (meth) acrylamide by liquid-phase thermal decomposition of an aminoamide, which is a substance, in the presence of a non-catalyst or an acidic catalyst (Patent Documents 1 to 3).

However, in the method (1), there is a problem that the Michael addition reaction of the (meth) acrylic acid ester and the amine proceeds at the same time as the amidation reaction, and a large amount of amino ester is produced as a by-product. In (2), an amino ester was first synthesized as a Michael adduct of a (meth) acrylic acid ester and an amine, and then the amino ester and the amine were amidated in the presence of a basic catalyst, and finally obtained. This is a method of thermally decomposing an aminoamide in the presence of a non-catalyst or an acidic catalyst. In this method, high-purity aminoamide can be easily obtained, but if the basic catalyst can be neutralized before being brought into the thermal decomposition step, polymerization trouble cannot be avoided. In addition, it is costly and time-consuming to remove the neutralized salt produced as a by-product by neutralization. Furthermore, when the thermal decomposition reaction is carried out without a catalyst, the decomposition reaction of deamine does not have a sufficient rate, so that the redeposition of the amine and the (meth) acrylic acid amide after the decomposition is likely to occur, which is aimed at high yield. The product cannot be obtained. In the thermal decomposition reaction in the presence of an acidic catalyst, there is a problem that the acidic catalyst by the amine after decomposition is neutralized and the catalytic activity is lost.

Japanese Unexamined Patent Publication No. 4-208258 Japanese Unexamined Patent Publication No. 6-199752 Japanese Unexamined Patent Publication No. 2012-97005

The subject of the present invention is to use an easy-to-handle (meth) acrylic acid ester as a starting material, and even under mild reaction conditions, N-substituted (meth) acrylamide, particularly (meth) acrylamide having a bulky cyclic substituent, long-chain alkyl. High-purity, high-yield, easy and inexpensive industrial production of N-substituted (meth) acrylamide, which is solid at room temperature and has a high boiling point such as (meth) acrylamide and polyfunctional (meth) acrylamide, which is difficult to produce by known methods. Is to provide a way to do it.

As a result of diligent studies to solve these problems, the present inventors have carried out a Michael addition reaction between the (meth) acrylic acid ester and alcohol and / or amine, and β-alkoxypropionic acid ester, β- After synthesizing an aminopropionic acid ester, a metal complex is added as a catalyst and an amidation reaction is carried out with an amine compound to obtain β-alkoxypropionic acid amide and β-aminopropionic acid amide as intermediates, and then a metal as a catalyst. We have found that the target compound N-substituted (meth) acrylamide is obtained by the liquid phase thermal decomposition reaction of β-alkoxypropionic acid amide and β-aminopropionic acid amide in the presence of a complex, and arrived at the present invention.

（各式中、Ｒ_１は水素原子またはメチル基を表す。ｎは１〜１０の整数であり、かつ、ｎ＝１の場合、Ｒ_２は炭素数１１〜３６の直鎖状又は分岐鎖状のアルキル基、アルキルエーテル基、脂環式炭化水素、芳香族炭化水素を表し、ｎ＝２〜１０の整数の場合、Ｒ_２は水素原子又は炭素数１〜３６の直鎖状又は分岐鎖状のアルキル基、アルキルエーテル基、脂環式炭化水素、芳香族炭化水素を表す。Ａは、一般式［３］もしくは［４］で表されるアルコキシ基もしくはアミノ基（式中のＲ_３は、炭素数１〜６の直鎖又は分岐鎖のアルキル基、アルキルエーテル基、脂環式炭化水素を表す。Ｒ_４とＲ_５は各々独立に水素原子又は炭素数１〜１０の直鎖状又は分岐鎖状のアルキル基、アルキルエーテル基、脂環式炭化水素、芳香族炭化水素を表す。又、Ｒ_４とＲ_５は、それらを担持する窒素原子と一緒になって、飽和５〜７員環（酸素原子を有するものを含む）を形成したものでもよい）を表し、Ｄは水素或いは炭素数１〜１０の直鎖又は分岐鎖のアルキレン基、アルキレンエーテル基、脂環式炭化水素、芳香族炭化水素、酸素原子を有する環状エーテル基を表し、Ｅはｎ価の連結基を表す。）

（２）一般式［１］で示されるβ−置換プロピオン酸アミドが、一般式［５］で示されるβ−置換プロピオン酸エステルと一般式［６］示されるアミン化合物とを、触媒として金属錯体の存在下で反応させて得ることを特徴とする前記（１）に記載の製造方法、

（各式中、Ｒ_１、Ｒ_２、ｎ、Ａ、ＤとＥは上記で定義したとおりである。Ｒ_６は炭素数１〜４の直鎖又は分岐鎖のアルキル基を表す。）
（３）金属錯体は、１分子中に１個の金属原子又は金属イオンを有する単核金属錯体、又は１分子中に２個以上の金属原子又は金属イオンを有する多核金属錯体であって、かつ、金属原子又は金属イオンはＨＳＡＢ則における硬いルイス酸或いは中間的な硬さのルイス酸であることを特徴とする前記（１）又は（２）に記載の製造方法、
（４）金属錯体は、１分子中に２個以上の有機配位子又は無機配位子を有し、かつ、少なくとも１個以上の配位子はＨＳＡＢ則における硬い塩基或いは中間的な硬さの塩基であり、ルイス酸とルイス塩基の組み合わせのいずれか１種であることを特徴とする前記（１）〜（３）のいずれか１項に記載の製造方法、
（５）金属錯体の金属原子又は金属イオンは、配位数が４〜１２、かつ、イオン半径が０．５〜１．５Åであることを特徴とする前記（１）〜（４）のいずれか１項に記載の製造方法、
（６）ルイス塩基は、ハロゲン化物イオン、水酸化イオン、酢酸イオン、トルエンスルホン酸イオン、メタンスルホン酸イオン、過塩素酸イオン、テトラフルオロホウ酸イオン、ヘキサフルオルリン酸イオン、フルオロスルホン酸イオン、トリフルオロメタンスルホン酸イオン、トリフルオロ酢酸イオン、２−（トリフルオロメチル）ベンゼンスルホン酸イオン、水、アミン、アルコ−ルからなる群より選ばれた少なくとも１種であることを特徴とする前記（１）〜（５）のいずれか１項に記載の製造方法、
（７）金属（原子又はイオン）は、鉄、ニッケル、銅（２価）、チタン、コバルト、ルテニウム、錫、インジウム、マンガン、亜鉛、ガリウム、スカンジウム、バナジウム、イットリウム、ランタノイドからなる群より選ばれた少なくとも１種であることを特徴とする前記（１）〜（６）のいずれか１項に記載の製造方法を提供するものである。 That is, the present invention
(1) N represented by the general formula [2], which comprises performing a liquid phase pyrolysis reaction in the presence of a metal complex as a catalyst using the β-substituted propionic acid amide represented by the general formula [1]. -Method for producing substituted (meth) acrylamide,

(In each equation, R ₁ represents a hydrogen atom or a methyl group. When n is an integer of 1 to 10 and n = 1, R ₂ is a linear or branched chain having 11 to 36 carbon atoms. Represents an alkyl group, an alkyl ether group, an alicyclic hydrocarbon, or an aromatic hydrocarbon, and in the case of an integer of n = 2 to 10, R ₂ is a hydrogen atom or a linear or branched chain having 1 to 36 carbon atoms. Represents an alkyl group, an alkyl ether group, an alicyclic hydrocarbon, or an aromatic hydrocarbon. A is an alkoxy group or an amino group represented by the general formula [3] or [4] (R ₃ in the formula is Represents a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl ether group, and an alicyclic hydrocarbon. R ₄ and R ₅ are independently linear or branched hydrogen atoms or 1 to 10 carbon atoms, respectively. chain alkyl group, alkyl ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon. Further, R ₄ and R ₅ together with the nitrogen atom carrying them, a saturated 5 to 7-membered ring It represents (including those having an oxygen atom), and D represents hydrogen or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene ether group, an alicyclic hydrocarbon, and an aromatic. It represents a cyclic ether group having a hydrocarbon and an oxygen atom, and E represents an n-valent linking group.)

(2) The β-substituted propionic acid amide represented by the general formula [1] is a metal complex using the β-substituted propionic acid ester represented by the general formula [5] and the amine compound represented by the general formula [6] as catalysts. The production method according to (1) above, which is obtained by reacting in the presence of.

(In each formula, R ₁ , R ₂ , n, A, D and E are as defined above. R ₆ represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
(3) The metal complex is a mononuclear metal complex having one metal atom or metal ion in one molecule, or a polynuclear metal complex having two or more metal atoms or metal ions in one molecule, and The production method according to (1) or (2) above, wherein the metal atom or metal ion is a hard Lewis acid or an intermediate hardness Lewis acid according to HSAB rules.
(4) The metal complex has two or more organic ligands or inorganic ligands in one molecule, and at least one or more ligands are hard bases or intermediate hardness according to HSAB rule. The production method according to any one of (1) to (3) above, wherein the base is any one of a combination of a Lewis acid and a Lewis base.
(5) Any of the above (1) to (4), wherein the metal atom or metal ion of the metal complex has a coordination number of 4 to 12 and an ionic radius of 0.5 to 1.5 Å. The manufacturing method according to item 1.
(6) Lewis bases are halide ion, hydroxide ion, acetate ion, toluene sulfonic acid ion, methane sulfonic acid ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, fluoro sulfonic acid ion. , Trifluoromethanesulfonic acid ion, trifluoroacetate ion, 2- (trifluoromethyl) benzenesulfonic acid ion, water, amine, alcohol, at least one selected from the group. 1) The production method according to any one of (5) to (5).
(7) The metal (atom or ion) is selected from the group consisting of iron, nickel, copper (divalent), titanium, cobalt, ruthenium, tin, indium, manganese, zinc, gallium, scandium, vanadium, ittrium, and lanthanoid. The production method according to any one of (1) to (6) above, which is characterized in that it is at least one kind.

According to the method of the present invention, N-substituted (meth) acrylamide can be easily produced from a starting material (meth) acrylic acid ester in high yield at low cost. Further, in the method of the present invention, a metal complex that is recyclable and has a small environmental load is used as a catalyst, and has a bulky cyclic substituent (meth) acrylamide, long-chain alkyl (meth) acrylamide, and polyfunctional (meth). ) Even with N-substituted (meth) acrylamide such as acrylamide, the reaction proceeds at a sufficient rate and high selectivity, troubles such as polymerization do not occur, there are few by-products of impurities, and high-purity products are produced in high yield. Can be obtained.

In the production method of the present invention, the catalytic mechanism of the metal complex consisting of Lewis acid and Lewis base in the amidation reaction of the amine compound and β-substituted propionic acid ester is not necessarily clear, but the amine is a hard Lewis base. Therefore, it is easy to coordinate to the empty coordination constellation of the metal or to replace the existing ligand of the metal, thereby activating the amine and smoothing the reaction even under mild conditions. The inventors speculate that it will progress. Also, in the liquid phase thermal decomposition of β-substituted propionic acid amide, alcohol and amine are easily coordinated to the metal complex, so that they are easily desorbed from β-substituted propionic acid amide, and the decomposition reaction is sufficient even in the low temperature region. The inventors speculate that it will proceed at a high speed.

The present invention comprises the following two steps (a) and (b), as β-substituted propionic acid amides, β-alkoxypropionic acid amide (general formula [7]) and β-aminopropionic acid amide (general formula [7]). 8]) _{(wherein, R 1 ~R 5, n,} a, D and E is to provide a method for producing is as defined above.) efficiently and industrially.

The present invention consists of three steps below (a) to (c), the general formula [9] _{(wherein, R 1, R 2, n} , D and E are as defined above.) In It provides a method for efficiently industrially producing the indicated N-substituted (meth) acrylamide.

(A) Production of β-substituted propionic acid ester (a-1) Production process of β-alkoxypropionic acid ester (Meta) Acrylic acid ester and alcohol are mixed in molar ratio (alcoal) in the presence of a basic catalyst. / (Meta) acrylic acid ester) can be reacted in the range of 1.0 or more and the reaction temperature in the range of 0 to 120 ° C. to produce β-alkoxypropionic acid ester.

(A-2) Production process of β-aminopropionic acid ester A reaction of a (meth) acrylic acid ester with a primary or secondary monofunctional amine in a molar ratio (amine / (meth) acrylic acid ester) of 1.0 or more. The β-aminopropionic acid ester can be produced by reacting in a temperature range of −10 to 120 ° C.

(B) Production process of β-substituted propionic acid amide
With the amine compound represented by the general formula [6] and the β-substituted propionic acid ester (β-alkoxypropionic acid ester and β-aminopropionic acid ester) represented by the general formula [5] and produced in the step (a). Can be reacted in the presence of a metal complex to produce β-substituted propionic acid amides (β-alkoxypropionic acid amides and β-aminopropionic acid amides) represented by the general formula [1].

(C) Production step of N-substituted (meth) acrylamide The β-substituted propionic acid amide produced in step (b) produces an alcohol or amine at the β-position by a liquid phase pyrolysis reaction in the presence of a metal complex. It can be desorbed to produce N-substituted (meth) acrylamide.

Hereinafter, each step of the present invention will be described in detail.
Step (a) This step is carried out by reacting the (meth) acrylic acid ester with alcohol in the presence of a basic catalyst, and the alkoxypropionic acid ester is produced in good yield without complicated operations. It can be obtained (a-1). Further, it is carried out by reacting a (meth) acrylic acid ester with a primary or secondary monofunctional amine in the presence of a basic catalyst or in a non-catalytic condition, and the yield is good without complicated operations. Aminopropionic acid ester can be obtained (a-2). Since the (meth) acrylic acid ester used in the step is easily polymerized, it is preferably carried out in the presence of a radical polymerization inhibitor.

In step (a), a stoichiometric amount of alcohol or amine should be used as the compounding ratio of alcohol or primary or secondary monofunctional amine to (meth) acrylic acid ester. However, it is preferable to use it in an excessive amount because it promotes the completion of the reaction. Generally, alcohol or amine is used in the range of 1 to 30 times by mole with respect to 1 mol of (meth) acrylic acid ester. Further, the range of 1.05 to 20 times mol is preferable, and the range of 1.1 to 10 times mol is particularly preferable. Alcor or amine can be used as a solvent for the reaction at the same time as the raw material for the reaction. Further, since the amine has a basic catalytic action, the reaction can proceed rapidly without adding a separate catalyst. If the compounding ratio of alcohol or amine exceeds 30 times the molar amount of the (meth) acrylic acid ester, it is disadvantageous in terms of economy such as recovery after the reaction.

The basic compound used in the step (a) is not particularly limited and may be either an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metals such as lithium, sodium and potassium, carbonates, hydrogen carbonates and phosphates, and examples of organic bases include tertiary amines, pyridines and alkoxides of the alkali metals. And so on. In addition, from the viewpoint of preventing the generation of impurities, lithium methoxide, lithium ethoxyoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide. , Potassium butoxide is preferable, and it is most preferable to use a metal alkoxide made of the same alcohol as the alcohol used in the step.

The basic compound may be used alone or in combination of two or more. Among these, basic metal alkoxides that are not usually commercially available can be prepared by utilizing the boiling point difference of alcohol. For example, when the primary alcohol of the raw material is butyl alcohol, sodium butoxide, potassium butoxide, and lithium butoxide are preferable. However, since the catalyst itself is expensive, it is necessary to add butanol to inexpensive sodium methoxide and distill off the metanol to easily obtain sodium butoxide before carrying out the reaction. Is preferable. The amount of these basic compounds added is preferably 0.05 to 20 mol% with respect to the (meth) acrylic acid ester in step (a).

The reaction temperature and reaction time of the step (a) are appropriately selected according to the (meth) acrylic acid ester and alcohol, which are the starting materials of the reaction, the type of amine, the type of catalyst, and the compounding ratio. However, usually, the reaction temperature is about 0 to 120 ° C., and the reaction time is in the range of 0.5 to 48 hours. The preferable reaction temperature is about 20 to 100 ° C., and the reaction time is in the range of 1 to 36 hours. If the reaction temperature is less than 0 ° C. or the reaction time is less than 0.5 hours, the rate of the Michael addition reaction will be significantly reduced, while if the reaction temperature exceeds 120 ° C., alcohol and amine will move out of the reaction system. It is not preferable because it facilitates desorption and at the same time increases decomposition of the product and other side reactions. If the reaction time exceeds 48 hours, there will be disadvantages in productivity and cost.

An excess of alcohol or amine, which is a starting material for the reaction, can provide an action as a reaction solvent, but a solvent may be used if necessary. The reaction solvent in the step (a) is not particularly limited, and a general solvent can be used as long as it does not cause a side reaction with the starting material, product and basic compound of the reaction.

After the reaction in step (a) is completed, the reaction solution is neutralized with an inorganic or organic acidic compound such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, etc., or by contact treatment with a strong acid cation exchange resin, if necessary. Neutralization can be carried out. Then, if there are precipitated salts, they are separated by filtration, and the reaction solvent, unreacted alcohol, amine and other by-products in the filtrate are removed under normal pressure or reduced pressure, and the target compound of the step is removed. Β-alkoxypropionic acid ester and β-aminopropionic acid ester can be obtained. Further, if necessary, purification can be achieved by a purification method such as vacuum distillation.

The reaction in the step (a) is preferably carried out in the presence of a radical polymerization inhibitor. Known polymerization inhibitors can be used. For example, hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butylparahydroquinone, 2,5-di-tert-butylhydroquinone, 2, Phenol compounds such as 4-dimethyl-6-tertbutylphenyl and hydroquinone monomethyl ether, N-isopropyl-N'-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl -Para-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-para-phenylenediamine, N, N'-diphenyl-para-phenylenediamine, N, N'-di-2-naphthyl-para- Paraphenylenediamines such as phenylenediamine, amine compounds such as thiodiphenylamine, 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1- Examples thereof include piperidine-1-oxylfree radical compounds such as oxyl and acetamidotetramethylpiperidin-1-oxyl. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor added is 1 to 10000 ppm, preferably 5 to 5000 ppm with respect to (meth) acrylic acid.

Step (b) In this step, the β-substituted propionic acid ester obtained in step (a) above is used in the presence of a metal complex as a catalyst, and the yield is good without complicated operations. The β-substituted propionic acid amide represented by the general formula [1] is produced by an amidation reaction with the amine compound represented by 6].

The amine compounds used in the present invention are monofunctional amine compounds having only one secondary amino group in one molecule and one or more primary amino groups in one molecule, and / and the first. A polyfunctional amine compound having two or more secondary amino groups is included. Any one of these monofunctional amine compounds or polyfunctional amine compounds may be used, or two or more thereof may be used in combination.

The monofunctional amine compound is an N-mono-substituted or N, N-disubstituted substituent having 11 to 36 carbon atoms (linear or branched alkyl group, alkyl ether group, alicyclic hydrocarbon, aromatic). Saturated or unsaturated, linear or branched or cyclic aliphatic monofunctional primary amines and monofunctional secondary amines (including those having an aromatic ring) having (including those representing hydrocarbons), said. Monofunctional primary aromatic amines and monofunctional secondary aromatic amines having similar substituents having 11 to 36 carbon atoms, and monofunctional primary alkanos having similar substituents having 11 to 36 carbon atoms. Luamine and monofunctional secondary alkanolamine, monofunctional primary etheramine and monofunctional secondary etheramine having the same substituents having 11 to 36 carbon atoms as described above, and the same substitutions having 11 to 36 carbon atoms as described above. A monofunctional primary aminoamine having a group and a monofunctional secondary aminoamine. Specific examples of linear or branched alkyl groups having 11 to 36 carbon atoms include undecyl group (C11), lauryl group (C12), tridecyl group (C13), myristyl group (C14), and cetyl group (Cetyl group). C16), stearyl group (C18), oleyl group (C18), araquil group (C20), behenyl group (C22), lignoceryl group (C24), cellotoyl group (C26), montanyl group (C28), melissyl group (C30) , Dotria-contanoyl group (C32), tetratria-contanoylamine (C34), hexatria-contanoyl group (C36) saturated or unsaturated linear or branched chains.

The polyfunctional amine compound is an N-mono-substituted or N, N-disubstituted substituent having 1 to 36 carbon atoms (linear or branched alkyl group, alkyl ether group, alicyclic hydrocarbon, aromatic). Saturated or unsaturated, linear or branched or cyclic aliphatic polyfunctional primary amines, polyfunctional secondary amines or polyfunctional primary and secondary having (including those representing hydrocarbons). Blended amines, polyfunctional primary aromatic amines having the same substituents having 1-36 carbon atoms, polyfunctional secondary aromatic amines, or polyfunctional primary and secondary blended aromatic amines. , Polyfunctional primary alkanolamines, polyfunctional secondary alkanolamines or polyfunctional primary and secondary blended alkanolamines having the same substituents having 1-36 carbon atoms, the same as above. Polyfunctional primary etheramine and polyfunctional secondary etheramine having substituents having 1 to 36 carbon atoms or a polyfunctional primary and secondary blended etheramine, the same as described above having 1 to 36 carbon atoms. It is a polyfunctional primary aminoamine, a polyfunctional secondary aminoamine, or a polyfunctional primary and secondary blended aminoamine having a substituent of. Specific examples of the linear or branched alkyl group having 1 to 36 carbon atoms include a methyl group (C1), an ethyl group (C2), a (iso) propyl group (C3), and an (iso) butyl group (iso) butyl group ( C4), (iso) pentyl group (C5), (iso) hexyl group (C6), (iso) heptyl group (C7), (iso) octyl group (C8), (iso) nonyl group (C9), (iso) ) Decyl group (C10), undecyl group (C11), lauryl group (C12), tridecyl group (C13), myristyl group (C14), cetyl group (C16), stearyl group (C18), oleyl group (C18), araquil Group (C20), behenyl group (C22), lignoceryl group (C24), cellotoyl group (C26), montanyl group (C28), meliscil group (C30), dotria-contanoyl group (C32), tetratria-contanoylamine ( C34), a saturated or unsaturated linear or branched chain of a hexatria-contanoyl group (C36) can be mentioned.

The polyfunctional amine compound has one or more primary amino groups or two or more secondary amino groups in one molecule, and is arbitrarily selected from the group consisting of amino groups of the monofunctional amine compound. It is composed of a combination of two or more selected amino groups. From the viewpoint of industrial availability and high safety, the aliphatic polyfunctional amines include ethylenediamine, propylenediamine, isopropylenediamine, 1,3-diamino-2-propanol, and 1,2-dihydroxyethylenediamine. , 2,3-Dihydroxy-1,4-butanediamine, 1,8-diamine-3,6-dioxaoctane, 1,10-diamino-4,7-dioxadecane, 1,1'-(1,2-) Ethandiyl bis (oxy)) bis (3-amino-2-propanol]), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, trimethylhexamethylenediamine, hexamethylenediamine, tris (2-Aminoethyl) amine, n-phenyl-ethylenediamine, ptolessin (1,4-butanediamine), spermidin (N- (3-aminopropyl) -1,4-diaminobutane), spermin (N, N-bis) (3-Aminopropyl) butane-1,4-diamine, tris (3-aminopropoxymethyl) aminomethane, 4,7,10-trioxa-1,13-tridecaneamine, 1,4-bis (2-hydroxy) -3-Aminopyropoxy) butane, polyetherdiamine and the like are preferable, and as the alicyclic polyfunctional amines, isophoronediamine, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, etc. 2,5-Dimethylpiperazin, 4-aminomethylpiperazin, mentandiamine, N-aminoethylpiperazin, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane Adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, methylenedianiline and the like are preferable. Examples of the aromatic polyfunctional amines include m-phenylenediamine and p-phenylenediamine. o-phenylenediamine, diaminodiphenylmethane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N'-dimethyl-m − Phenylene diamine, 2,4-diaminoanisole, amidol, xylylene diamine and the like are preferable. These polyfunctional amine compounds may be used alone or in combination of two or more.

The metal complex used in the present invention is selected from the group consisting of a mononuclear metal complex having one metal atom or metal ion in one molecule and a polynuclear metal complex having two or more metal atoms or metal ions in one molecule. One or more of the above.

The metal atom or metal ion of the mononuclear metal complex and the polynuclear metal complex is a hard Lewis acid or an intermediate hardness Lewis acid according to HSAB law. The HSAB rule (Hard and Soft Acids and Bases rule) is known to classify the compatibility of Lewis acid and Lewis base using the expression hard and soft, and "hard Lewis acid" has a high charge density and is known to be classified. A cation that is difficult to be polarized and has a small size, "soft Lewis acid," is a cation that has a low charge density, is relatively easy to be polarized, and has a large size. On the other hand, the "hard Lewis base" is a small base having a large electronegativity and is difficult to be polarized, and the "soft Lewis base" is a large base having a small electronegativity and being easily polarized. There are also intermediate acids (Lewis acid with intermediate hardness) and bases (Lewis base with intermediate hardness), and according to HSAB rules, "hard Lewis acid" and "hard Lewis base". , "Soft Lewis acid" and "soft Lewis base" are empirical rules that easily interact with each other.

Further, the metal atom or metal ion of the metal complex used in the present invention is characterized by having a coordination number of 4 to 12 and an ionic radius of 0.5 to 1.5 Å. If the coordination number and the ionic radius are within this range, the metal atom or metal ion corresponds to a hard Lewis acid or an intermediate hardness Lewis acid according to HSAB law, and is a hard Lewis base or an intermediate hardness Lewis acid. When combined with a base, it can exhibit sufficiently high activity as a catalyst for the amidation reaction of the present invention. Specifically, the metal (atom or ion) is composed of iron, nickel, copper (divalent), titanium, ruthenium, tin, indium, magnesium, calcium, manganese, zinc, gallium, scandium, vanadium, yttrium, and lanthanoid metal. At least one metal selected from the group.

The metal complex used in the present invention has two or more organic or inorganic ligands in one molecule, and at least one or more ligands are hard Lewis bases or intermediates in HSAB law. It is a Lewis base with a high hardness.

The Lewis base used in the present invention is a halide ion, a hydroxide ion, an acetate ion, a toluene sulfonate ion, a methane sulfonate ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a fluorosulfone. It is at least one ligand selected from the group consisting of acid ion, trifluoromethanesulfonic acid ion, trifluoroacetate ion, 2- (trifluoromethyl) benzenesulfonic acid ion, water, amine, and alcohol.

When at least one metal atom or metal ion selected from the group of Lewis acids and at least one ligand selected from the group of Lewis bases are arbitrarily combined, any one or more metal complexes are used. Can be obtained. The metal complex catalyst used in the present invention is a mononuclear metal complex composed of two or more same or different ligands centered on one metal atom or metal ion in one molecule, and one molecule. It is a polynuclear metal complex composed of two or more same or different ligands per one metal atom or metal ion centered on two or more same or different metal atoms or metal ions. Furthermore, it includes a metal cluster having a bond between metal atoms as a polynuclear metal complex. Specifically, the catalysts that can be used in steps (b) and (c) of the present invention include iron, nickel, copper (divalent), titanium, cobalt, ruthenium, tin, indium, magnesium, calcium, manganese, as metals. Zinc, gallium, scandium, vanadium, yttrium, lanthanoid, and as ligands, halide ion, hydroxide ion, acetate ion, toluene sulfonate ion, methane sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexa Consists of any combination of fluorinate ion, fluorosulfonic acid ion, trifluoromethanesulfonic acid ion, trifluoroacetate ion, 2- (trifluoromethyl) benzenesulfonic acid ion, water, amine, alcohol Examples thereof include mononuclear metal complexes and / or polynuclear metal catalysts containing clusters. These metal complexes can be used alone or in admixture of two or more. Iron, nickel, copper, tin, indium, manganese, zinc, scandium, vanadium, yttrium, lanthanoid acetate, toluene sulfonate, methane sulfonate, perchlorate from the standpoint of being generally industrialized and readily available. , Tetrafluoroborate, fluorosulfonate, trifluoromethanesulfonate, trifluoroacetate are more preferred.

(B) The reaction in the step may be a batch method or a continuous method. For example, in the case of a batch reaction, the shape of the metal complex is preferably powder or fine particles. Further, in a powdery or fine particle catalyst, a state of being uniformly dissolved or dispersed by an amine compound as a raw material, a β-substituted propionic acid ester obtained in step (a), or an organic solvent added as needed. Since it is easy to handle, it is more preferable to use it. For example, in the case of a continuous reaction, it is preferable to use the metal complex in a state of being fixed to an appropriate catalyst carrier in the reaction.

In step (b), the molar ratio of the β-substituted propionic acid ester to the amine compound is such that either the functional group (amino group) of the amine compound or the functional group (ester group) of the β-substituted propionic acid ester is excessively used. This promotes the completion of the reaction. In the present invention, the amount of the ester group compounded is in the range of 1.00 to 20 times the molar amount of the amino group from the viewpoint that the product β-substituted propionic acid amide of step (b) can be easily separated and purified from the reaction solution. Is preferable, and a range of 1.01 to 10 times mol is more preferable. The β-substituted propionic acid ester used in excess can be used as a solvent for the reaction at the same time, but if the amount exceeds this amount, it is disadvantageous in terms of economy such as recovery of the excess charged after the reaction.

(B) The amount of the metal complex used in the step depends on the type and properties (liquid or solid at the reaction temperature) of the β-substituted propionic acid ester and amine compound, the number of amino groups, solubility, reaction temperature and the solvent used. Although there is an optimum range, it is usually in the range of 0.1 to 50 mol%, preferably 0.5 to 20 mol%, particularly preferably 1 to 10 mol% with respect to the amino group.

The reaction temperature and reaction time of step (b) are appropriately selected according to the type and compounding ratio of the β-substituted propionic acid ester synthesized in step (a) and the raw material amine compound, but the reaction selectivity is selected. The reaction temperature is about 0 to 150 ° C., and the reaction time is in the range of 0.1 to 48 hours because of the high reaction rate and the relatively high reaction rate. The preferred reaction temperature is about 20 to 150 ° C. and the reaction time is in the range of 0.5 to 36 hours, and the particularly preferable reaction temperature is about 40 to 100 ° C. and the reaction time is in the range of 1.0 to 24 hours. Is. (A) The β-substituted propionic acid ester obtained in the step can be excessively blended to provide an action as a reaction solvent, but a solvent may be used if necessary. The reaction can be carried out under normal pressure, reduced pressure, or under pressure using a pressurizing device such as an autoclave. The reaction solvent is not particularly limited, and a general solvent can be used as long as it does not cause a side reaction with the starting material, product and metal complex of the reaction. Examples thereof include hydrophobic solvents such as toluene and xylene, and hydrophilic solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), ethylene glycol and glycerin. When a solvent is used, the amount used is usually in the range of 20 to 1000% by weight, preferably in the range of 50 to 500% by weight, particularly preferably 100, based on the total amount of the β-substituted propionic acid ester and the amine compound. It is in the range of ~ 300% by weight. When the reaction solvent is used for the purpose of dissolving the raw material or improving the stirring efficiency, a sufficient effect may not be expected if it is less than 20% by weight, and if it exceeds 1000% by weight, it is uneconomical at the same time. It may cause a decrease in reaction rate.

When the reaction in step (b) is carried out by a batch method, for example, the β-substituted propionic acid ester obtained in step (a), the amine compound as a raw material, a metal complex and a solvent are charged in a reaction vessel, and if necessary. After replacing the inside of the reaction vessel and the inside of the reaction solution with an inert gas, the reaction temperature is adjusted to a predetermined value while maintaining a suspended or dissolved state by stirring, and the reaction is carried out in a predetermined time. Further, in the reaction solution mixture after the reaction is completed, for example, when the metal complex exists in a solid state, the solid solution may be separated and recovered by filtration or centrifugation with a filter, or separated. Instead, it may be decanted, concentrated, precipitated with water or another solvent, extracted, etc., and then reused as it is (step B) or carried over to the next step (step C). On the other hand, when the metal complex after completion of the reaction is dissolved in the reaction solution, the reaction solution may be concentrated and then reused as it is (step B) or carried over to the next step (step C). Further, regardless of the dissolved state or the dispersed state of the metal complex after the completion of the reaction, the reaction solution can be carried over to the next step (step c) without being concentrated.

In steps (b) and (c) of the present invention, the coordination structure of the metal complex as a catalyst may be changed as the reaction progresses, and the hard acid or intermediate in the HSAB rule described above may be changed. A combination of a metal atom or metal ion corresponding to an acid and various ligands corresponding to a hard base or a base having an intermediate hardness according to HSAB law, for example, a raw material amine compound, a reaction product or an intermediate, and the like. The metal complex composed of the above is not particularly limited. That is, the type, concentration, proportionality, etc. of the ligand may change as the reaction progresses, and the type and number of metal complexes may change according to the change, and as a result, the metal complex may change. The optimum coordination structure in the reaction system will be taken. The reason why the amidation reaction between the amine compound of the present invention and the β-substituted propionic acid ester can proceed at low temperature with high yield and high selectivity is not clearly understood, but the inventors have stated that the reaction state. It is presumed that the high activity of the catalyst is provided by the fact that the structure of the metal complex can always maintain the optimum state by self-adjustment.

Step (c) In this step, the β-substituted propionic acid amide obtained in step (b) is used to desorb the solvent or amine by the liquid phase pyrolysis reaction at a predetermined reaction temperature and operating pressure. , (B) Distillation and recovery in order of boiling point together with the reaction solvent, unreacted raw materials, by-products, etc. brought in from step (b) to obtain the desired N-substituted (meth) acrylamide as a distillate component or distillate residue. be able to. Further, depending on the physical properties of the target product, raw material, by-product and reaction solvent, the target product is separated and purified by a known method such as precipitation, washing, extraction, centrifugation, or separation with an ion exchange resin instead of distillation. Can be obtained. Further, if necessary, the obtained target product can be obtained with a high-purity target product by a known method such as precision distillation, recrystallization, sublimation, permeation, and adsorption. The reaction in this step can be carried out using a mixture of the crude β-substituted propionic acid amide obtained in step (b) and the metal complex, and the metal complex is added to the separated and purified β-substituted propionic acid amide. Can be done. It is preferable to carry out in the presence of a polymerization inhibitor as in the step (a). As the polymerization inhibitor, known ones can be used as in step (a).

In the step (c), the same or different metal complex catalyst as in the step (b) may be used, or the same or different polymerization inhibitor as in the step (a) may be used. The amount of the metal complex added is preferably 1 to 50 mol% with respect to the raw material β-substituted propionic acid amide (alkoxypropionic acid amide or aminopropionic acid amide) in step (c). The amount of the polymerization inhibitor added is 1 to 10000 ppm, preferably 5 to 5000 ppm with respect to the β-substituted propionic acid amide.

(C) The reaction temperature of the step is usually about 80 to 200 ° C., and the reaction time is in the range of 1 to 40 hours. The preferable reaction temperature is about 100 to 150 ° C., and the reaction time is in the range of 2 to 30 hours. If the reaction temperature is less than 80 ° C. or the reaction time is less than 1 hour, the pyrolysis reaction rate will be significantly reduced, while if the reaction temperature exceeds 200 ° C., the polymerization of products and other side reactions will increase. Not preferred. Further, when the reaction time exceeds 40 hours, there are disadvantages in productivity and cost.

(C) In the step, a solvent may be used if necessary. The reaction solvent is not particularly limited, and a general solvent can be used as long as it does not cause a side reaction with the reaction starting material, product or metal complex. The appropriate range when a solvent is used is usually in the range of 10 to 1000% by weight, preferably 50 to 500% by weight, based on the β-substituted propionic acid amide.

Table 1 shows the catalysts used in the examples and comparative examples of the present invention. The metal complex shown here is merely for explaining the present invention, and does not limit the present invention in any way.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. The abbreviations for β-substituted propionic acid ester, β-substituted propionic acid amide, N-substituted (meth) acrylamide and the materials used described in Examples and Comparative Examples are as follows.
(1) (Meta) Acrylic acid ester MA: Methyl acrylate EA: Ethyl acrylate BA: Butyl acrylate MMA: Methyl methacrylate (2) Amine compound DMA: Dimethylamine DEA: Diethylamine DBA: Dibutylamine LA: Laurylamine SA : Stearis amine
BAN: Bis (aminomethyl) norbornane
EDA: Ethylenediamine
IPDA: Isopropylenediamine
BDA: Butyrene diamine
OBBA: 4,4'-oxybis (benzeneamine)
DTA: Diethylenetriamine
APDA: N- (3-aminopropyl) -1,3-propanediamine
TETA: Triethylenetetramine
BPDA: N, N'-bis (2-aminoethyl) -1,3-propanediamine
TEPA: Tetraethylene pentamine
NEDA: Nonaethylenedecamine
BABB: 1,4-bis (2-hydroxy-3-aminopropoxy) butane
DAHO: 1,6-diamino-2,5-hexanediol
DADO: 1,8-diamine-3,6-dioxaoctane
DADD: 1,10-diamino-4,7-dioxadecane
BHBA: N, N'-bis (2-hydroxyethyl) -1,4-butanediamine
BMHA: N, N'-bismethoxymethyl-1,6-hexanediamine
TAPA: Tris (3-aminopropoxymethyl) aminomethane
TODA: 4,7,10-trioxatridecane-1,3-diamine
PTPA: 3,3', 3 "-(1,2,3-propanetriyltriyltris (oxy) tris (1-propanamin)
(3) β-substituted propionic acid ester MPM: β-methoxypropionate methyl MPE: β-methoxypropionate ethyl EPE: β-ethoxypropionate ethyl EPM: β-ethoxypropionic acid methyl MPB: β-methoxypropionate butyl DMAPM : Methyl β-dimethylaminopropionate DEAPM: Methyl β-diethylaminopropionate DMAPE: Ethyl β-dimethylaminopropionate DEAPE: Ethyl β-diethylaminopropionate DBAPM: Methyl β-dibutylaminopropionate (4) β-alkoxypropionic acid Amide EPM-LA: MPM and LA amidation reaction product MPM-SA: EPM and SA amidation reaction product MPM-BAN: MPM and BAN amidation reaction product EPE-EDA: EPE and EDA amidation Reaction product MPB-BDA: MPB and BDA amidation reaction product MPM-OBBA: MPM and OBBA amidation reaction product MPM-DAHO: MPM and DAHO amidation reaction product MPE-BPDA: MPE and BPDA Amidation reaction product MPM-BHBA: Amidation reaction product of MPM and BHBA MPE-BMHA: Amide reaction product of MPE and BMHA (5) β-aminopropionic acid amide DMAPM-DTA: Amidation of DMAPA and DTA Reaction product DEAPM-IPDA: Amide reaction product of DEAPM and IPDA DBAPM-SA: Amide reaction product of DBAPM and SA DEAPM-APDA: Amide reaction product of DEAPM and APDA DMAPE-TETA: DMAPE and TETA Amidation reaction product DEAPM-TEPA: Amidation reaction product of DEAPM and TEPA DEAPE-NEDA: Amidation reaction product of DEAPE and NEDA DMAPM-BABB: Amidation reaction product of DMAPM and BABB DEAPE-DADO: With DEAPE DADO amidation reaction product DEAPE-DADD: DEAPE and DADD amidation reaction product DBAPM-TAPA: DBAPM and TAPA amidation reaction product DEAPM-TODA: DEAPM and TODA amidation reaction product DEAPE-PTPA: Amidation reaction product of DEAPE and PTPA (6) N-substituted (meth) acrylamide LMAM: Lauryl methacrylate SAM: Stearyl acrylamide
NBBAM: Norbornane Bisacrylamide EBA: N, N'-Ethylene Bisacrylamide IPBA: Isopropylene Bisacrylamide
BBA: Butylene bisacrylamide
OBBAM: 4,4'-oxybis (benzeneacrylamide)
TADTA: N, N', N "-tris-acryloyl diethylenetriamine
BPPA: N, N-bis (3-((1-oxo-2-propen-1-yl) amino) propyl) -2-propene amide
TAETA: N, N', N ", N'"-tetraacryloylethylenetetraamine PPPA: N, N'-1,3-propane Özilbis (N- (2- (1-oxo-2-propene-1-) Il) amino) ethyl) -2-propene amide
PAETA: Pentaacryloyl ethylenepentaamine
NAEDA: Nonacryloyl ethylenedecaamine
BBBA: N, N'-(1,4-butane Özil bis (oxo (2-hydroxy-3,1-propane Özil)) bis (2-propene amide)
BAMHO: 1,6-bisacrylamide-2,5-hexanediol
BHBAM: N, N'-bis (2-hydroxyethyl) -1,4-butylene bisacrylamide
BAMDO: 1,8-bisacrylylamide-3,6-dioxaoctane
BMADO: 1,8-bismethacrylamide-3,6-dioxaoctane
BAMDD: 1,10-bisacrylamide-4,7-dioxadecane
BMWA: N, N'-bismethoxymethyl-1,6-hexyldiacrylamide
TAPAM: N- (tris (3-acrylamide propoxymethyl) methyl) acrylamide TDBAM: N, N'-(4,7,10-trioxatridecamethylene) bisacrylamide PTPAM: N, N'', N ""- (1,2,3-Propanetriyl (oxy-3,1-propanediyl)) Tris (2-propenamide)
(7) Alcor compound MeOH: Methanol EtOH: Ethanol BuOH: Butanol (8) Basic catalyst SM: Sodium methoxyde SE: Sodium ethoxydo LiOMe: Lithium methoxyde KOMe: Potassium methoxyde KOEt: Potassium ethoxy Do KOBu: Potassium Butoxyd NaOH: Sodium Hydroxide KOH: Potassium Hydroxide (9) Antipolymer TDA: Thiodiphenylamine HQ: Hydroquinone MeOH: Hydroquinone Monomethyl Ether TEMPO: 2,2,6,6-Tetramethylpiperidin-1-oxyl TBC: 4-tert-Butylcatechol BHT: Dibutylhydroxytoluene DDA: Styrylated-N-aminobiphenyl W-300: 4,4'-butylidenebis (6-tert-butyl-m-cresol)

Example 1
(A-1) 259.0 g (3 mol) of methyl acrylate (MA) and 0.13 g of MEHQ were placed in a 1000 mL flask equipped with a stirrer, a thermometer, a dropping device and a condenser, and sodium methoxyde (SM) was charged therein. ) A mixed solution consisting of 0.16 g (3 mmol) and 106.0 g (3.3 mol) of methanol (MeOH) was gradually added with stirring. During that time, the temperature of the reaction mixture was kept below 40 ° C. After completion of the addition, the temperature of the reaction mixture was raised to 60 ° C. with stirring, and the reaction was continued for 6 hours while further refluxing the metalol. Then, the reaction solution was returned to room temperature and neutralized with the equivalent amount of sulfuric acid, and then the unreacted raw material was removed by distillation to obtain 352.5 g of methyl β-methoxypropionate (abbreviated as MPM). The purity was 99.9% and the yield was 99%.

(B-1) 300 g (2.5 mol, purity 99.9%) of MPM obtained in step (a-1), SA 539 g (2) in a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser. .0 mol), 34.6 g (0.1 mol) of iron (II) trifluoromethanesulfonate as a metal complex and 420 mL of DMF as a solvent were added, and the reaction solution was heated to 80 ° C. with stirring, and further as a by-product. The reaction was continued at 80 ° C. for 2 hours while removing some methanol. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and it was confirmed by sampling that the reaction yield reached 98%. Then, the reaction solution was transferred to a distillation apparatus, and the solvent and unreacted raw materials were recovered. The distillate residue was recrystallized twice with acetone to obtain a white solid. The purity of the product was 99.9% by gas chromatography analysis, and the product was the target compound β-methoxy-N by analysis of the infrared absorption spectrum (IR) with the ^{nuclear magnetic resonance spectrum (1 H-NMR).} -It was confirmed that it was stearylamide (abbreviated as MPM-SA).

Examples 2-8
(A-2) to (I-10) and (B-2) to (B-10) In Example 1, the starting material, catalyst, solvent, polymerization inhibitor and reaction conditions of each step are as shown in Table 2. The reaction of step (a) and step (b) was carried out in the same manner as in Example 1, and the identification of each product was carried out by ¹ H-NMR and IR analysis. Table 2 shows the reaction yield of each step. Depending on the reaction temperature, the alcohol produced as a by-product during the reaction can be removed by distillation under normal pressure or reduced pressure after the reaction is completed. When a solvent is used in the reaction, the solvent can be recovered by distillation after the reaction is completed. Further, purification can be performed by a known method such as neutralization, washing, extraction, recrystallization, ion exchange resin treatment, and chromatography, depending on the state of the target compound and physical properties such as solubility.

Example 11
(A-11) MA 216.0 g (2.5 mol), MEHQ 0.11 g, and SM 0.07 g (1 mmol) were charged in this order in a 1000 mL autoclave, and then the mixed solution was cooled to 0 ° C. and liquefied DMA 124. .4 g (2.8 mol) was added. After the addition, the reaction mixture was heated to 40 ° C. with stirring, and the reaction was continued for 6 hours under pressurized conditions. Then, the reaction solution was returned to room temperature, neutralized with an equivalent amount of sulfuric acid, and then the unreacted raw material was removed by distillation to obtain 323.7 g of methyl β-dimethylamino-propionate (abbreviated as DMAPM). The purity was 99.9% and the yield was 98%.

(B-11) DMAPM 300 g (2.3 mol, purity 99.9%), DTA 51.6 g obtained in step (a-11) in a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser. (0.5 mol), 11.1 g (0.03 mol) of nickel trifluoromethanesulfonate (II) was added, the reaction solution was heated to 60 ° C. with stirring, and 60 while removing methanol as a by-product. The reaction was continued at ° C. for 1 hour. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and it was confirmed by sampling that the reaction yield reached 98%. Then, the reaction solution was transferred to a distillation apparatus, and the solvent and unreacted raw materials were recovered to obtain a white solid. The purity of the product was 99.2% by gas chromatography analysis, and the product was an amidation reaction between DMAPM and DTA by analysis of infrared absorption spectrum (IR) with ^{nuclear magnetic resonance spectrum (1 H-NMR).} It was confirmed that it was the target compound (abbreviated as DMAPM-DTA) obtained in.

Examples 12-22
(I-12) to (I-22) and (B-12) to (B-22) In Example 11, the starting material, catalyst, solvent, polymerization inhibitor and reaction conditions of each step are as shown in Table 3. The reaction of step (a) and step (b) was carried out in the same manner as in Example 11, and the identification of each product was carried out by ¹ H-NMR and IR analysis. The reaction yield of each step is shown in Table 3. Depending on the reaction conditions, the alcohol produced as a by-product during the reaction can be removed by distillation under normal pressure or reduced pressure after the reaction is completed. In the reaction under normal pressure, a 1000 mL flask equipped with a stirrer, a thermometer and a condenser was used instead of the autoclave. When a solvent is used in the reaction, the solvent can be recovered by distillation after the reaction is completed. Further, purification can be performed by a known method such as neutralization, washing, extraction, recrystallization, ion exchange resin treatment, and chromatography, depending on the state of the target compound and physical properties such as solubility.

Example 23
(H-23) The high-purity MPM-SA 355 obtained in Example 1 of step (1) using a 1000 mL reactive distillation apparatus equipped with a stirrer, a thermometer, a gas introduction line and a condenser. 6 g (1.0 mol), 0.711 g of TDA as a polymerization inhibitor, 36.2 g (0.1 mol) of copper (II) trifluoromethanesulfonate as a metal complex, and 250 g of xylene as a solvent were added. Then, a trace amount of nitrogen gas was flowed as a carrier, the temperature of the reaction mixture was raised to 110 ° C. while stirring, and MeOH produced by the liquid phase pyrolysis reaction was distilled off under normal pressure. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and the precipitated solid substance was separated by filtration to obtain a crude monomer. The obtained crude monomer was recrystallized twice with acetone to obtain a white powder having a melting point of 71 to 72 ° C. The purity of the product was 99.4% by gas chromatography analysis, and the product was obtained by analysis of the infrared absorption spectrum (IR) with a ^{nuclear magnetic resonance spectrum (1 H-NMR).} ) Was confirmed.

Examples 24-32
(H-24) to (C-32) In Example 23, the starting material, catalyst, solvent, polymerization inhibitor and reaction conditions of each step were changed as shown in Table 4, and thermal decomposition was carried out in the same manner as in Example 23. The reaction was carried out to obtain each target product. The thermal decomposition step (c) can be used without purifying the reaction solution obtained in the step (b). Also. Purification can be performed by a known method such as washing, extraction, recrystallization, ion exchange resin treatment, and chromatography, depending on the physical characteristics of the target compound.

Example 33
(C-33) Using 500 g of the step reaction solution obtained in the step (Low 21) after the completion of the 16-hour reaction, the mixture was charged into the same reaction distillation apparatus as in (C-23), heated to 80 ° C., and depressurized. Below, butylene diamine produced by a thermal decomposition reaction for 6 hours was distilled off to obtain a crude monomer. The obtained crude monomer was recrystallized twice with a mixed solvent of methanol and acetone to obtain a white powder having a melting point of 57 to 58 ° C. The purity of the product was 99.0% by gas chromatography analysis, and the product was found to be the target compound N, N'-by analysis of the infrared absorption spectrum (IR) with the ^{nuclear magnetic resonance spectrum (1 H-NMR).} It was confirmed that it was (4,7,10-trioxatris decamethylene) bisacrylamide (abbreviated as TDBAM).

Examples 34-44
(C-34) to (C-44) In Example 23 or 33, the starting material, catalyst, solvent, polymerization inhibitor and reaction conditions of each step were changed as shown in Table 5, and Example 23 or The thermal decomposition reaction was carried out in the same manner as in Example 33, and the respective target products were obtained. Depending on the physical properties of the target compound, neutralization (for example, neutralization and separation of the amino group of the residual β-aminopropionic acid ester with an acid), washing, extraction, recrystallization, adsorption treatment with an ion exchange resin, and chromatography. Purification can be performed by a known method such as.

Comparative Examples 1 to 4
In Example 1, the reaction was carried out according to the method described in Example 1 except that the starting material, the catalyst, the solvent, the polymerization inhibitor and the reaction conditions of each step were changed as shown in Table 6. The reaction results are shown in Table 6. No product purification operation was performed in these comparative examples.

Comparative Examples 5-10
In Example 23, the reaction was carried out according to the method described in Example 23, except that the starting material, the catalyst, the solvent, the polymerization inhibitor and the reaction conditions of each step were changed as shown in Table 7. The results are shown in Table 7. No product purification operation was performed in these comparative examples.

From the results of Examples 1-22 and Comparative Example 1-4, in the amidation reaction of step (b), even if the reaction conditions such as the charging ratio of the raw materials, the reaction temperature, and the time are the same, the metal complex proposed in the present invention It was found that the reaction did not proceed in the absence of.

From the results of Examples 23-44 and Comparative Example 5-10, even if the reaction conditions such as the charging ratio of the raw materials, the reaction temperature, and the time are the same in the thermal decomposition reaction of the step (c), the metal complex of the present invention is proposed. It was found that the reaction did not proceed in the absence of. Further, in the conventional thermal decomposition reaction using an acidic catalyst, the reaction does not occur unless the temperature is high, and on the other hand, polymerization troubles due to the high temperature reaction are likely to occur, and in particular, polyfunctional N-substituted (meth) acrylamide is obtained. I couldn't.

As described above, in the method of the present invention, when a metal complex is used as a catalyst using a (meth) acrylic acid ester as a starting material, β-alkoxypropionic acid can be efficiently used for a short time even under mild reaction conditions. Esters, β-aminopropionic acid esters and high-purity N-substituted (meth) acrylamides can be produced. In addition, by selecting a metal complex catalyst, the reaction proceeds at a sufficient rate and high selectivity even at normal pressure and low temperature, troubles such as polymerization do not occur, there are few by-products of impurities, and a high-purity product is produced in high yield. You can get it at.
The N-substituted (meth) acrylamide obtained by the production method of the present invention is used as a functional polymer alone or copolymerized with other polymerizable monomers in daily life because of its convenience, and is used as a paint, an adhesive, or an adhesive. , Various coating agents, paper-making agents such as paper strength enhancers, polymer flocculants used in the treatment of industrial wastewater and domestic wastewater, polymer modifiers, dispersants, thickeners, contact lenses and biological gels. It can be suitably used in extremely various fields such as synthetic raw materials such as, and reactive diluents for UV curable resins.

Claims (6)

Using the β-substituted propionic acid amide represented by the general formula [1], the liquid phase pyrolysis reaction is carried out in the presence of a metal complex as a catalyst, and the N-substituted (N-substituted) represented by the general formula [2]. Meta) A method for producing acrylamide,

(In each equation, R ₁ represents a hydrogen atom or a methyl group. When n is an integer of 1 to 10 and n = 1, R ₂ is a linear or branched chain having 11 to 36 carbon atoms. Represents an alkyl group, an alkyl ether group, an alicyclic hydrocarbon, or an aromatic hydrocarbon, and in the case of an integer of n = 2 to 10, R ₂ is a hydrogen atom or a linear or branched chain having 1 to 36 carbon atoms. Represents an alkyl group, an alkyl ether group, an alicyclic hydrocarbon, or an aromatic hydrocarbon. A is an alkoxy group or an amino group represented by the general formula [3] or [4] (R ₃ in the formula is Represents a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl ether group, and an alicyclic hydrocarbon. R ₄ and R ₅ are independently linear or branched hydrogen atoms or 1 to 10 carbon atoms, respectively. chain alkyl group, alkyl ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon. Further, R ₄ and R ₅ together with the nitrogen atom carrying them, a saturated 5 to 7-membered ring It represents (including those having an oxygen atom), and D represents hydrogen or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene ether group, an alicyclic hydrocarbon, and an aromatic. It represents a cyclic ether group having a hydrocarbon and an oxygen atom, and E represents an n-valent linking group.)

The metal complex comprises a combination of at least one metal atom or metal ion selected from the group of Lewis acids below and at least one selected from the group of Lewis bases below. A method for producing a substituted (meth) acrylamide.
Lewis acid: iron, nickel, copper (divalent), cobalt, zinc, scandium, yttrium and lanthanides
Lewis base: acetate ion, toluene sulfonate ion, trifluoromethane sulfonate ion and trifluoro acetate ion Formula [1] beta-substituted propionic acid amide represented by is a general formula beta-substituted propionic acid esters of the general formula represented by [5] [6] amine compound represented, the presence of the metal complex as a catalyst The method for producing N-substituted (meth) acrylamide according to claim 1, which is obtained by reacting underneath.

(In each formula, R ₁ , R ₂ , n, A, D and E are as defined above. R ₆ represents a linear or branched alkyl group having 1 to 4 carbon atoms.) The N-substituted (meth) according to claim 1 or 2, wherein the β-substituted propionic acid amide represented by the general formula [1] is the β-alkoxypropionic acid amide represented by the general formula [7]. ) Method for producing acrylamide.

The N-substituted (meth) according to claim 1 or 2, wherein the β-substituted propionic acid amide represented by the general formula [1] is the β-aminopropionic amide represented by the general formula [8]. Method for producing acrylamide.

The method for producing N-substituted (meth) acrylamide according to claim 1, wherein the amount of the metal complex used is 1 to 30 mol% with respect to β-substituted propionic acid amide. The N-substituted (meth) acrylamide according to claim 2, wherein the amount of the metal complex used is 0.1 to 50 mol% with respect to the number of amino groups which are functional groups of the amine compound. Production method.