JP2015209419A - Method of producing n-substituted (meth)acrylamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing N-substituted (meth)acrylamide of high purity under mild conditions.SOLUTION: This invention relates to a method of obtaining N-substituted (meth)acrylamide [3] by the detachment of an amine compound through the liquid-phase thermal decomposition of an aminopropionic acid amide derivative [1] in the presence of a catalyst mainly composed of silica, wherein R-Rare represented by H, a C1-32 alkyl group, and a hydroxyalkyl group.

Description

  The present invention provides a simple industrial production of N-substituted (meth) acrylamide useful as various polymer raw materials, characterized in that an aminopropionamide derivative is desorbed by liquid phase pyrolysis under mild conditions. It relates to a manufacturing method.

  N-substituted (meth) acrylamide is a functional polymer obtained by copolymerization with a single polymerizable monomer or other polymerizable monomer in daily life because of its convenience, paint, pressure-sensitive adhesive, adhesive, various coating agents, paper strength enhancer. Paper making chemicals, polymer flocculants, polymer modifiers, dispersants, thickeners, synthetic raw materials such as contact lenses and biogels, and UV curable resin reactivity. It is used in a wide variety of fields such as diluents. Accordingly, methods for producing N-substituted (meth) acrylamide have been extensively studied and reported.

  As an industrial production method of N-substituted (meth) acrylamide, there are mainly four types as shown below when summarized from starting materials. In the first production method, an amine exchange reaction and a Michael addition reaction are performed at 100 to 250 ° C. in the presence of an amine using (meth) acrylamide and an amine acrylate as a catalyst, and at a high temperature of 160 to 350 ° C. In this method, amine is removed by liquid phase pyrolysis to obtain N-substituted (meth) acrylamide (Patent Document 1). In the second production method, a (meth) acrylic acid ester is used to perform an amidation reaction directly with an amine in the presence of a strongly basic catalyst or an organotin catalyst, or after an addition reaction with an amine and a Michael, followed by an amidation reaction. This is a method for synthesizing N-substituted (meth) acrylamide by subjecting the product amide adduct to liquid phase pyrolysis at about 150 to 200 ° C. in the presence of a non-catalytic, acidic catalyst or polymerization inhibitor (Patent Documents 2 to 8). ). The third production method is a method for producing N-substituted (meth) acrylamide by reacting acrylonitrile with an olefin or alcohol in the presence of concentrated sulfuric acid, Lewis acid or the like (Patent Document 9). The fourth production method uses (meth) acrylic acid and directly amidates with an amine in the presence of a mesoporous silica catalyst (Patent Document 10) or (meth) acrylic acid and 3 to 10 moles of a secondary amine under pressure. To synthesize N, N-disubstituted β-amino acids, and then amidate with a low-boiling secondary amine under conditions of 120 to 200 ° C. and 0.17 to 0.87 MPa using an alumina catalyst and a convection system. This is a method of synthesizing N-substituted (meth) acrylamide by performing a reaction, further adding a gas phase polymerization inhibitor and decomposing it under the conditions of 200 to 300 ° C. and 0.15 to 0.95 MPa (patent document) 11).

However, these methods still have problems and problems. That is, in the first and second production methods, after the amidation reaction, when the obtained amide adduct is thermally decomposed in the liquid phase, it is necessary to carry out in a high temperature condition of 150 ° C. or higher or in the presence of a strongly acidic catalyst. . Therefore, polymerization of the N-substituted (meth) acrylamide, which is the target product generated by thermal decomposition, is extremely likely to occur, and there are problems such as a decrease in yield and an increase in purification cost. Moreover, when using a strong base or a strong acidic catalyst, neutralization operation is required after completion | finish of reaction, and the neutralization process, the removal process of neutralization salt, and the processing process of neutralization waste_water | drain must be performed separately. Furthermore, toxic gas ammonia by-produced in the first production method, organic tin catalyst used in the second production method, and the like had to be separated, recovered, and removed. Since these additional steps require excessive energy and capital investment, none of these methods are inexpensive and simple methods suitable for industrial production.

Similarly, in the third production method, since an acidic catalyst or a Lewis acid catalyst is used for the reaction, a removal step or extraction step by extraction from the reaction system of the catalyst is required. This method was also not an industrially advantageous method. In addition, since the reaction yield varies greatly depending on the alcohol or olefin used, it was insufficient as a method for synthesizing various N-substituted (meth) acrylamides.

Regarding the fourth production method, in recent years, amidation reaction of carboxylic acid and amine using silica or alumina as a catalyst has attracted attention. However, in unsaturated carboxylic acids such as (meth) acrylic acid, the double bond is extremely reactive, and thus the other Michael addition reaction with an amine proceeds preferentially, as reported in Patent Document 10. The reaction yield of direct amidation of (meth) acrylic acid and amine was as low as about 40%. On the other hand, in Patent Document 11, an amine is added to a double bond as a protecting group in advance, and an amine-protected N, N-disubstituted β-amino acid is synthesized and then an amidation reaction with an amine is performed. However, a large excess of amine (3 to 10 moles) is required for the other Michael addition reaction of (meth) acrylic acid and secondary amine, and complicated post-processing such as recovery and reuse of excess amine. There was an economic disadvantage. In addition, it is natural that excess amine produces a large amount of N, N-disubstituted β-amino acids and organic neutralized salts as a by-product, resulting in a decrease in the purity of the target product, an increase in the viscosity of the reaction solution, and catalyst contamination in the next step. Numerous problems remain, such as inactivation by.

Furthermore, in Patent Document 11, gas phase pyrolysis was carried out at a high temperature of 200 to 300 ° C. using a special polymerization inhibitor. However, N-substituted (meth) acrylamide having a high boiling point, high viscosity and non-volatility was used. There was a disadvantage that did not apply to. That is, at a predetermined temperature and pressure, monomers (N-substituted (meth) acrylamide) and their amine adducts (mono in which the double bond of N-substituted (meth) acrylamide is protected by amine addition) can be volatilized, Only N-substituted (meth) acrylamides can be synthesized which are capable of thermally decomposing adducts and which are not polymerized and thermally stable. However, as is well known, N-substituted (meth) acrylamide is easy to form a hydrogen bond, has a boiling point, viscosity, volatility, etc. higher than (meth) acrylate having a similar structure and is extremely easy to polymerize. Therefore, in such a method, even in the case of a synthesizable monomer, the operation in a severe case becomes difficult, the yield further decreases, and the target product may not be obtained.

As described above, an industrial production method of N-substituted (meth) acrylamide under mild conditions, in particular, a high yield, high purity, and simple process that does not use a strongly acidic catalyst or high temperature conditions in the thermal decomposition step, Not yet established.

JP 58-18346 A JP-A-4-208258 JP-A-6-199752 JP 2000-273072 A JP 2012-97005 A Japanese Patent Laid-Open No. 4-154748 JP 7-188135 A JP-A-11-302240 JP 2000-264865 A JP 2012-46431 A WO2010 / 126086

An object of the present invention is to thermally decompose an aminopropionic acid amide derivative under mild conditions without causing by-product impurities or polymerization of the product, and by purifying N-substituted (meth) acrylamide (N-mono) with high purity. It is to provide a method for industrially producing substituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide) at high yield, simply and inexpensively.

As a result of intensive studies to solve these problems, the present inventors have found that an aminopropionic acid amide derivative represented by the general formula [1] is mild by adding an inorganic substance mainly composed of silica as a catalyst. The target compound N-substituted (meth) acrylamide (general formula [3]) was obtained by desorbing the amine compound (general formula [2]) by liquid phase pyrolysis under mild conditions, and the present invention was achieved. .

（各式中、Ｒ_１、Ｒ_２、Ｒ_４とＲ_５は各々独立に水素原子または炭素数１〜３２の直鎖状又は分岐鎖状のアルキル基（但し、Ｒ_１とＲ_２が同時に水素原子である場合及びＲ_４とＲ_５が同時に水素原子である場合を除く。）、または、炭素数１〜３２の直鎖状又は分岐鎖状のヒドロキシアルキル基、または、炭素数１〜３２の直鎖状又は分岐鎖状のアミノアルキル基であり、互いに同一であっても異なっていてもよく、また、Ｒ_１とＲ_２、および／または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、酸素原子を含む飽和５〜７員環を形成してもよく、Ｒ_３は水素原子またはメチル基を表す）

_{(Wherein, R 1, R 2, R} 4 and _{R 5} each independently represent a linear or branched alkyl group of a hydrogen atom or 1 to 32 carbon atoms (wherein, _{R 1} and _{R 2} are simultaneously hydrogen Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, and R ₃ represents a hydrogen atom or a methyl group)

（各式中、Ｒ_１、Ｒ_２、Ｒ_４とＲ_５は各々独立に水素原子または炭素数１〜３２の直鎖状又は分岐鎖状のアルキル基（但し、Ｒ_１とＲ_２が同時に水素原子である場合及びＲ_４とＲ_５が同時に水素原子である場合を除く。）、または、炭素数１〜３２の直鎖状又は分岐鎖状のヒドロキシアルキル基、または、炭素数１〜３２の直鎖状又は分岐鎖状のアミノアルキル基であり、互いに同一であっても異なっていてもよく、また、Ｒ_１とＲ_２、および／または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、酸素原子を含む飽和５〜７員環を形成してもよく、Ｒ_３は水素原子またはメチル基を表す。）
（２）一般式［１］で示される化合物が、一般式［４］で示されるアミノプロピオン酸エステル誘導体と１モル以上の一般式［２］で示されるアミン化合物とを反応させて得ることを特徴とする前記（１）に記載のＮ−モノ置換（メタ）アクリルアミド、またはＮ，Ｎ−二置換（メタ）アクリルアミドの製造方法、

（各式中、Ｒ_１、Ｒ_２、Ｒ_４とＲ_５は各々独立に水素原子または炭素数１〜３２の直鎖状又は分岐鎖状のアルキル基（但し、Ｒ_１とＲ_２が同時に水素原子である場合及びＲ_４とＲ_５が同時に水素原子である場合を除く。）、または、炭素数１〜３２の直鎖状又は分岐鎖状のヒドロキシアルキル基、または、炭素数１〜３２の直鎖状又は分岐鎖状のアミノアルキル基であり、互いに同一であっても異なっていてもよく、また、Ｒ_１とＲ_２、および／または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、酸素原子を含む飽和５〜７員環を形成してもよく、Ｒ_３は水素原子またはメチル基を表し、Ｒ_６は炭素数１〜６の直鎖状又は分岐鎖状のアルキル基を表す。）
（３）一般式［１］で示される化合物が、一般式［５］で示される(メタ)アクリル酸エステルと２モル以上の一般式［２］で示されるアミン化合物とを反応させて得ることを特徴とする前記（１）に記載のＮ−モノ置換（メタ）アクリルアミド、またはＮ，Ｎ−二置換（メタ）アクリルアミドの製造方法、

（各式中、Ｒ_１、Ｒ_２、Ｒ_４とＲ_５は各々独立に水素原子または炭素数１〜３２の直鎖状又は分岐鎖状のアルキル基（但し、Ｒ_１とＲ_２が同時に水素原子である場合及びＲ_４とＲ_５が同時に水素原子である場合を除く。）、または、炭素数１〜３２の直鎖状又は分岐鎖状のヒドロキシアルキル基、または、炭素数１〜３２の直鎖状又は分岐鎖状のアミノアルキル基であり、互いに同一であっても異なっていてもよく、また、Ｒ_１とＲ_２、および／または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、酸素原子を含む飽和５〜７員環を形成してもよく、Ｒ_３は水素原子またはメチル基を表し、Ｒ_７は炭素数１〜６の直鎖状又は分岐鎖状のアルキル基を表す。）
（４）一般式［１］で示される化合物が、一般式［６］で示されるアミノプロピオン酸誘導体と１モル以上の一般式［２］で示されるアミン化合物とを反応させて得ることを特徴とする前記（１）に記載のＮ−モノ置換（メタ）アクリルアミド、またはＮ，Ｎ−二置換（メタ）アクリルアミドの製造方法、

（各式中、Ｒ_１、Ｒ_２、Ｒ_４とＲ_５は各々独立に水素原子または炭素数１〜３２の直鎖状又は分岐鎖状のアルキル基（但し、Ｒ_１とＲ_２が同時に水素原子である場合及びＲ_４とＲ_５が同時に水素原子である場合を除く。）、または、炭素数１〜３２の直鎖状又は分岐鎖状のヒドロキシアルキル基、または、炭素数１〜３２の直鎖状又は分岐鎖状のアミノアルキル基であり、互いに同一であっても異なっていてもよく、また、Ｒ_１とＲ_２、および／または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、酸素原子を含む飽和５〜７員環を形成してもよく、Ｒ_３は水素原子またはメチル基を表す。）
（５）前記のシリカを主成分とする無機物は多孔質のシリカゲル、メソポーラスシリカ、シリカアルミナ、ゼオライトからなる群から選択された１種または２種以上であることを特徴とする前記（１）〜（４）の何れか一項に記載のＮ−モノ置換（メタ）アクリルアミド、またはＮ，Ｎ−二置換（メタ）アクリルアミドの製造方法、
（６）前記のシリカを主成分とする無機物中のシリカ含量は６０〜１００重量％であることを特徴とする前記（１）〜（５）の何れか一項に記載のＮ−モノ置換（メタ）アクリルアミド、またはＮ，Ｎ−二置換（メタ）アクリルアミドの製造方法
を提供するものである。 That is, the present invention
(1) By desorbing the amine compound represented by the general formula [2] from the aminopropionic acid amide derivative represented by the general formula [1] by liquid phase pyrolysis in the presence of an inorganic substance mainly composed of silica. A method for producing the obtained N-monosubstituted (meth) acrylamide represented by the general formula [3] or N, N-disubstituted (meth) acrylamide,

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, and R ₃ represents a hydrogen atom or a methyl group.)
(2) A compound represented by the general formula [1] is obtained by reacting an aminopropionic acid ester derivative represented by the general formula [4] with at least 1 mol of an amine compound represented by the general formula [2]. A method for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide as described in (1) above,

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, R ₃ represents a hydrogen atom or a methyl group, and R ₆ is a linear or branched chain having 1 to ₆ carbon atoms Represents an alkyl group of
(3) A compound represented by the general formula [1] is obtained by reacting a (meth) acrylic acid ester represented by the general formula [5] with 2 mol or more of an amine compound represented by the general formula [2]. A process for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to (1),

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them May form a saturated 5- to 7-membered ring containing an oxygen atom, R ₃ represents a hydrogen atom or a methyl group, and R ₇ is a linear or branched chain having 1 to 6 carbon atoms Represents an alkyl group of
(4) A compound represented by the general formula [1] is obtained by reacting an aminopropionic acid derivative represented by the general formula [6] with at least 1 mol of an amine compound represented by the general formula [2]. A method for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to (1),

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, and R ₃ represents a hydrogen atom or a methyl group.)
(5) The inorganic substance containing silica as a main component is one or more selected from the group consisting of porous silica gel, mesoporous silica, silica alumina, and zeolite. A method for producing N-monosubstituted (meth) acrylamide according to any one of (4) or N, N-disubstituted (meth) acrylamide,
(6) The N-mono-substitution according to any one of (1) to (5) above, wherein the silica content in the inorganic substance mainly composed of silica is 60 to 100% by weight ( The present invention provides a method for producing (meth) acrylamide or N, N-disubstituted (meth) acrylamide.

According to the method of the present invention, high-purity N-monosubstituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide can be easily produced from general-purpose industrial raw materials at a high yield at low cost. In addition, the method of the present invention uses a silica-based catalyst with a small environmental load, does not require the use of an acidic catalyst, does not cause troubles such as polymerization, and is manufactured at a low cost under conditions of mild temperature and pressure. be able to.
In the production method of the present invention, the catalytic mechanism of the inorganic substance mainly composed of silica in the liquid phase thermal decomposition reaction of the aminopropionic amide derivative is not necessarily clear, but the isolated silanol group on the surface of the catalyst, and further the acid strength Inventor said that the reaction proceeds smoothly even under mild conditions by activating the carbonyl oxygen of the amide as an active site due to having a high acid point, and as a result, the carbonyl group β hydrogen is easily eliminated. Have guessed.

Hereinafter, the present invention will be described in detail.
In the present invention, an aminopropionic acid amide derivative represented by the general formula [1] is subjected to liquid phase pyrolysis in the presence of an inorganic substance mainly composed of silica, and one molecule of an amine compound is eliminated, whereby the general formula [1] 3], or N, N-disubstituted (meth) acrylamide.

The aminopropionic acid amide derivatives used in the present invention include N-monosubstituted-β-alkylaminopropionic acid amide, N-monosubstituted-β-dialkylaminopropionic acid amide, N, N-disubstituted-β-alkylaminopropionic acid. Acid amide, N, N-disubstituted-β-dialkylaminopropionic acid amide, N-monosubstituted-β-hydroxyalkylaminopropionic acid amide, N-monosubstituted-β-dihydroxyalkylaminopropionic acid amide, N, N- Disubstituted-β-hydroxyalkylaminopropionic acid amide, N, N-disubstituted-β-dihydroxyalkylaminopropionic acid amide, N-monosubstituted-β-aminoalkylaminopropionic acid amide, N-monosubstituted-β-diamino Alkylaminopropionic acid amide, N, N-disubstituted-β-aminoalkyl Ruaminopropionic acid amide, N, N-disubstituted-β-diaminoalkylaminopropionic acid amide, N-monosubstituted-β-morpholine aminopropionic acid amide, N, N-disubstituted-β-morpholine aminopropionic acid amide, N-morpholine-β-morpholine aminopropionic acid amide. Here, alkyl means carbon number such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, betyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, oleyl, icosyl, docosyl, hexacosyl, octacosyl, dotriacontyl, etc. 1 to 32 linear or branched saturated or unsaturated alkyl groups. Also, from the viewpoint of easy industrial production, N, N-dimethyl-β-dimethylaminopropionic acid amide, N, N-diethyl-β-diethylaminopropionic acid amide, N, N-dipropyl-β-dipropylaminopropionic acid Acid amide, N-isopropyl-β-isopropylaminopropionic acid amide, N, N-dibutyl-β-dibutylaminopropionic acid amide, N-isobutyl-β-isobutylaminopropionic acid amide, N, N-diethyl-β-hydroxy Ethylaminopropionic acid amide, N, N-dimethyl-β-propylaminopropionic acid amide, morpholyl-β-morpholylpropionic acid amide are preferred.

The inorganic substance containing silica as a main component (silica main component inorganic substance) used in the present invention is one or more selected from the group consisting of porous silica gel, mesoporous silica, silica alumina, and zeolite.

The shape of the silica-based inorganic catalyst is not particularly limited, such as a powder, fine particle, granule, thin film, or other molded product, and a shape suitable for a fluidized bed, a fixed bed, etc. can be appropriately selected according to the reaction method. . The reaction may be a batch system or a continuous system. For example, in the case of a batch-type liquid phase suspension reaction, the shape of the catalyst is preferably a powder or a fine particle in view of the reaction active point. Further, the fine particles can be used because they are easy to handle in the state of a uniformly dispersed liquid with water or an organic solvent. When used as a dispersion, in addition to the reaction system, the dispersant can be removed by distillation or the like, and then adjusted to predetermined conditions to perform a thermal decomposition reaction.

In the present invention, the porous silica gel is a silica gel having pores and can be used without being limited by a production method or the like. The shape of the porous silica gel may be crushed non-spherical silica gel or spherical silica gel, but spherical silica gel is more preferable because it has high strength and is easy to recycle. Further, the “spherical” in the present invention is not limited to a true sphere, but includes a slightly deformed sphere such as an elliptic sphere, and an average sphericity of 0.5 or more, more preferably 0.85 or more. . Moreover, in a spherical silica gel, the average particle diameter is usually 0.1 to 10,000 μm, preferably 1 to 5,000 μm. The average pore diameter is 0.5 to 100 nm, preferably 2 to 50 nm. The specific surface area is 10~10000m ² / g, more preferably 30~1000m ² / g. When outside these ranges, the content of the two effective particles and pores may decrease, leading to a decrease in the reaction rate and the progress of side reactions. The porous silica gel used in the present invention can be easily obtained as a commercial industrial product, and can also be synthesized and processed by a known method. Examples thereof include silica gel 40, silica gel 60, Wakosil C-200, and Wakosil C-300, which are often used as chromatographic carriers.

In the present invention, mesoporous silica is an inorganic substance mainly composed of silicon dioxide having uniform and regular mesopores (pores having a diameter of 2 to 50 nm). Mesoporous silica may be a powder, a fine particle, or a molded product such as a thin film. In addition, spherical fine particles are more preferable because they have a large specific surface area, high strength, are easy to recycle, and can be easily industrialized. Mesoporous silica has a pore diameter of 2 to 50 nm, preferably 2 to 10 nm. When the pore diameter of mesoporous silica is smaller than 2 nm, the diffusion rate of raw material molecules and product molecules is low, and the reactivity may be lowered. On the other hand, when the pore diameter of mesoporous silica is larger than 50 nm, it is difficult to form a transition state between the raw material molecules and the product molecules, and there is a possibility that high selectivity and high yield cannot be obtained.

The specific surface area of mesoporous silica is 10 to 3000 m ² / g, and preferably 50 to 3000 m ² / g. A particulate catalyst having a specific surface area in this range can be easily produced, and can act in contact with raw material molecules efficiently. The specific surface area can be determined by, for example, the BET method in which nitrogen gas is adsorbed and the specific surface area is measured. Moreover, an average particle diameter is 0.2-10,000 micrometers, Preferably it is 1-5,000 micrometers.

Representative examples of mesoporous silica include MCM-41, MCM-48, MCM-50, SBA-1, SBA-11, SBA-15, SBA-16, FSM-16, KIT-5, KIT-6, and HMS. (Hexagonal crystal), MSU-F, MSU-H and the like. These mesoporous silicas can be obtained and used commercially, or can be synthesized using known methods.

The method for synthesizing mesoporous silica used in the present invention is not particularly limited, but basically a known method of firing a reaction complex of a silica source and a cationic or neutral surfactant as a mold is used. be able to. As the type of silica source, colloidal silica, silica gel, silicates such as sodium silicate, and alkoxysilanes such as tetramethoxysilane and tetraethoxysilane can be used alone or in combination. Quaternary ammonium salts having an alkyl group with 8 or more carbon atoms as templates (templates), especially alkyltrimethylammonium halide cationic surfactants and neutral surfactants based on poly (ethylene glycol-ethylene) block copolymers An agent can be suitably used. Further, the mold remaining in the reaction complex is treated with an acidic solution and then removed by baking to synthesize mesoporous silica.

The firing treatment is preferably performed in the presence of air or oxygen. The firing temperature is 200 to 800
More preferably, the temperature is 300 ° C to 700 ° C. If the firing temperature is less than 200 ° C., the burning of the mold will be slow, and it may not be sufficiently removed. Moreover, when the firing temperature is 800 ° C. or higher, there is a defect that silica constituting the pore walls is partially collapsed.

In the present invention, silica alumina is a composite oxide mainly composed of silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), and is crystalline or amorphous. Also good. The total content of silica and alumina in silica alumina is preferably 95% by weight or more, and the silica content is preferably 50 mol% or more. The silica alumina catalyst used in the present invention may be a powder, fine particles, or a molded product such as a thin film. In addition, spherical fine particles are more preferable because they have a large specific surface area, high strength, are easy to recycle, and can be easily industrialized. In the spherical particle-based silica alumina, the average particle diameter is usually 0.2 to 20,000 μm, preferably 1 to 10,000 μm. The average pore diameter is 1 to 100 nm, preferably 2 to 50 nm. The specific surface area is 10~10000m ² / g, more preferably 30~1000m ² / g. Spherical particle catalysts with an average particle size and specific surface area in this range can be easily produced, the diffusion rate of raw material molecules and product molecules is high, transition states are easily formed, high selectivity, and high yield. There is an advantage that rate is obtained.

The silica alumina used in the present invention can be easily obtained as a commercially available industrial product, and can also be synthesized and processed by a known method. For example, it is prepared by coprecipitation method, gel kneading method, gel deposition method, cogelation method, impregnation method, etc. from silica sources such as water glass and silica gel and alumina sources such as aluminum sulfate, sodium aluminate and alumina gel. Silica alumina hydrogel can be produced by drying and baking. Moreover, it can also manufacture by the alkoxide method (sol-gel method) and chemical vapor deposition which hydrolyze the mixed solution of tetraethoxysilane and aluminum isopropoxide. The silica alumina produced in this manner is sufficiently washed with water and fired at about 400 to 700 ° C. for several to several tens of hours, whereby it can be highly purified. Examples of commercially available products include silica alumina 308 manufactured by Fuji Silysia Chemical Co., Ltd., N633HN, N631HN, N633L, N631L manufactured by JGC Catalysts & Chemicals, Al-MCM-41 manufactured by Sigma-Aldrich, and Al-MSU-F.

In the present invention, zeolite is a crystalline composite oxide of silicon and aluminum having regular fine pores (micropores), and may be either a natural product or a synthetic product. In addition, as structural types, MFI type, β type, mordenite type (MOR), faujasite type (FAU), ferrierite type (FER), LTL type, LTA type, MWW type, MSE type, Y type FAU, X type FAU. The SiO ₂ / Al ₂ O ₃ molar ratio, which is a constituent component of zeolite, is 1 or more, preferably 2 or more. When the SiO ₂ / Al ₂ O ₃ molar ratio is less than 1, the amount of acid sites derived from alumina increases and side reactions tend to occur. The zeolite may be any of powder, granule, and molded product. Spherical fine particles are more preferable because they have a large specific surface area, high strength, are easy to recycle, and can be easily industrialized. In the spherical particle-based zeolite, the average particle diameter is usually 1 to 500 μm, the specific surface area is 150 m ² / g or more, and the pore volume is about 0.1 to ² cm ³ / g. If the specific surface area and the pore volume are within these ranges, the activity of the catalyst is not lowered, which is preferable. The zeolite used in the present invention may be a commercially available product, or may be prepared and used by a known method such as crystallization of silica alumina gel in a high pH range under 100 to 200 ° C. hydrothermal conditions. Examples of commercially available products include Y type 320HOA, FER type 720KOA, MOR type 640HOA, 690HOA, and MFI type 890HOA manufactured by Tosoh Corporation.

The silica-based inorganic substance used in the present invention, for example, porous silica gel, mesoporous silica, silica alumina, zeolite, etc. can be prepared by the above-mentioned known methods, and the preparation method is not limited. Specifically, it can prepare by the method of patent documents 10, 12-15, and nonpatent literature 1-5.

Patent Document 12: Japanese Patent Laid-Open No. 10-130013 Patent Document 13: Japanese Patent Laid-Open No. 2004-182492 Patent Document 14: Japanese Patent Laid-Open No. 2011-532 Patent Document 15: Japanese Patent Laid-Open No. 2013-47166 Non-Patent Document 1: Sakthivel SJ Huang, WH Chen, ZH Lan, KH Chen, HP Lin, CY Mou, SB Liu, Adv. Funct. Mater., 2005, 15, 253 Non-Patent Document 2: S. Inagaki, M. Ogura, T. Inami, Y. Sasaki, E. Kikuchi, M. Matsukata, Micropours and Mesoporoua Materials, 2004, 74, 163 Non-Patent Document 3: Inagaki, A. Koiwai, N. Suzuki, Y. Fukushima and K Kuroda, Bull. Chem. Soc. Jpn., 1996, 69, 1449 Non-Patent Document 4: JS Beck, JC Vartuli, WJ Roth, ME Leonowicz, CT Kresge, KD Schmitt, CT-W. Chu, DH Olson, EW Sheppard, SB McCullen, JB Higgins and JL Schlenker, J. Am. Chem. Soc. 1992, 114, 10834 Non-Patent Document 5: PD Yan g, DY Zhao, DI Margolese, BF Chmelka, GD Stucky, Nature 1998, 396, 152

The silica-based inorganic material used in the present invention preferably has an isolated silanol group on the surface. A silica main component inorganic substance is added to heavy acetonitrile, and a proton peak derived from an isolated silanol group can be confirmed in the vicinity of 3.3 ppmm by 1H-MAS-NMR analysis. The higher the content of isolated silanol groups on the surface of the silica-based inorganic material, the higher the activity as a catalyst. However, the higher concentration of isolated silanol groups increases the manufacturing cost of the catalyst such as special processing technology and precise control. . In the present invention, the content of the isolated silanol group is 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, and particularly preferably 1.00 mmol / g or more. Moreover, it is more preferable that an acid point with high acid strength is simultaneously present on the surface of the silica-based inorganic material. The presence of an acid point with high acid strength can be easily discriminated from a proton peak broad in the vicinity of 5 ppm in the 1H-MAS-NMR spectrum of the silica-based inorganic substance added to deuterated acetonitrile.

The amount of the silica-based inorganic substance used in the liquid phase pyrolysis of the present invention has an optimum range depending on the type and properties of the aminopropionic acid amide derivative (liquid or solid at the reaction temperature), solubility, reaction temperature and solvent used. Usually, it is in the range of 0.1 to 200% by weight, preferably in the range of 0.5 to 100% by weight, particularly preferably in the range of 2 to 50% by weight, based on the amount of the aminopropionic acid amide derivative. .

The reaction temperature and reaction time for liquid phase pyrolysis are appropriately selected according to the type of aminopropionic acid amide derivative that is the starting material for the reaction, but the reaction temperature is 100 to Below about 150 ° C., the reaction time ranges from 0.1 to 48 hours. The preferred reaction temperature is about 110 to less than 150 ° C, the reaction time is in the range of 0.5 to 40 hours, the particularly preferred reaction temperature is about 115 to 145 ° C, and the reaction time is in the range of 1 to 36 hours. is there. Since the aminopropionic acid amide derivative, which is a starting material for the reaction, can disperse the silica-based inorganic substance, it can provide an action as a reaction solvent, but a solvent may be used as necessary. The reaction can be carried out under normal pressure or under reduced pressure using a device such as a vacuum pump. 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 silica-based inorganic substance. For example, hydrophobic solvents such as toluene and xylene, hydrophilic solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc), 1-butyl-2,3-dimethylimidazolium hexafluorophos Fert, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium thiocyanate, 1,3-dimethylimidazolium Dimethyl phosphate, 1-ethyl-3-methylimidazolium 2- (2-methoxyethoxy) ethyl sulfate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3- ( Hydroxymethyl) pyridinium ethyl sulfate, triethylpentylammonium bis (trifluoromethanesulfo Nyl) imide, tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide and the like. 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 in the range of 100 to 300% by weight, based on the aminopropionic acid amide. is there. When the reaction solvent is used for the purpose of dissolving the raw materials and 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. The reaction rate may be reduced.

In the reaction of liquid phase pyrolysis, a batch system or a continuous system may be used, and the silica main component inorganic material may be supplied by a fluidized bed or a fixed bed. In the case of a batch system, for example, a raw material aminopropionamide amide derivative, a silica main component inorganic substance and a solvent are charged into a reaction vessel, and the reaction vessel and reaction solution are replaced with an inert gas as necessary, followed by stirring. While maintaining the suspended state, the reaction temperature and operating pressure are adjusted to a predetermined level, one molecule of the amine compound is eliminated by liquid phase decomposition reaction, and distilled and recovered together with the reaction solvent in the order of boiling point. N-monosubstituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide. The distillate residue after completion of the reaction can be recycled by, for example, separating the solid silica-based inorganic substance with a filter, separating it from the reaction solution, washing it, and drying it by heating.

The aminopropionic acid amide derivative used in the present invention can be synthesized by reacting an aminopropionic acid ester derivative with 1 mol or more of an amine compound. The molar ratio of the amine compound to the aminopropionic ester derivative (amine compound / aminopropionic ester derivative) is preferably reacted in the range of 1.0 to 3.0. Although this reaction proceeds stoichiometrically, that is, theoretically in a 1: 1 molar ratio reaction, it is desirable to add either one of the reaction raw materials excessively in order to promote and complete the reaction. From the viewpoint of utilization, excessive penetration of the amine compound is more preferable. On the other hand, when the charge ratio of the amine compound exceeds 3.0 times mol, a large amount of unreacted amine remains, and it may be difficult to separate the target product from the aminopropionic acid amide derivative depending on the type of amine. .

The reaction between the aminopropionate derivative and the amine compound proceeds at a sufficient rate even without a catalyst, but the reaction temperature decreases due to the use of a basic catalyst in consideration of the amine compound type, reaction equipment, efficiency, etc. It is possible to make adjustments such as shortening the reaction time. The basic catalyst can be used in an inorganic system, an organic system, or a heterogeneous system that is easily separated even in a general-purpose homogeneous system. Examples of the inorganic base include hydroxides of alkali metals such as lithium, sodium, and potassium, and examples of the organic base include tertiary amines, pyridine, and alkali metal alkoxides. Moreover, these basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type. When using a catalyst, it is preferable that the compounding quantity is 0.005-10 mol% with respect to an aminopropionic ester derivative. After completion of the reaction, the basic catalyst is preferably neutralized with an acidic compound such as sulfuric acid or hydrochloric acid and then carried over to the next step.

In the reaction of an aminopropionate derivative with an amine compound, the reaction temperature and reaction time are appropriately selected according to the type of the amine compound and the charged molar ratio of the amine compound to the aminopropionate derivative. Is about 40 to 120 ° C., and the reaction time is in the range of 0.5 to 48 hours. Moreover, preferable reaction temperature is about 60-100 degreeC, and reaction time is the range of 2-36 hours. When the reaction temperature is less than 20 ° C. or the reaction time is less than 0.5 hour, the reaction rate is remarkably lowered, and the aminopropionic acid amide derivative may not be sufficiently obtained. On the other hand, when the reaction temperature exceeds 120 ° C., the low boiling point amine compound tends to be removed from the reaction system, and when the reaction time exceeds 48 hours, disadvantages occur in productivity and cost.

The reaction between the aminopropionic acid ester derivative and the amine compound can provide an action as a reaction solvent at the same time as the amine compound is a raw material for the reaction. Moreover, you may use a solvent as needed. The reaction solvent is not particularly limited, and a general solvent can be used as long as it does not cause side reactions with the raw materials, products and reaction catalyst of the reaction. Examples thereof include hydrophobic solvents such as toluene and xylene, and hydrophilic solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc). When a solvent is used, the amount used is preferably in the range of 20 to 1000% by weight with respect to the aminopropionic acid ester. Moreover, this reaction can be implemented under normal pressure or the pressurization using apparatuses, such as an autoclave.

The aminopropionic acid amide derivative used in the present invention can be synthesized by reacting (meth) acrylic acid ester with 2 mol or more of an amine compound. The molar ratio of the amine compound to the (meth) acrylic acid ester (amine compound / (meth) acrylic acid ester) is preferably reacted in the range of 2.0 to 5.0. This reaction proceeds stoichiometrically, that is, theoretically a 1: 2 molar ratio reaction, but it is desirable to add an excess of amine in order to promote and complete the reaction. On the other hand, when the feed ratio of the amine compound is 5.0 times mole or more, a large amount of unreacted amine remains, and it may be difficult to separate the target product from the aminopropionic acid amide derivative depending on the type of amine. is there.

Although the reaction between (meth) acrylic acid ester and amine compound proceeds at a sufficient rate even without a catalyst, considering the variety of amine compound, reaction equipment, efficiency, etc., the use of a basic catalyst reduces the reaction temperature. It is possible to adjust the shortening of the reaction time. As described above, the basic catalyst can be used in an inorganic system or an organic system, or in a heterogeneous system that can be easily separated in a general-purpose homogeneous system. It is preferable that the usage-amount of a catalyst is 0.01-10 mol% with respect to (meth) acrylic acid ester. After completion of the reaction, the basic catalyst is preferably neutralized with an acidic compound such as sulfuric acid or hydrochloric acid and then carried over to the next step.

In the reaction of the (meth) acrylic acid ester and the amine compound, the reaction temperature and reaction time are appropriately selected according to the variety of the amine compound and the charged molar ratio of the amine compound and the (meth) acrylic acid ester. The reaction temperature is about 20 to 120 ° C., and the reaction time is in the range of 1 to 48 hours. Moreover, preferable reaction temperature is about 40-100 degreeC, and reaction time is the range of 2 to 36 hours. When the reaction temperature is less than 20 ° C. or the reaction time is less than 1 hour, the reaction rate is remarkably lowered, and the aminopropionic acid amide derivative may not be sufficiently obtained. On the other hand, when the reaction temperature exceeds 120 ° C., the low boiling point amine compound tends to be removed from the reaction system, and when the reaction time exceeds 48 hours, disadvantages occur in productivity and cost.

The reaction between the (meth) acrylic acid ester and the amine compound can provide an action as a reaction solvent at the same time as the amine compound is a raw material for the reaction. Moreover, you may use a solvent as needed. The reaction solvent is not particularly limited, and a general solvent can be used as described above as long as it does not cause side reactions with the raw materials, products and reaction catalyst of the reaction. When using a solvent, the amount used is preferably in the range of 20 to 1000% by weight based on the (meth) acrylic acid ester. Moreover, this reaction can be implemented under normal pressure or the pressurization using apparatuses, such as an autoclave.

The aminopropionic acid amide derivative used in the present invention can be synthesized by reacting an aminopropionic acid derivative with 1 mol or more of an amine compound. It is preferable that the molar ratio of the amine compound to the aminopropionic acid derivative (amine compound / aminopropionic acid) be reacted in the range of 1.0 to 3.0. This reaction proceeds stoichiometrically, that is, theoretically a 1: 1 molar ratio reaction, but in order to promote and complete the reaction, it is desirable to charge one of the raw materials in excess, but it is recovered and reused. From the viewpoint, excessive penetration of the amine compound is more preferable. On the other hand, when the feed ratio of the amine compound exceeds 3.0 times mol, a large amount of unreacted amine remains, and it may be difficult to separate the target product from the aminopropionic acid amide derivative depending on the type of amine. is there.

In the present invention, the reaction between aminopropionic acid and an amine compound can be performed in the presence of the same silica-based inorganic substance as described above as a catalyst. The reaction temperature and reaction time are appropriately selected according to the variety of amine compound and the charged molar ratio of the amine compound and aminopropionic acid derivative. Usually, the reaction temperature is about 40 to 120 ° C., and the reaction time is 1 to 1. The range is 48 hours. Moreover, preferable reaction temperature is about 60-100 degreeC, and reaction time is the range of 2-36 hours. When the reaction temperature is less than 40 ° C. or the reaction time is less than 1 hour, the reaction rate is remarkably reduced, and the aminopropionic acid amide derivative may not be sufficiently obtained. On the other hand, when the reaction temperature exceeds 120 ° C., the low boiling point amine compound tends to be released from the reaction system, and when the reaction time exceeds 48 hours, disadvantages occur in productivity and cost.

Although an action as a reaction solvent can be provided by adding an excessive amount of the amine compound as a starting material for the reaction, a solvent may be used as necessary. The reaction can be carried out under normal pressure or under pressure using an apparatus capable of pressurization such as an autoclave. The reaction solvent is not particularly limited, and a general solvent can be used as described above as long as it does not cause a side reaction with the starting material, product and silica-based inorganic substance. When the 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 in the range of 100 to 300% by weight, based on the total of aminopropionic acid and the amine compound. % Range. When the reaction solvent is used for the purpose of dissolving the raw materials and 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. The reaction rate may be reduced.

The reaction between the aminopropionic acid and the amine compound may be a batch system or a continuous system, and the silica-based inorganic material supply system may be a fluidized bed or a fixed bed. In the case of a batch system, for example, a raw material aminopropionic acid derivative, an amine compound, a silica main component inorganic substance, and a solvent are charged into a reaction vessel, and the inside of the reaction vessel and the reaction liquid are replaced with an inert gas as necessary. While maintaining the suspended state by stirring, the reaction temperature is adjusted to a predetermined value and the reaction is carried out for a predetermined time. In addition, the reaction mixture after completion of the reaction may be separated from the reaction solution by separating the solid silica-based inorganic material with a filter, etc., and recovered or carried over to the next step without separation. Also good. When the viscosity at room temperature of the reaction mixture after completion of the reaction is 1000 mPa · s or less, the silica-based inorganic substance is preferably recovered and reused by filtration, centrifugation, or the like.

Furthermore, in the reaction between an aminopropionic acid derivative and an amine compound, when the reaction temperature is higher than the boiling point of the amine compound, the reaction can be performed under pressure using a pressure-resistant reaction vessel. The reaction pressure at that time does not particularly affect the progress of the reaction and is not limited, but is generally in the range of 0.101 to 0.981 MPa.

In the present invention, the liquid phase pyrolysis reaction of the aminopropionic acid amide derivative and the reaction between the (meth) acrylic acid ester and the amine compound are preferably carried out in the presence of a radical inhibitor. Known polymerization inhibitors can be used, such as hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2, Phenol compounds such as 4-dimethyl-6-tertbutylphenol and hydroquinone monomethyl ether, N-isopropyl-N′-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-para-phenylene Such as diamine, N- (1-methylheptyl) -N′-phenyl-para-phenylenediamine, N, N′-diphenyl-para-phenylenediamine, N, N′-di-2-naphthyl-para-phenylenediamine, etc. Paraphenylenediamines, thiodiphenylamine, etc. Piperidine such as amine compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, acetamidotetramethylpiperidine-1-oxyl Examples thereof include -1-oxyl free radical compounds. These polymerization inhibitors may be used alone or in combination of two or more. Moreover, the addition amount of a polymerization inhibitor is 1-10000 ppm with respect to a (meth) acrylic acid ester or an aminopropionic acid amide derivative, Preferably it is 5-5000 ppm.

The amine compound used in the present invention is an N-mono-substituted or N, N-disubstituted saturated or unsaturated, linear or branched aliphatic primary amine and secondary amine having 1 to 32 carbon atoms. , Morpholine, the primary alkanolamine and secondary alkanolamine having a hydroxyl group, and the primary amine and secondary amine having an amino group. Specifically, (di) methylamine, (di) ethylamine, (di) propylamine, (di) isopropylamine, (di) butylamine, (di) isobutylamine, t-butylamine, (di) pentylamine, ( Di) hexylamine, cyclohexylamine, (di) heptylamine, (di) octylamine, t-octylamine, (di) nonylamine, laurylamine, stearylamine, oleylamine, amine (di) allylamine, methylethylamine, methyl (iso ) Propylamine, methyl (iso) butylamine, methyl (iso) hexylamine, ethylhexylamine, ethyl (iso) propylamine, ethyl (iso) butylamine, ethyl (iso) hexylamine, propylisopropylamine, propylbutylamine, propylhexylamine , Isopropyl butylamine, isop Isopropyl isobutylamine, isopropylhexylamine, butylisobutylamine, butylhexylamine, morpholine, monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, diethanolamine, propanolamine; isopropanolamine, butanol Amine, pentanolamine, hexanolamine, N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine, N, N-dimethylaminopropylamine, N , N-diethylaminopropylamine, N, N-diisopropylaminopropylamine, N, N-diallylaminopropylamine and the like.

Aminopropionic acid amide derivatives obtained by the above-mentioned various production methods are subjected to liquid phase pyrolysis in the presence of an inorganic substance containing silica as a main component, thereby desorbing one molecule of the amine compound and the desired N-mono-substitution (in the order of boiling point together with the reaction solvent). (Meth) acrylamide and N, N-disubstituted (meth) acrylamide can be obtained. In addition, if necessary, the obtained distillate component can be obtained as a distillate component with higher purity by precision distillation.

Table 1 shows silica-based inorganic substances used in Examples and Comparative Examples of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The abbreviations of N-substituted (meth) acrylamide and the materials used in the examples and comparative examples are as follows.
(1) N-substituted (meth) acrylamide
DEAA: N, N-diethylacrylamide
DMAA: N, N-dimethylacrylamide
HEAA: N-hydroxyethylacrylamide
NMAA: N-methylacrylamide
MHEAA: N-methyl-N-hydroxyethylacrylamide
ACMO: acryloylmorpholine
NIPAM: N-isopropylacrylamide
DMAPAA: Dimethylaminopropylacrylamide
HEMAA: N-hydroxyethyl methacrylamide
TBAA: tert-butylacrylamide
DHEAA: N, N-dihydroxyethylacrylamide
NLAA: n-laurylacrylamide
TOAA: tert-octylacrylamide
NSAA: n-stearylacrylamide
LMAA: Lauryl methacrylamide (2) (meth) acrylic acid ester
MA: Methyl acrylate
EA: Ethyl acrylate
MMA: Methyl methacrylate
BA: butyl acrylate (3) (meth) acrylic acid
AAc: Acrylic acid
MAc: Methacrylic acid (4) amine compound
DEA: diethylamine
DMA: Dimethylamine
EA: Ethanolamine
NMA: n-methylamine
Mor: Morpholine i-PA: Isopropylamine
DMAPA: Dimethylaminopropylamine
TBA: tert-butylamine
MEA: Methylethanolamine
DEtA: Diethanolamine
NLA: n-laurylamine
TOA: tert-octylamine
NSA: n-stearylamine (5) Polymerization inhibitor
TDA: Thiodiphenylamine
HQ: Hydroquinone
TEMPO: 2,2,6,6-tetramethylpiperidine-1-oxyl
MEHQ: Hydroquinone monomethyl ether
DDA: styrylated-N-aminobiphenyl
TBC: 4-tert-butylcatechol
BHT: Dibutylhydroxytoluene
W-300: 4,4′-butylidenebis (6-tert-butyl-m-cresol)
(6) Basic catalyst
NaOH: Sodium hydroxide
SM: sodium methoxide (7) ionic liquid ionic liquid 1: 1-butyl-2,3-dimethylimidazolium hexafluorophosphate ionic liquid 2: 1-butyl-1-methylpyrrolidinium bis (trifluoromethane Sulfonyl) imide ionic liquid 3: triethylpentylammonium bis (trifluoromethanesulfonyl) imide

Example 1
In a 1000 mL pressure-resistant reaction vessel (autoclave) equipped with a stirrer and a temperature sensor, 47,7 g (3.0 mol) of methyl N, N-diethylaminopropionate (abbreviation DEA-MA), 263.3 g (3.6 mol) of DEA, SM 8.1 g (0.15 mol) was added and stirred at 90 ° C. for 48 hours. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and 7.4 g (0.075 mol) of sulfuric acid was added under ice cooling to neutralize SM. Then, the reaction solution is cut at a low boiling point by distillation (removing unreacted DEA and by-produced alcohol) to give 622 g of N, N-diethyl-β-diethylaminopropionic acid amide (abbreviation DEA-AAm) (purity 97% ) Was obtained as a pale yellow liquid.
To a 1000 mL four-necked flask equipped with a stirrer and a thermometer, 400 g of the obtained DEA-AAm, 40 g of silica 60 as a silica-based inorganic substance, and 0.4 g of TDA as a polymerization inhibitor were added. Then, a four-necked flask is equipped with a packed tower, a condenser and a distillation receiver, and a small amount of nitrogen gas is flowed as a carrier. The reaction liquid is stirred and adjusted to a kettle temperature of 130 ° C. and a vacuum of 7.0 kPa. The reaction was carried out for 3 hours, and 245 g (purity = 95%) of crude “DEAA” was obtained from the water condenser.
Furthermore, the obtained crude “DEAA” is transferred to a distillation purification apparatus equipped with a packed tower and purified by distillation under reduced pressure (60 ° C./0.13 kPa) to obtain 222 g of a high-purity product “DEAA” as a colorless liquid. The yield was 99.7% and the total yield was 90%. The results are shown in Table 2.

Example 2
In a 1000 mL pressure-resistant reaction vessel (autoclave) equipped with a stirrer and a temperature sensor, MA 258.3 g (3.0 mol), DEA 526.6 g (7.2 mol), SM 8.1 g (0.15 mol) and TDA 0.79 g And stirred at 90 ° C. for 48 hours. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and 7.4 g (0.075 mol) of sulfuric acid was added under ice cooling to neutralize SM. Thereafter, the boiling point was cut by distillation to obtain 621 g of DEA-AAm (purity 99%) as a pale yellow liquid.
In the same manner as in Example 1, 400 g of the obtained DEA-AAm, 40 g of silica 60, and 0.4 g of TDA were used, and a liquid phase pyrolysis reaction was performed in the same manner as in Example 1 to obtain 251 g of crude “DEAA” (purity = 94% )
Further, the crude “DEAA” was purified by distillation in the same manner as in Example 1 to obtain 225 g (purity 99.6%, total yield = 91%) of a high-purity product “DEAA” as a colorless liquid (Table 2). .

Example 3
A 1000 mL pressure-resistant reaction vessel (autoclave) equipped with a stirrer and a temperature sensor was charged with 435.2 g (3.0 mol) of N, N-diethylaminopropionic acid, 263.3 g (3.6 mol) of DEA, and 60 g of silica 60. Stir at 24 ° C. for 24 hours. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, the reaction solution was transferred to a four-necked flask equipped with a packed tower, a condenser and a distillation receiver, and 0.6 g of TDA was added as a polymerization inhibitor. Thereafter, a thermal decomposition reaction was carried out for 3 hours under the conditions of a kettle temperature of 130 ° C. and a vacuum degree of 7.0 kPa in the same manner as in Example 1 to obtain 378 g of crude “DEAA” (purity = 96%).
Further, the obtained crude “DEAA” was purified by distillation in the same manner as in Example 1 to obtain 345 g of a high-purity product “DEAA” (purity 99.7%, total yield = 90%) as a colorless liquid ( Table 2).

Examples 4-10
In Example 1, the aminopropionate derivative and amine compound, the reaction catalyst, the reaction solvent, the polymerization inhibitor, and the reaction conditions as starting materials for the reaction were changed as shown in Table 3, and the synthesis was performed in the same manner as in Example 1. went. Crude N-substituted (meth) acrylamide shown in Table 3 was obtained and further purified by distillation under the conditions shown in Table 2 to obtain N-substituted (meth) acrylamide (purity 99% or more), which was the target compound.

Examples 11-14
In Example 2, the starting material for the reaction, (meth) acrylic acid ester, amine compound, reaction catalyst, reaction solvent, polymerization inhibitor, and reaction conditions were changed as shown in Table 4, and synthesized in the same manner as in Example 4. Went. The crude N-substituted (meth) acrylamide shown in Table 4 was obtained and further purified by distillation or recrystallization under the conditions shown in Table 4 to obtain the target compound, N-substituted (meth) acrylamide (purity 99% or more). did.

Examples 15-20
In Example 3, synthesis was carried out in the same manner as in Example 3 except that aminopropionic acid and amine compound, reaction catalyst, reaction solvent, polymerization inhibitor and reaction conditions, which are starting materials for the reaction, were changed as shown in Table 5. . The crude N-substituted (meth) acrylamide shown in Table 5 was obtained and further purified by distillation or recrystallization under the conditions shown in Table 5 to obtain the target compound, N-substituted (meth) acrylamide (purity 98% or more). did.

Comparative Examples 1-3
In Example 1, the reaction was carried out according to the method described in Example 1, except that the starting materials, catalyst, polymerization inhibitor and reaction conditions were changed as shown in Table 6. The reaction results are shown in Table 6. In these comparative examples, the final product is not purified, and the yield of the obtained crude N-substituted (meth) acrylamide is shown.

Comparative Examples 4-5
In Example 2, the reaction was carried out according to the method described in Example 2 except that the starting materials, catalyst, polymerization inhibitor and reaction conditions were changed as shown in Table 6. The reaction results are shown in Table 6. In these comparative examples, the final product is not purified, and the yield of the obtained crude N-substituted (meth) acrylamide is shown.

Comparative Example 6
In Example 3, the reaction was performed according to the method described in Example 3 except that the starting materials, catalyst, polymerization inhibitor and reaction conditions were changed as shown in Table 6. The reaction results are shown in Table 6. In these comparative examples, the final product is not purified, and the yield of the obtained crude N-substituted (meth) acrylamide is shown.

In Comparative Example 1, the rate of the thermal decomposition reaction was remarkably reduced because of the small amount of inorganic catalyst based on silica used. On the other hand, in Comparative Example 3, since the amount of the catalyst added was too large, the fluidity of the reaction mixture was lost, and the yield of the crude monomer remained at a low level. Also, from the results of Comparative Example 2 and Comparative Example 4, when the thermal decomposition temperature was low, the reaction did not proceed sufficiently. On the other hand, if the thermal decomposition temperature was too high, polymerization troubles occurred in the reaction kettle. This made it impossible to obtain the desired N-substituted (meth) acrylamide. Furthermore, from the results of Comparative Examples 5 and 6, in the production method of the present invention, the charged molar ratio of the amine compound is an important factor for obtaining high yield and high purity N-substituted (meth) acrylamide. Was confirmed. In particular, when synthesizing a high-boiling N-substituted long-chain alkyl (meth) acrylamide that cannot be purified by distillation, as shown in Comparative Example 6, if the charge ratio of the amine compound exceeds 3.0 times mol, unreacted amine In many cases, it was difficult to separate from the target crude monomer, and the yield and purity were low.

As described above, by using the method of the present invention, high-purity N-substituted (meth) acrylamide and N, N can be efficiently used in a short time even under mild reaction conditions using an aminopropionic acid amide derivative as a starting material. -Disubstituted (meth) acrylamides can be produced. Further, by selecting a silica-based catalyst, the reaction proceeds at a sufficient rate even at normal pressure and low temperature, and it can be produced at low cost without any trouble such as polymerization. Furthermore, inorganic substances containing silica as a main component, such as silica and silica alumina, can be separated stably and easily, and thus can be recycled. Moreover, if necessary, it can be applied to various solvents such as organic solvents and ionic liquids.
N-substituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide obtained by the production method of the present invention are useful in daily life as a functional polymer obtained by copolymerization alone or with other polymerizable monomers. Properties, paints, pressure-sensitive adhesives, adhesives, inks, various coating agents, paper strength agents such as paper strength agents, polymer flocculants, polymer modifiers, dispersants used in the treatment of industrial and domestic wastewater, It can be suitably used in a wide variety of fields such as thickeners, synthetic raw materials such as contact lenses and biogels, and reactive diluents for UV curable resins.

Claims (6)

The aminopropionic acid amide derivative represented by the general formula [1] is obtained by desorbing the amine compound represented by the general formula [2] by liquid phase pyrolysis in the presence of an inorganic substance mainly composed of silica. A method for producing N-monosubstituted (meth) acrylamide represented by the general formula [3] or N, N-disubstituted (meth) acrylamide.

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, and R ₃ represents a hydrogen atom or a methyl group.) The compound represented by the general formula [1] is obtained by reacting an aminopropionic acid ester derivative represented by the general formula [4] with at least 1 mol of an amine compound represented by the general formula [2]. A method for producing the N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to claim 1.

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, R ₃ represents a hydrogen atom or a methyl group, and R ₆ is a linear or branched chain having 1 to ₆ carbon atoms Represents an alkyl group of The compound represented by the general formula [1] is obtained by reacting a (meth) acrylic acid ester represented by the general formula [5] with 2 mol or more of an amine compound represented by the general formula [2]. The method for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to claim 1.

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them May form a saturated 5- to 7-membered ring containing an oxygen atom, R ₃ represents a hydrogen atom or a methyl group, and R ₇ is a linear or branched chain having 1 to 6 carbon atoms Represents an alkyl group of The compound represented by the general formula [1] is obtained by reacting an aminopropionic acid derivative represented by the general formula [6] with at least 1 mol of an amine compound represented by the general formula [2]. Item 2. A method for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to Item 1.

(In each formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms (provided that R ₁ and R ₂ are simultaneously hydrogenated) Except when it is an atom and when R ₄ and R ₅ are hydrogen atoms at the same time), or a linear or branched hydroxyalkyl group having 1 to 32 carbon atoms, or 1 to 32 carbon atoms A linear or branched aminoalkyl group which may be the same or different from each other, and R ₁ and R ₂ , and / or R ₄ and R ₅ are nitrogen atoms supporting them And may form a saturated 5- to 7-membered ring containing an oxygen atom, and R ₃ represents a hydrogen atom or a methyl group.) The inorganic substance mainly composed of silica is one or two or more selected from the group consisting of porous silica gel, mesoporous silica, silica alumina, and zeolite. A method for producing N-monosubstituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide according to one item. The N-monosubstituted (meth) acrylamide according to any one of claims 1 to 5, wherein the silica content in the inorganic substance mainly composed of silica is 60 to 100% by weight, or N , Method for producing N-disubstituted (meth) acrylamide.