JP2017031046A - Absorber and generator of carbon dioxide derived from air - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon dioxide generator capable of being used as a carbon source by efficiently absorbing and immobilizing carbon dioxide from air and releasing the immobilized carbon dioxide at proper amount timely and a generation method of carbon dioxide derived from air using the same.SOLUTION: The invention relates to an absorber of carbon dioxide in air containing alkylamine substituted by a hydroxyl group or an amino group which may be substituted, a carbon dioxide generator containing a compound represented by the formula (I), where each symbol is as defined in the description, and a generation method of carbon dioxide from the carbon dioxide generator.SELECTED DRAWING: None

Description

  The present invention relates to an absorbent for carbon dioxide in the air, a carbon dioxide generator comprising a compound in which carbon dioxide in the air is absorbed and immobilized by the absorbent, and the carbon dioxide generator. The present invention relates to a method for generating carbon dioxide derived from air.

  Recently, from the viewpoint of global environmental protection, active discussions have been made on reducing the emission of carbon dioxide, a greenhouse gas, but no truly effective solution has yet been found. As a solution, carbon dioxide capture and storage (CCS) technology that efficiently collects high-concentration carbon dioxide from exhaust gas discharged from thermal power plants, etc., and stores it in the ground or in the sea is considered promising. (Non-Patent Document 1). However, since CCS requires a large investment in large-scale facilities and the like, it cannot be said that it is a realistic solution at the private level (individual level). In addition to carbon dioxide, exhaust gases contain toxic gases such as nitrogen oxides and sulfur oxides at high concentrations, and in order to utilize carbon dioxide recovered with these toxic gases as a carbon source. Many problems remain (Patent Documents 1 and 2). If carbon dioxide in the air (the carbon dioxide ratio in the air is usually only 0.04 to 0.05 v / v%) can be used as a carbon source simply and effectively, a truly effective solution Can be.

To date, research on various chemical reactions using carbon dioxide as a carbon source and research on artificial photosynthesis have been actively conducted, but in most cases, in a carbon dioxide atmosphere (ie, in 100% carbon dioxide). And supercritical carbon dioxide (reactions that exceed the limit temperature and pressure (critical point) at which gas and liquid can coexist) and carbon dioxide cylinders (mainly oil and coal) It is common to use a cylinder filled with liquefied carbon dioxide obtained by completely desulfurizing and deodorizing carbon dioxide recovered as a by-product from the hydrogen production process from LNG, and passing through a compression liquefaction process. Therefore, it does not require any carbon dioxide cylinders that require a lot of labor and energy during the production process, and efficiently absorbs and stores carbon dioxide that is inexhaustible in the air without heating and / or pressurizing. If it can be generated in an appropriate amount and used as a carbon source in a timely manner, it can be a truly environmentally friendly technology.
Currently, the most promising method to collect only carbon dioxide in the air is to absorb the carbon dioxide in the air in an aqueous sodium hydroxide solution, make it an aqueous sodium carbonate solution, and then react with the calcium hydroxide slurry. A method of generating carbon dioxide gas by obtaining solid calcium carbonate and heating it at 900 ° C. is known (Non-Patent Document 2). However, in this method, sodium hydroxide used as an absorbent for carbon dioxide is a deleterious substance, and high temperature conditions (about 900 ° C.) are required when generating carbon dioxide. There was a problem that four steps were required from absorption to generation.

JP 2003-53134 A JP 2005-40683 A

Iijima, M. and Nakatani, S., Kagaku Kogaku, 2013, Vol.77, pages 300-303 Baciocchi, R. Storti, G. and Mazzotti, M. Chemical Engineering and Processing, 2006, Vol. 45, pages 1047-1058.

  An object of the present invention is to efficiently absorb and immobilize carbon dioxide from the air at normal temperature and normal pressure, and to release the immobilized carbon dioxide in an appropriate amount in a timely manner and use it as a carbon source. It is to provide a carbon dioxide generating agent capable of performing the above and a method for generating air-derived carbon dioxide using the same.

  As a result of intensive studies under these circumstances, the present inventors have found that an alkylamine derivative substituted with a hydroxy group or an optionally substituted amino group can efficiently produce carbon dioxide simply by leaving it in the air. It was found that it can be absorbed well and immobilized. Further, carbon dioxide is absorbed and immobilized, formula (I):

(Wherein X is 1, Y is 1 to 3, and Z is 0 to 10) (hereinafter sometimes referred to as “compound (I)”). )) Is found to be storable, and the carbon dioxide absorbed and immobilized from the air by reacting or heating the compound or a composition comprising the compound with an acid, The present inventors have found that the carbon dioxide generator can be generated in a timely manner under mild conditions, and have completed the present invention.

That is, the present invention is as follows.
[1] Formula (I):

(Wherein X is 1, Y is 1 to 3 and Z is 0 to 10). A method for generating carbon dioxide, characterized by generating carbon.
[2] Formula (I):

(Wherein X is 1, Y is 1 to 3 and Z is 3 to 10). By reacting the compound represented by the above with an acid, carbon dioxide is generated. A method of generating carbon dioxide characterized by the above.
[3] The above-mentioned [1], wherein the compound is obtained by leaving an alkylamine substituted with a hydroxy group or an optionally substituted amino group in an air atmosphere to absorb carbon dioxide in the air. Or the method as described in [2].
[4] Alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (Ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The method according to any one of [1] to [3] above, which is selected from the group consisting of:
[5] An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- The above [2] or [3], selected from the group consisting of (ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine and diethylenetriamine. the method of.
[6] The above [1] to [5], wherein the acid is selected from the group consisting of hydrochloric acid, perchloric acid, phosphoric acid, oxalic acid, malonic acid, malic acid, glycolic acid, and trifluoroacetic acid. The method described.
[7] The alkylamine substituted with a hydroxy group or an optionally substituted amino group is o-xylylenediamine, m-xylylenediamine or p-xylylenediamine, X is 1, Y The method according to any one of [1], [3] or [4] above, wherein Z is 1 and Z is 0.
[8] The method of the above-mentioned [7], wherein the heating is performed at about 120 to 140 ° C.
[9] A carbon dioxide absorbent in air comprising an alkylamine substituted with a hydroxy group or an optionally substituted amino group.
[10] Alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (Ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The carbon dioxide absorbent according to [9] above, which is selected from the group consisting of:
[11] An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- The carbon dioxide absorbent as described in [9] above, selected from the group consisting of (ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine and diethylenetriamine. .
[12] Formula (I):

(In formula, X is 1, Y is 1-3, and Z is 0-10.) The carbon dioxide generator formed by containing the compound represented.
[13] Formula (I):

(In formula, X is 1, Y is 1-3, and Z is 3-10.) The carbon dioxide generator containing the compound represented.
[14] An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (Ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The carbon dioxide generator according to [12] above, selected from the group consisting of:
[15] An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- The carbon dioxide generator according to [13] above, selected from the group consisting of (ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine and diethylenetriamine. .

  According to the present invention, it contains an alkylamine substituted with a hydroxy group or an optionally substituted amino group, which can easily and efficiently absorb carbon dioxide in the air at normal temperature and normal pressure. It is possible to provide an absorbent for carbon dioxide in the air. According to the present invention, the following formula (I):

(Wherein X is 1, Y is 1 to 3, and Z is 0 to 10). A carbon dioxide generator containing a compound represented by Or by heating at about 120 to 140 ° C., it is possible to provide a method for effectively generating air-derived carbon dioxide in an appropriate amount in a timely manner regardless of location or environment. The carbon dioxide generator of the present invention can be effectively used for various organic synthesis reactions using carbon dioxide derived from air as a carbon source. Furthermore, according to the present invention, the use of external energy (heating, pressurization, stirring, etc.) is suppressed as much as possible, and carbon dioxide in the air is efficiently absorbed and immobilized, and the carbon dioxide derived from air is relaxed. It is possible to provide a carbon dioxide absorbent and a carbon dioxide generator that are friendly to the global environment in that they can be released at a low temperature.
Among them, o-xylylenediamine, m-xylylenediamine or p-xylylenediamine does not absorb water (humidity) in the air when carbon dioxide is absorbed, so that the carbon dioxide adduct is an organic compound that requires anhydrous conditions. It is particularly useful as a carbon dioxide generator that can also be used for the reaction.

Figure 1 shows changes in carbon dioxide concentration (ppm) over time when alkylamines substituted with various hydroxy groups or optionally substituted amino groups in a desiccator are left in a petri dish. Represent. FIG. 2 shows the carbon dioxide concentration over time when o-xylylenediamine (OXDA), m-xylylenediamine (MXDA) or p-xylylenediamine (PXDA) is left in a petri dish in a petri dish. It represents the change in (ppm). FIG. 3 shows the change in mass (increased g number) with the passage of time when alkylamines substituted with various hydroxy groups or optionally substituted amino groups were left in the air, respectively. FIG. 4 shows mass change (increased g number) with the passage of time when m-xylylenediamine (MXDA) is left in the air. FIG. 5 shows an ORTEP diagram by single crystal X-ray crystal structure analysis of m-xylylenediamine carbon dioxide adduct (compound (I-6)) (MXDA · CO ₂ ). FIG. 6 shows a carbon dioxide adduct of m-xylylenediamine (compound (I-6)) (MXDA · CO ₂ ) and a carbon dioxide adduct of o-xylylenediamine (compound (I-7)) (OXDA · CO ₂₎ and p- xylylene carbon dioxide adduct of the amine (compound (I-8)) shows a (PXDA · CO ₂ solid state NMR spectrum) ^(C 13 -NMR).

  Hereinafter, the present invention will be described in detail.

(Definition)
In the present specification, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In the present specification, examples of the “alkyl (group)” include linear or branched alkyl groups having 1 or more carbon atoms. When there is no particular limitation on the carbon number range, C _{1- 10} alkyl group, more preferably C _1-6 alkyl group, and particularly preferably C _1-4 alkyl group. Preferable specific examples in the case where the carbon number range is not limited include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like.

In the present specification, examples of the “aralkyl (group)” include a C _7-20 aralkyl group, preferably a C _7-16 aralkyl group (C _6-10 aryl-C _1-6 alkyl group). Specific examples include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, naphthylmethyl, 1-naphthylethyl, 1-naphthylpropyl, and the like, and benzyl is particularly preferable.

In the present specification, examples of the “alkoxy (group)” include an alkoxy group having 1 or more carbon atoms, and particularly when there is no limitation on the carbon number range, a C _1-10 alkoxy group is preferable. Is a C _1-6 alkoxy group. Preferable specific examples in the case where the carbon number range is not limited include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and the like.

In the present specification, the “alkenyl (group)” is preferably a linear or branched C _2-6 alkenyl group, such as vinyl, 1-propenyl, allyl, isopropenyl, butenyl, isobutenyl and the like. Can be mentioned. Among them, a C _2-4 alkenyl group is preferable.

In the present specification, as the “alkynyl (group)”, a C _2-6 alkynyl group and the like are preferable. For example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1- Examples include pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like. Among these, a C _2-4 alkynyl group is preferable.

In the present specification, “cycloalkyl (group)” means a cyclic alkyl group, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Among these, C _3-6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are preferable.

In the present specification, “aryl (group)” means a monocyclic or polycyclic monovalent hydrocarbon group exhibiting aromaticity. Specifically, for example, phenyl, 1-naphthyl, 2 _-C6-14 aryl groups such as naphthyl, biphenylyl, 2-anthryl and the like. Among them, a C _6-10 aryl group is more preferable, and phenyl is particularly preferable.

In the present specification, “arylene (group)” means a monocyclic or polycyclic divalent hydrocarbon group exhibiting aromaticity. Specifically, for example, 1,2-phenylene, 1 , 3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,4-naphthylene, _{C 6-14} arylene groups such as biphenylene, and the like. Among them, a C _6-10 arylene group is preferable, and a phenylene group (1,2-phenylene, 1,3-phenylene or 1,4-phenylene) is particularly preferable.

In the present specification, the “optionally substituted amino group” in the “alkylamine substituted with a hydroxy group or an optionally substituted amino group” means one of two hydrogen atoms of the amino group. This means a group in which one or two may be substituted with a group other than a hydrogen atom. Examples of the “optionally substituted amino group” include, for example, an amino group, a C _1-10 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _{3- Examples} thereof include an amino group mono- or di-substituted with a substituent selected from a ₆ cycloalkyl group, a C _6-14 aryl group, a C _7-16 aralkyl group, and the like.

Here, as the C _1-10 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-6 cycloalkyl group, C _6-14 aryl group and C _7-16 aralkyl group, Among these, a C _1-4 alkyl group (eg, methyl, ethyl, propyl, etc.) is preferable.

C _1-10 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-6 cycloalkyl group, C _6-14 constituting the substituent of the “ _optionally substituted amino group”. The aryl group and the C _7-16 aralkyl group each have 1 to 3 substituents (eg, halogen, nitro, cyano, hydroxy, amino, C _1-6 alkylamino, di (C _1-6 ) at substitutable positions. Alkyl) amino, C _1-6 alkyl, C _1-6 alkoxy, carboxy, etc.). When there are two or more substituents, each substituent may be the same or different.

  The “optionally substituted amino group” is preferably an amino group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, a 2-hydroxyethylamino group, a 2-aminoethylamino group, or the like. Among them, an amino group, a methylamino group, dimethylamino, a 2-hydroxyethylamino group and the like are preferable.

  In the present specification, “an alkylamine substituted with a hydroxy group or an optionally substituted amino group” means that an alkyl group substituted with a “hydroxy group or an optionally substituted amino group” is an amino group. It means a bound compound. The alkyl group may be a hydroxy group or an optionally substituted amino group and an amino group as long as the bonding site of the amino group. In addition to the “alkyl group”, an alkyl group via an arylene group (eg, It may be a phenylenebis (methylene) group (eg, m-xylylene group, o-xylylene group, p-xylylene group). Specific examples of the “alkylamine substituted with a hydroxy group or an optionally substituted amino group” include, for example, monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- ( Methylamino) ethanol, 2- (ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine Examples include amines and p-xylylenediamine, among which monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, ethylenediamine, and N, N′-dimethylethylenediamine. Jie Rentriamine, o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine are preferred. Monoethanolamine, 2- (methylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylene Range amine, m-xylylenediamine, p-xylylenediamine and the like are more preferable.

  In this specification, “normal temperature” refers to normal temperature (15 ° C. to 25 ° C.) defined by the 16th revised Japanese Pharmacopoeia General Rules.

  In the present specification, “about” is defined as ± 5 ° C.

(Carbon dioxide absorbent of the present invention)
The carbon dioxide absorbent of the present invention is an alkylamine itself substituted with a hydroxy group or an optionally substituted amino group, or a composition containing the same.

  Examples of the “alkylamine substituted with a hydroxy group or an optionally substituted amino group” include those described above. Among them, monoethanolamine, diethanolamine, 2- (methylamino) ethanol, 2-amino- 2-Methyl-1-propanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine or p-xylylenediamine are particularly suitable because of their high carbon dioxide absorption capacity. used. These are commercially available and can be easily obtained. Monoethanolamine, 2- (methylamino) ethanol, diethanolamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine or p-xylylenediamine also have advantages such as low volatility and low toxicity. . Furthermore, o-xylylenediamine, m-xylylenediamine or p-xylylenediamine does not absorb water (moisture in the air) upon absorption of carbon dioxide, and thus is particularly suitable as a hydrophobic carbon dioxide fixing agent. .

  In the carbon dioxide absorbent of the present invention, an alkylamine itself substituted with a hydroxy group or an optionally substituted amino group can be used, but a composition containing the same can also be used. This composition may contain only 1 type in the alkylamine substituted by the hydroxy group or the amino group which may be substituted, and may contain 2 or more types.

  Further, the carbon dioxide absorbent of the present invention includes a compound capable of absorbing carbon dioxide other than alkylamine substituted with a hydroxy group or an optionally substituted amino group, for example, methanol, polyethylene glycol and the like. You may go out.

  The carbon dioxide absorbent of the present invention may contain a desiccant (magnesium sulfate, molecular sieves, etc.) for removing moisture.

  However, considering the carbon dioxide absorption capacity, the content of the alkylamine substituted with the hydroxy group or the optionally substituted amino group in the carbon dioxide absorbent of the present invention is 80% by weight or more of the entire absorbent. Among them, those consisting only of an alkylamine substituted with a hydroxy group or an optionally substituted amino group are particularly preferred.

(Method of absorbing and fixing carbon dioxide in the air using the carbon dioxide absorbent of the present invention)
By leaving the carbon dioxide absorbent of the present invention at room temperature, normal pressure and in the air (in an air atmosphere), the carbon dioxide in the air is absorbed, and the carbon dioxide absorbent in the air is absorbed into the carbon dioxide absorbent of the present invention. Fix carbon.

  Specifically, for example, a carbon dioxide concentration meter and a petri dish are prepared in an openable / closable desiccator, the carbon dioxide absorbent of the present invention is added to the petri dish in the desiccator, the door is immediately closed, and left for several hours to seven days. To do. Observe the carbon dioxide concentration in the desiccator over time at normal temperature and pressure. And when the carbon dioxide concentration in a desiccator stops changing, it can confirm that the fixation | immobilization of the carbon dioxide in the air to the carbon dioxide absorbent of this invention was completed.

  As the carbon dioxide absorbent of the present invention, either a liquid or a solid can be used, but it is preferable to use a liquid.

(Carbon dioxide generating agent of the present invention)
The carbon dioxide generating agent of the present invention is a method of leaving carbon dioxide in the air by allowing the alkylamine substituted with the hydroxy group or the optionally substituted amino group to stand for several hours to seven days in an air atmosphere. The following formula (I) obtained by sufficient absorption:

(Wherein X is 1, Y is 1 to 3, and Z is 0 to 10), or the compound represented by (Compound (I)) itself or containing it It is the composition which becomes. Although it does not restrict | limit especially as compound (I), Especially suitable compound (I) has the following formula:

,

,

,

Or

It is a compound represented by these.
Moreover, as a compound (I) which does not contain water, following formula:

,

Or

Is particularly preferred.

  Although the compound (I) itself can be used for the carbon dioxide generator of this invention, the composition containing it can also be used. This composition may contain only 1 type of compound (I), and may contain 2 or more types of different types of compound (I).

  The carbon dioxide generator of the present invention may contain a desiccant (magnesium sulfate, molecular sieves, etc.) for removing water.

  However, considering the carbon dioxide generating ability, the content of the compound (I) in the carbon dioxide generating agent of the present invention is preferably 80% by weight or more of the entire generating agent, and particularly the compound (I) only consists of the compound (I). preferable.

  As the carbon dioxide generator of the present invention, either a liquid or a solid can be used.

(Method for generating air-derived carbon dioxide using the carbon dioxide generator of the present invention)
The carbon dioxide generating agent of the present invention generates carbon dioxide by reacting with an acid at normal temperature or normal pressure, or by heating at about 120 to 140 ° C.

  Specifically, for example, when the generated carbon dioxide is used as a carbon source for an organic synthesis reaction, a reaction device (its material is not particularly limited) that can be connected to a reaction vessel that performs the organic synthesis reaction is prepared. The carbon dioxide generator (compound (I)) of the present invention is weighed and added thereto. After diluting with a solvent as necessary, the generation of carbon dioxide can be visually confirmed by dropping an acid or heating.

  When the carbon dioxide generating method and the carbon dioxide generating agent of the present invention are used for an organic synthesis reaction or the like, the amount of carbon dioxide to be generated depends on the total volume of the reaction apparatus rather than the amount of the reaction substrate. Therefore, it is desirable to set the amount of compound (I) and / or acid used so that carbon dioxide is generated about twice as much as the total volume of the reactor used.

  In the carbon dioxide generating method of the present invention, a solvent is not always necessary, but examples of the solvent that can be used include alcohols such as methanol, ethanol, and isopropanol.

The acid used in the carbon dioxide generating method of the present invention is not particularly limited. Specifically, for example, dilute hydrochloric acid (eg, 10% hydrochloric acid), perchloric acid, phosphoric acid aqueous solution (eg, 85% phosphoric acid) Aqueous solution, etc.), oxalic acid, malonic acid, malic acid, glycolic acid, trifluoroacetic acid and the like. Among them, dilute hydrochloric acid (eg, 10% hydrochloric acid) is preferably used.
The amount of the acid to be used is generally 0.01 to 3 mol, preferably 0.1 to 2 mol, per 1 mol of compound (I). It is also possible to adjust the amount of carbon dioxide generated depending on the amount of acid used.

  Moreover, in the carbon dioxide generating method by heating of this invention, it is possible to generate carbon dioxide effectively only by heating at about 120-140 degreeC. This generation method is an extremely mild carbon dioxide generation method as compared with the conventional method which requires heating conditions at a high temperature of 900 ° C.

  As described above, the carbon dioxide absorbent and carbon dioxide generator of the present invention can significantly reduce the amount of external energy used such as heating, pressurization, and stirring when used. It is an environmentally friendly reagent.

  In addition, when the carbon dioxide generator of the present invention is used, carbon dioxide absorbed and immobilized from the air by addition of acid and adjustment of the amount of acid used or mild heating, when necessary under mild conditions. Since only the necessary amount can be generated, it can be effectively used as a carbon source in various organic synthesis reactions and the like.

EXAMPLES The present invention will be described more specifically with reference to the following examples and experimental examples. However, the present invention is not limited thereby, and may be changed without departing from the scope of the present invention.
Melting | fusing point measurement was measured using the Yanagimoto Seisakusho melting | fusing point measuring device (Micro Melting Point Apparatus MP-J3).
¹ H and ¹³ C-NMR spectra were measured using JEOL ECS400 or ECA600 using deuterated chloroform or deuterated methanol as a solvent. The data for ¹ H-NMR are chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = double doublet, dt = double triplet, brs. = Broad singlet, sep = septet), coupling constant (Hz), integration and assignment.
Solid state NMR was measured by CP-MAS method using JEOL JNM-ECA300. The measurement conditions are as follows.
¹³ C resonance frequency: 74.175 MHz,
¹ H resonance frequency: 294.988 MHz,
¹ H decoupling frequency: 50 kHz,
MAS speed: 12 kHz and measurement temperature: room temperature Infrared absorption measurement is carried out by transmission measurement with a chloroform solution in a NaCl plate-fixed cell using an infrared spectrophotometer FT / IR-8700 manufactured by Shimadzu, or Thermo Scientific It measured by ATR method using manufactured Nicolet iS5 FT-IR spectrometer.
Elemental analysis was performed using J-SCIENCE LAB JM10.
The concentration of carbon dioxide was measured using a carbon dioxide concentration meter (GC-02) manufactured by God Ability (GA).
X-ray crystal structure analysis was performed using a Rigaku X-ray crystal structure analyzer (model: R-AXIS RAPID II).
“Room temperature” in the following examples usually indicates about 10 ° C. to about 25 ° C. The ratio shown in the mixed solvent is a volume ratio unless otherwise specified. Unless otherwise indicated, “%” indicates “% by weight”.

  The alkylamine substituted with a hydroxy group or an optionally substituted amino group, which is the carbon dioxide absorbent used in the preparation of the compound (I) used as the carbon dioxide generator of the present invention, is a commercially available product (monoethanolamine). (Manufactured by Tokyo Chemical Industry Co., Ltd.), diethanolamine (manufactured by Nacalai Tesque Co., Ltd.), 2- (methylamino) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-amino-2-methyl-1-propanol (Kanto Chemical Co., Ltd.) ), Ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N, N'-dimethylethylenediamine (manufactured by Sigma Aldrich Japan Co., Ltd.), diethylenetriamine (manufactured by Wako Pure Chemical Industries, Ltd.), o-xylylenediamine (sigma aldrich japan stock) Company-made), m-xylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Or p- xylylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)) can be prepared according to the method it may be used as it is, or per se equivalent methods known or thereto.

Example 1
Changes in the amount of carbon dioxide in the air over time when alkylamines substituted with various hydroxy groups or optionally substituted amino groups are used as carbon dioxide absorbents

(Experimental operation example)
A carbon dioxide concentration meter and a petri dish were prepared in an openable / closable desiccator (35.7 L). Thereafter, alkylamine (5 mmol) substituted with various hydroxy groups or optionally substituted amino groups was added to the petri dish in the desiccator, the door was immediately closed, and the carbon dioxide concentration in the desiccator was kept at room temperature for 24 hours. Measured. The initial concentration of carbon dioxide depends on the concentration of carbon dioxide in the air, but the concentration of carbon dioxide in the air is not always constant and varies within a range of 437 to 640 ppm, and thus varies from experiment to experiment (see FIG. 1 and FIG. 2).

(Measurement of carbon dioxide absorption)
Alkylamine (0.33 mol) substituted with various hydroxy groups or optionally substituted amino groups was added to the petri dish, and allowed to stand in air at room temperature, and the increase in mass (g) was 90 hours. Weighed with an electronic balance over time (see FIG. 3).
m-Xylylenediamine and p-xylylenediamine (0.073 mol) were added to the petri dish and allowed to stand in air at room temperature. The increase in mass (g) was weighed with an electronic balance over 7 days. (See FIG. 4).
The amount of carbon dioxide absorbed can be calculated from the increased amount and the composition of the compound after carbon dioxide absorption (compound (I)) determined by the following method.

(Method for determining composition of compound (I))
The component composition of compound (I) produced by leaving alkylamine (carbon dioxide absorbent) substituted with various hydroxy groups or optionally substituted amino groups in air at room temperature is as follows: Can be determined. That is, various carbon dioxide absorbents were respectively added to the petri dish and allowed to stand in air at room temperature for 7 days. Then, component ratio etc. were specified by the elemental analysis of the compound (Compound (I-1)-Compound (I-8)) after carbon dioxide absorption. The results are shown in the following Table 1 (compounds (I-1) to (I-5)) and Table 2 (compounds (I-6) to (I-8)).

The results of the above experiment using various carbon dioxide absorbents are shown in FIGS. According to FIG. 1, monoethanolamine, diethanolamine, 2- (methylamino) ethanol, 2-amino-2-methyl-1-propanol, ethylenediamine, N, N′-dimethylethylenediamine or diethylenetriamine are used as carbon dioxide absorbents. When used, it was confirmed that any of them can efficiently absorb carbon dioxide in the air. In addition, according to FIG. 3, when monoethanolamine, 2- (methylamino) ethanol or diethylenetriamine is used as the carbon dioxide absorbent, it is saturated by leaving it in the air for about one day. It was confirmed that carbon dioxide could not be absorbed.
In addition, according to FIG. 2, when any of o-xylylenediamine, m-xylylenediamine and p-xylylenediamine is used as the carbon dioxide absorbent, the carbon dioxide absorption capacity equivalent to that of monoethanolamine is used. It was confirmed that Moreover, according to FIG. 4, when m-xylylenediamine is used as the carbon dioxide absorbent, it is saturated by leaving it in the air for about two days, and is quantitatively equivalent to m-xylylenediamine and the like. It was confirmed to absorb molar amounts of carbon dioxide.
Furthermore, according to single crystal X-ray crystal structure analysis data (FIG. 5) and solid state ¹³ C-NMR data (FIG. 6) of compound (I-6), compound (I-6) was obtained from m-xylylenediamine and It was confirmed that carbon dioxide had a structure of [3- (aminomethyl) benzyl] carbamic acid in which a bond was formed 1: 1.

Example 2
Carbon dioxide generation test by acid treatment from compound (I) that absorbs and immobilizes carbon dioxide in the air

(Experimental operation example 1)
Compound (I-1) to Compound (I-5) (1 mmol) obtained in Example 1 above were diluted with dilute hydrochloric acid (eg, 10% hydrochloric acid), perchloric acid, phosphoric acid aqueous solution (eg, 85% phosphoric acid aqueous solution). Etc.), acids (1 mmol) such as oxalic acid, malonic acid, malic acid, glycolic acid and trifluoroacetic acid were added, and gas generation was confirmed. As a result of passing the produced gas through lime water, the lime water became cloudy, and it was confirmed that carbon dioxide was generated from the compounds (I-1) to (I-5).

(Experimental operation example 2)
The compound (I-1) obtained in Example 1 (280 mg, 1 mmol), 10% hydrochloric acid, and a carbon dioxide concentration meter were prepared in a desiccator (35.7 L) that can be opened and closed. After closing the door, 10% hydrochloric acid (0.1-0.9 mL) is added to compound (I-1) at room temperature and stirred, and the carbon dioxide increase in the desiccator (ie, the amount of carbon dioxide generated) is increased. It was measured after 3 hours. The increased amount of carbon dioxide was calculated on the assumption that the internal pressure in the desiccator did not change. The results are shown in Table 3 below.

  According to Table 3, it was confirmed that the amount of generated carbon dioxide can be adjusted by increasing or decreasing the amount of acid added. Therefore, by using the carbon dioxide generator of the present invention, it is possible to generate carbon dioxide absorbed and immobilized from the air by the addition of an acid in a necessary amount when necessary. It can be effectively used for organic synthesis reactions.

Example 3
Carbon dioxide generation test by heating from compound (I) that absorbs and immobilizes carbon dioxide in the air

(Experimental operation example)
Generation of gas was confirmed by heating the compound (I-6) (50 mmol) obtained in Example 1 at about 120 to 140 ° C. (oil bath temperature). As a result of passing the produced gas through lime water, the lime water became cloudy, and it was confirmed that carbon dioxide was generated from the compound (I-6).
Since the compound (I-6) does not contain moisture, the use of the carbon dioxide generator of the present invention requires anhydrous reaction conditions using carbon dioxide absorbed and immobilized from the air as a carbon source. It can also be effectively used for organic synthesis reactions (eg, Grignard reaction).

Example 4 (Application Example 1 for Organic Synthesis Reaction)
Conversion reaction of propargylamine to 5-methylene-2-oxazolidinone using compound (I-1) as a carbon dioxide generator

In a first flask (reaction vessel), propargylamine (0.1 mmol), and (acetonitrile) [(2-biphenyl) di-tert-butylphosphine] hexafluoroantimonate (I) ([Au (JohnPhos) ( NCMe)] SbF ₆ ); Sigma Aldrich Japan Co., Ltd.) (0.002 mmol) in methanol (1 mL) solution is prepared, and (CO ₂ ) ₁ · (monoethanolamine) is added to the second flask (carbon dioxide generator). ) ₃ · (H ₂ O) ₃ (Compound (I-1)) (2.8 g, 10 mmol) was prepared. At room temperature and normal pressure, both flasks are connected with a glass tube that can be opened and closed, the entire apparatus is opened, and dilute hydrochloric acid (10% hydrochloric acid, 6 mL, 17 mmol) is added dropwise to the second flask to generate carbon dioxide. The entire apparatus was replaced with the generated carbon dioxide. The whole apparatus was shaken with stirring or hand for a while, and after the generation of carbon dioxide was stopped, the whole reaction apparatus was sealed and stirred or left at room temperature for 1 day. Thereafter, the solvent on the reaction vessel side was distilled off, and the residue was purified by silica gel column chromatography to obtain 5-methylene-2-oxazolidinone (9.0 mg, yield 91%). The amount of carbon dioxide generated from the carbon dioxide generator depends on the total volume of the reactor rather than the amount of reaction substrate. Therefore, the amounts of compound (I-1) and dilute hydrochloric acid used were calculated so that about twice as much carbon dioxide as the total volume (about 90 mL) of the reactor used was generated.
¹ H NMR (CDCl ₃ ) δ 6.15 (brs, 1H), 4.79-4.77 (m, 1H), 4.32-4.30 (m, 1H), 4.27-4.25 (m, 2H);
¹³ C NMR (CDCl ₃ ) δ 157.7, 151.3, 86.8, 44.3;
IR 3472, 3290, 3026, 1786, 1726, 1695, 1674, 1472, 1352, 1279, 1186, 1080, 986 cm ^-1 .

  From the above results, by using the carbon dioxide generator of the present invention, the use of air-derived carbon dioxide as a carbon source efficiently while suppressing the use of external energy such as heating and pressurization as much as possible. It is possible to synthesize oxazolidinone derivatives, which are important synthesis precursors, in good yield.

Example 5 (Application Example 2 for Organic Synthesis Reaction)
(1) Conversion reaction from phenylmagnesium bromide to benzoic acid (Grignard reaction) using compound (I-6) as a carbon dioxide generator

(A) [3- (Aminomethyl) benzyl] carbamic acid (Compound (I-6)) (9.01 g, 50 mmol) was heated at about 120 to 140 ° C. (oil bath temperature) to generate carbon dioxide. .
(B) Magnesium in THF (288 mg, 12 mmol) and iodine (catalytic amount) were added, and then bromobenzene (1.05 mL, 10 mmol) was added dropwise and heated at room temperature for 1 hour in a nitrogen atmosphere. Then, it cooled to 0 degreeC, the carbon dioxide generated by said (A) was added, and it stirred for 3 hours. The reaction solution was quenched with an aqueous ammonium chloride solution, extracted with diethyl ether, and purified by silica gel column chromatography to obtain benzoic acid (1.19 g, 99% yield).

(2) Conversion reaction from cyclohexylmagnesium bromide to cyclohexylcarboxylic acid (Grignard reaction) using compound (I-6) as a carbon dioxide generator

(C) [3- (Aminomethyl) benzyl] carbamic acid (Compound (I-6)) (9.01 g, 50 mmol) was heated at about 120 to 140 ° C. (oil bath temperature) to generate carbon dioxide. .
(D) Magnesium (288 mg, 12 mmol) and iodine (catalytic amount) were added in THF, and then bromocyclohexane (1.23 mL, 10 mmol) was added dropwise, followed by heating at room temperature for 1 hour in a nitrogen atmosphere. Then, it cooled to 0 degreeC, the carbon dioxide generated by said (C) was added, and it stirred for 3 hours. The reaction solution was quenched with an aqueous ammonium chloride solution, extracted with diethyl ether, and purified by silica gel column chromatography to obtain cyclohexylcarboxylic acid (1.26 g, 99% yield).

  From the above results, it is confirmed that by using the carbon dioxide generator of the present invention, air-derived carbon dioxide can be efficiently used as a carbon source for anhydrous reaction even under extremely mild heating conditions as compared with the conventional method. It was done.

  According to the present invention, it contains an alkylamine substituted with a hydroxy group or an optionally substituted amino group, which can easily and efficiently absorb carbon dioxide in the air at normal temperature and normal pressure. It is possible to provide an absorbent for carbon dioxide in the air. Also, according to the present invention, the carbon dioxide in the air can be fixed and stored, formula (I):

(Wherein X is 1, Y is 1 to 3, and Z is 0 to 10). Can do. Then, the carbon dioxide generator reacts with an acid or is heated at about 120 to 140 ° C. to effectively generate air-derived carbon dioxide in an appropriate amount in a timely manner regardless of location or environment. Can be provided. The carbon dioxide generator of the present invention can be effectively used for various organic synthesis reactions including reactions that require anhydrous conditions using carbon dioxide derived from air as a carbon source. In addition, according to the present invention, carbon dioxide in the air can be efficiently absorbed and fixed, and carbon dioxide derived from air can be released while suppressing the use of external energy (heating, pressurization, stirring, etc.) as much as possible. It is possible to provide a carbon dioxide absorbent and a carbon dioxide generator that are friendly to the global environment.

Claims (11)

Formula (I):

(Wherein X is 1, Y is 1 to 3 and Z is 0 to 10). A method for generating carbon dioxide, characterized by generating carbon.   The method according to claim 1, wherein the compound is obtained by allowing an alkylamine substituted with a hydroxy group or an optionally substituted amino group to stand to absorb carbon dioxide in the air in an air atmosphere.   An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (ethylamino) ) Group consisting of ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The method according to claim 1, wherein the method is selected from:   The method according to any one of claims 1 to 3, wherein the acid is selected from the group consisting of hydrochloric acid, perchloric acid, phosphoric acid, oxalic acid, malonic acid, malic acid, glycolic acid and trifluoroacetic acid.   The alkylamine substituted with a hydroxy group or an optionally substituted amino group is o-xylylenediamine, m-xylylenediamine or p-xylylenediamine, X is 1, Y is 1 The method according to any one of claims 1 to 3, wherein Z is 0.   The method of claim 5, wherein the heating is performed at about 120-140 ° C.   A carbon dioxide absorbent in air comprising an alkylamine substituted with a hydroxy group or an optionally substituted amino group.   An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (ethylamino) ) Group consisting of ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The carbon dioxide absorbent according to claim 7, which is selected from: Formula (I):

(In formula, X is 1, Y is 1-3, and Z is 0-10.) The carbon dioxide generator formed by containing the compound represented.   An alkylamine substituted with a hydroxy group or an optionally substituted amino group is monoethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, 2- (methylamino) ethanol, 2- (ethylamino) ) Group consisting of ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, ethylenediamine, N, N′-dimethylethylenediamine, diethylenetriamine, o-xylylenediamine, m-xylylenediamine and p-xylylenediamine The carbon dioxide generator according to claim 9, which is selected from:   The alkylamine substituted with a hydroxy group or an optionally substituted amino group is o-xylylenediamine, m-xylylenediamine or p-xylylenediamine, X is 1, Y is 1 The carbon dioxide generator according to claim 9, wherein Z is 0.