JP2003252842A - Method for producing n-hydroxyalkyl compound and tris(2-hydroxyethyl)isocyanurate composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an N-hydroxyalkyl compound through suppressing discoloration caused by solvent decomposition and suppressing impurities due to the catalyst, and also in high selectivity, and to provide a highly heat-resistant and high-quality tris(2-hydroxyethyl) isocyanurate composition with suppressed discoloration and slight impurities. <P>SOLUTION: The method for producing the N-hydroxyalkyl compound comprises carrying out a reaction between an amido- or imido-functional compound and an epoxy compound in the presence of a catalyst; wherein the catalyst consists of a solid ion exchanger. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an N-hydroxyalkyl compound and a tris (2-hydroxyethyl) isocyanurate composition.

[0002]

2. Description of the Related Art N-hydroxyalkyl compounds are industrially important compounds as raw materials for polyester resins, polyurethane resins, oxazolidones, fiber treatment agents, plasticizers, etc., and as solvents. Among such N-hydroxyalkyl compounds, tris (2-hydroxyethyl) isocyanurate [abbreviation: THEI] having a structure in which hydroxyethyl groups are added to all nitrogen atoms of the triazine ring
C] is excellent in heat resistance and flame retardancy due to the triazine ring, and is also excellent in compatibility. Therefore, in addition to insulating varnish, it is difficult to use as a raw material for various paint resins, a stabilizer for vinyl chloride resin, and various plastics. It is a compound useful as a flame retardant.

In Japanese Patent Publication No. 43-26862, DM
A method of producing tris (2-hydroxyethyl) isocyanurate by introducing ethylene oxide into cyanuric acid in F is disclosed. In this manufacturing method, DMF is used because cyanuric acid, which is a reaction raw material, is difficult to dissolve in a general solvent. However, DMF is decomposed during the reaction, and impurities are mixed in the product, and the product may be colored due to the impurities to deteriorate the product quality. In this production method, the reaction is carried out without catalyst using DMF, but it is considered that DMF as the solvent has a weak catalytic action.

In Japanese Patent Publication No. 44-23332, cyanuric acid and alkylene oxide are reacted in an aliphatic nitrile solvent having 5 or less carbon atoms with a tertiary amine or a quaternary ammonium hydroxide as a catalyst. A method of making a hydroxyalkyl isocyanurate is disclosed. In this production method, a catalyst is used to compensate for the slow reaction rate because the raw material isocyanuric acid is difficult to dissolve in the solvent, but impurities derived from the catalyst are mixed in the product, It may reduce the quality. In addition, there is room for adding alkylene oxide to all the nitrogen atoms of cyanuric acid to enhance the selectivity.

JP-B-45-8865 discloses a tris for reacting cyanuric acid in water with alkylene oxide in the presence of a hydroxide of an alkali metal or an alkaline earth metal, a salt thereof or a metal halide as a catalyst. A method of synthesizing (β-hydroxyalkyl) isocyanurate is disclosed. However, even in this synthetic method,
Impurities derived from the catalyst are mixed in the product, which causes troubles when the product is used for various purposes, and there is a risk of degrading the product quality. Therefore, there is room for improvement in this respect.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is possible to suppress coloration due to the decomposition of a solvent and to suppress impurities due to a catalyst, Moreover, it is intended to provide a method for producing an N-hydroxyalkyl compound having a high selectivity, and to provide a high-quality tris (2-hydroxyethyl) isocyanurate composition which is suppressed in coloring, has few impurities, and has high heat resistance. With the goal.

[0007]

Means for Solving the Problems The present inventors have conducted various studies on a method for producing an N-hydroxyalkyl compound by reacting a compound having an amide group or an imide group with an epoxy compound in the presence of a catalyst. As a result, when the compound having an amide group or an imide group is a solid and is difficult to dissolve in a general solvent, a solvent having a strong polarity such as DMF is used, or the reaction rate is slow because it is difficult to dissolve in the solvent. In order to make up for this, if a catalyst is used, the reaction between the active hydrogen possessed by the amide group or imide group and the epoxy compound will proceed, but in the case of using a strongly polar solvent, the solvent will decompose. This will cause the product to be colored, and when a catalyst is used, the catalyst will be mixed in the product, which will cause a problem when the N-hydroxyalkyl compound is used. However, when a solid ion exchanger is used, (1) since it is a solid heterogeneous catalyst, there are no impurities derived from the catalyst, and (2) the reaction rate is increased by the catalytic reaction (high activity). Therefore, it becomes possible to select a solvent without being bound by a solvent forcibly dissolving the raw materials for production, such as a solvent having a high polarity such as DMF.
(3) It has been found that the selectivity of addition of an epoxy compound to an amide group or an imide group is increased, and (4) the reaction at a low temperature can be achieved, and the above problems are solved satisfactorily. The present invention has been made, and has reached the present invention.

That is, the present invention is a method for producing an N-hydroxyalkyl compound by reacting a compound having an amide group or an imide group with an epoxy compound in the presence of a catalyst, wherein the catalyst is a solid ion. It is a method for producing an N-hydroxyalkyl compound that is an exchanger.
The present invention is described in detail below.

In the method for producing an N-hydroxyalkyl compound of the present invention, a compound having an amide group or an imide group is reacted with an epoxy compound, that is, active hydrogen contained in an amide group or an imide group is reacted with an epoxy compound. This will produce an N-hydroxyalkyl compound. These manufacturing raw materials may be used alone or in combination of two or more kinds. In the present invention, tris (hydroxyalkyl) isocyanurate is preferable as the product N-hydroxyalkyl compound, and tris (2-hydroxyethyl) isocyanurate useful for various applications is particularly preferable. . In addition, due to the effect of the present invention, since the amount of impurities is particularly small, a product having high heat resistance and high quality can be obtained.

The compound having an amide group or an imide group is preferably a cyclic amide or a cyclic imide, and the cyclic amide is isocyanuric acid, 2-pyrrolidone or ε-.
As caprolactam, hydantoin, cyclic imide,
Succinimide is suitable, and among these, when producing tris (2-hydroxyethyl) isocyanurate, isocyanuric acid is used. As the compound having an amide group or an imide group, a linear or branched compound can also be used. Further, in the case of a compound having a tautomer, any isomer may have an amide group or an imide group. The urea-derived ureido group and ureylene group are also included in the scope of the amide group and imide group of the present invention.

Examples of the above-mentioned epoxy compound include aliphatic alkylene oxides such as ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and pentylene oxide; aromatic alkylene oxides such as styrene oxide. Cyclohexene oxide and the like are preferred. Among these, aliphatic alkylene oxides having 2 to 3 carbon atoms, that is, ethylene oxide and propylene oxide are preferable. More preferably, it is ethylene oxide.

As the ratio of the compound having an amide group or imide group to the epoxy compound, the number of moles of epoxy group relative to 1 mole of amide group or imide group in the compound is 0.
It is 5 mol or more and preferably 3 mol or less.
If it is less than 0.5 mol, the productivity of the N-hydroxyalkyl compound may decrease. If it exceeds 3 mol, the selectivity may decrease. It is more preferably 0.8 mol or more, further preferably 0.9 mol or more, and more preferably 1.5 mol or less,
More preferably, it is 1.2 mol or less. The reaction time may be appropriately selected depending on the pulverization degree of the compound having an amide group or an imide group such as isocyanuric acid, the catalyst, the reaction temperature, the reaction molar ratio, the kind of the solvent and the like. It is preferably 0.1 to 12 hours.

In the present invention, the solvent may or may not be used, but it is used when the melting point of the compound having an amide group or an imide group is higher than the reaction temperature or when the compound itself does not have a melting point. In this case, it can be appropriately selected depending on the properties of the compound having an amide group or an imide group. In the present invention, a solid ion exchanger will be used. The above-mentioned solid ion exchanger is generally called a heterogeneous catalyst, and has an ion-exchange ability because the ion-exchange group which can be an active site is immobilized and it is not uniformly eluted in the reaction system. Is. Examples of these ion exchangers include hydrotalcite, zeolite, hydroxyapatite, silica gel, alumina gel, alumino-silica gel, clay minerals, and ion exchange resin catalysts, and among them, ion exchange resin catalysts are preferable because of their high catalytic activity. The ion-exchange resin catalyst may be any polymer compound having an ion-exchange ability, but strong basic anion exchange resins, weak basic anion exchange resins and the like are particularly preferable. In the present specification, the term “polymer compound” is used as a general term for polymers and compounds having a molecular weight distribution, and does not mean that the molecular weight is a specific molecular weight or more.

The ion exchange resin catalyst used in the present invention is 4
It preferably has a quaternary ammonium salt structure, and more preferably a quaternary ammonium salt structure having a cyclic structure. As such an ion exchange resin catalyst, a main chain is essential, preferably a main chain and a cross-linking site are essential, and the main chain is formed mainly of a repeating unit having a quaternary ammonium salt structure. It is preferable that it is composed of an organic polymer compound. More preferably, an organic polymer compound in which the repeating unit having a quaternary ammonium salt structure is formed by a cyclic amine structure, that is, an organic polymer in which a repeating unit having a cyclic quaternary ammonium salt structure is formed as a main component It is composed of a compound. The quaternary ammonium salt structure preferably has a structure in which a cationized nitrogen atom is incorporated into the main chain through two bonds and incorporated into the cross-linking site through four bonds. In addition, you may have additionally the repeating unit which does not have these quaternary ammonium salt structures.
The organic polymer compound means a polymer compound whose main chain serving as a skeleton is formed mainly of hydrocarbon. When the main chain and the crosslinking site are essential, the organic polymer compound is also referred to as an organic polymer crosslinked product.

Since the above cyclic amine structure is less susceptible to oxidative decomposition than the aliphatic amine structure, the thermal decomposition resistance of the ion exchange resin catalyst is more excellent. As a form of such a cyclic amine structure, a 5-membered ring, a 6-membered ring and the like are preferable, and a 5-membered ring is preferable. Further, since it becomes easy to form a main chain with a repeating unit having a cyclic quaternary ammonium salt structure as a main component, it is preferable that the main chain is formed of a diallyldimethylammonium salt.

As the above-mentioned ion exchange resin catalyst,
It is preferable that the organic polymer compound has a hetero atom as an essential element in the main chain and / or the cross-linking site and does not have a hydrogen atom bonded to the hetero atom.

The above organic polymer compound has a structure in which a hetero atom is incorporated in either or both of the main chain and the cross-linking site. That is, having a heteroatom in the main chain and / or the cross-linking site as essential means having a hetero atom incorporated in the structure of the main chain and / or the cross-linking site as essential, and the main chain and / or the cross-linking site. It does not mean that a group having a hetero atom is bonded to the group like a side chain. Since the organic polymer compound has such a structure, unlike the case where the active site is on the side chain, heat resistance is improved, chemical deterioration is suppressed, and ion exchange is performed during the production of the N-hydroxyalkyl compound. It becomes difficult for the resin catalyst to elute into the reaction solution.

In the above organic polymer compound, the cross-linking site means a site where the main chains are bonded to each other, and the cross-linking site is a part of the main chain and the cross-linking structure connecting the main chains. It is composed of a combined structure. Such a main chain and a crosslinked structure are usually linked by a covalent bond. The presence of the cross-linking site increases the mechanical strength of the ion exchange resin catalyst.

The heteroatom present in the main chain and / or the cross-linking site of the above organic polymer compound has a catalytic ability in the reaction of forming the N-hydroxyalkyl compound from the compound having the amide group or imide group and the epoxy compound. It can be an active point that exerts As described above, since the active sites of the organic polymer compound constituting the ion exchange resin catalyst are incorporated in the structure of the main chain and / or the cross-linking site, they are chemically structurally less likely to be thermally decomposed, so As compared with the molecular catalyst, the active sites are less likely to be separated or decomposed due to the influence of heat during the reaction, and the ion exchange resin catalyst has excellent heat resistance.

As the above hetero atom, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, aluminum atom, boron atom, zinc atom, copper atom, nickel atom, iron atom and the like are preferable. These may be one kind or two or more kinds. Among these, it is preferable to have a nitrogen atom, a sulfur atom and a phosphorus atom. Most preferably, it is a nitrogen atom. Further, these hetero atoms are preferably ionized because the catalytic activity is improved. More preferably, it is cationized. Therefore, the most preferable form of the ion exchange resin catalyst in the present invention is that the organic polymer compound constituting the ion exchange resin catalyst has a cationized nitrogen atom in the main chain and / or the cross-linking site, that is, cationized nitrogen. Atoms have a structure incorporated into the main chain and / or the bridging site. In such a structure, in order to increase the ratio of active sites in the ion exchange resin catalyst and improve the catalytic activity, a structure in which a cationized nitrogen atom is incorporated into the main chain by two bonds and / or a cationized structure is used. It is preferable to have a structure in which the above-mentioned nitrogen atom is incorporated into the cross-linking site by three or four bonds.

The organic polymer compound preferably does not have a hydrogen atom bonded to a hetero atom as described above. When the organic polymer compound has a hydrogen atom bonded to a hetero atom, the reaction between the epoxy compound and the compound having an amide group or an imide group proceeds due to, for example, the hydrogen reacting with the epoxy compound. As a result, the ion exchange resin catalyst expands and the reaction efficiency decreases, and the ion exchange resin catalyst is hindered from being repeatedly used. The hydrogen atom bonded to the hetero atom, -OH group, -NH group, -NH ₂ group, -SH
A hydrogen atom directly covalently bonded to a hetero atom such as a group or a —COOH group, and the one formed by a coordinate bond is not limited to this. Further, the hydrogen atom bonded to the hetero atom contained in the polymerization initiator, the suspending agent, the precipitation preventing agent and the like is not limited to this.

The above organic polymer compound also preferably has a counter anion. The above-mentioned counter anion means an anion coordinated with a cationized hetero atom present in the main chain and / or a cross-linked site as a cationized site in the organic polymer compound. The number of such counter anions in one molecule of the organic polymer compound is not particularly limited.

As the counter anion, a halogen is used.
Oxide ion, hydroxide ion, anion of organic acid or
Anions of inorganic acids and the like are suitable. Halide ion
As the halogen atom in, fluorine, chlorine, bromine,
Iodine and the like are preferred. Anion of organic acid or inorganic acid
Anion has fewer hydrogen ions than organic or inorganic acids
Means that at least one is eliminated, and the anion of inorganic acid
For sulfate ion and phosphonate ion (phosphorous acid ion)
), Borate ion, cyanide ion, carbonate ion,
Hydrogen carbonate ion, thiocyanate ion, thiosulfate ion
Ion, sulfite ion, bisulfite ion, nitrate ion,
Anion ion, phosphate ion, hydrogen phosphate ion, meta
Rate ions (eg molybdate, tongs)
Tenate, metavanadate, pyrovanadate
Ion, hydrogen pyrovanadate, niobate,
Tantalate ion, perrhenate ion, etc.), tetraf
Luoroaluminate ion, tetrafluoroborate ion
Hexafluorophosphate ion, tetrachloroaluminum
Nitrate ion, Al_TwoCl₇ ^-And the like, of organic acids
Examples of anions include sulfonate ion, formate ion, and
Oxalate ion, acetate ion, (meth) acrylic acid ion
Ion, trifluoroacetate ion, trifluoromethanesulfur
Fonate ion, bis (trifluoromethanesulfonic acid)
Amide ion, (CF _ThreeSO_Two)_ThreeC^-Etc. are suitable
It These counter anions are organic polymer compounds.
There may be one kind or two or more kinds. these
Among them, halide ions, hydroxide ions, carbonic acid
Hydrogen ion, hydrogen sulfite ion, formate ion, metalley
Trion is preferred. More preferably, halide
Chloride ion, hydroxide ion, hydrogencarbonate ion which are on
And formate ion. Most preferably, when using a catalyst
Is a hydroxide ion, which is a chlorine ion during catalyst synthesis.
is there. Therefore, in the present invention, the counter anion
However, it is preferable that a hydroxide ion is essential. this
Thereby, the catalytic activity is further improved. Sanawa
If the compound has two amide or imide groups
Is 2 with 1 mol of epoxy compound added to each
The adduct also has an amide group or an imide group in the compound.
If you have one, each epoxy compound is 1 mol
The selectivity of the three-adducts
It

When the above organic polymer compound has a cross-linking site, the structure of the cross-linking site is not particularly limited, and the number of the existing is not particularly limited, and the number is 1 in one molecule of the organic polymer compound. There will be one or more. When two or more crosslinking sites are present in one molecule of the organic polymer compound, the structures of the crosslinking sites may be the same or different. The structure of the organic polymer compound having such a cross-linking site is usually a network structure composed of a main chain and a cross-linking site, and the average number of main chains in one molecule of the organic polymer compound is two. The above is not particularly limited.

The cross-linking density of the organic polymer compound having a cross-linking site is the ratio of the monomer (cross-linking agent) forming a cross-linking structure to the total number of moles of the monomer forming the organic polymer compound. Is 0.1 mol% or more, and preferably 80 mol% or less. When it is less than 0.1 mol%,
There is a possibility that the mechanical strength of the ion exchange resin catalyst may decrease, and when it exceeds 80 mol%, in the production of the N-hydroxyalkyl compound, the liquid permeability of the reaction solution passing through the ion exchange resin catalyst is decreased and the catalyst becomes less. The activity may not be fully exerted. It is more preferably 0.5 mol% or more, further preferably 1 mol% or more, more preferably 50 mol% or less, and further preferably 20 mol% or less.
It is not more than mol%.

The structure of the cross-linked site is preferably represented by the following general formula (1) and / or general formula (2).

[0027]

[Chemical 1]

In the general formula (1), R¹And R^TwoIs the same young
Differently, a hydrogen atom, a halogen atom, and a carbon number of 1 to
10 represents an alkyl group or a hydroxyl group. R^Three, R^Four, R⁵
And R ⁶Are the same or different, hydrogen atom, halogen
Represents a hydrogen atom, a methyl group or an ethyl group. X1^-And X2^-
Are counter anions, the same or different
Halide ions, hydroxide ions, organic acid
Represents anion of anion or inorganic acid. a is 0-10
Represents an integer.

[0029]

[Chemical 2]

In the general formula (2), R⁷, R⁸, R⁹And R
¹⁰Are the same or different and are hydrogen atom, halogen atom
Represents a child, an alkyl group having 1 to 10 carbon atoms or a hydroxyl group. R
^llAnd R¹²Are the same or different and have 1 to 1 carbon atoms.
Represents 10 alkyl groups. R^{1 Three}, R¹⁴, R¹⁵as well as
R¹⁶Are the same or different and are hydrogen atom, halogen
Represents an atom, a methyl group or an ethyl group. X3^-And X4
^-Are counter anions, the same or different
Halide ions, hydroxide ions, organic acid
Represents anion of anion or inorganic acid. b and c are the same
Or, differently, it represents an integer of 0 to 10, and p is 0 or
Represents 1. However, b + c + p ≧ 1 is satisfied. Z is
-NH- group, -N (CH_Three) -Group, -NH- (CH_Two)
_Three-NH- group, -NH- (CH_Two)_Four-NH- group, -O
-Group, -CH (OH)-group, -O-CH _Two-C (C
H_Three)_Two-CH_Two-O- group, -O- (CH_Two)_Two-(O
-CH_Two-CH_Two)_n-O- group, 1,4-piperazinyl
Group, 3-methyl-2,6-pyridyl group, 4-methyl-
2,6-pyridyl group, 2,6-pyridyl group or 2,5-
Represents a pyridyl group. n represents an integer of 0 or more.

More preferably as the structure of the cross-linking site
Is R in the general formula (1).¹~ R ⁶Is all hydrogen
Is an atom and X1^-And X2^-Is chlorine ion and / or water
An oxide ion in which a is 3, ie, N,
N, N ', N'-tetraallyl dipiperidyl propanium
What is formed by muzi chloride and chlorine ions
It is replaced with hydroxide ion.

The preferred method for producing the ion exchange resin catalyst used in the method for producing the N-hydroxyalkyl compound of the present invention will be described below. As this preferable ion exchange resin catalyst, an ammonium compound represented by the following general formula (3) and a diallylammonium group are used in the molecule.
It is preferable to use an organic polymer cross-linked product obtained by copolymerizing an aqueous solution containing at least one compound with a water-insoluble organic solvent as a medium by reverse phase suspension polymerization or reverse phase emulsion polymerization. In such a crosslinked organic polymer, a compound having two or more diallylammonium groups in the molecule forms a crosslinked structure as a crosslinking agent, and is produced as spherical particles. The ion exchange resin catalyst of the present invention can also be obtained by solution polymerization of the above aqueous solution, molding into a desired shape, and granulation.

[0033]

[Chemical 3]

In the general formula (3), R¹⁷And R¹⁸Is the same
One or different, a hydrogen atom, a methyl group, an ethyl group or
Represents a halogen atom. R¹⁹And R²⁰Is the same young
Or an alkyl group, an alkoxyalkyl group or
Represents an aryl group or R ¹⁹-N⁺-R²⁰Is
R¹⁹And R²⁰To form a piperidine ring or morpholine.
Represents a nickel ring. A¹And A^TwoAre the same or different
Represents a hydrogen atom, an alkyl group or a halogen atom. Y
^-Represents a counter anion.

As the halogen atom, fluorine, chlorine, bromine, iodine and the like are preferable. The alkyl group or alkoxyalkyl group preferably has a total carbon number of 1 to 18. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group and the like are preferable.
More preferably, it has 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. The aryl group preferably has 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms. As such an aryl group, a phenyl group,
A tolyl group, a xylyl group and the like are preferable. The piperidine ring and the morpholinium ring have 1 to 13 carbon atoms.
One or two or more hydrogen atoms may be substituted by the alkyl group.

Preferred examples of the ammonium compound represented by the above general formula (3) include diallyldialkylammonium salts such as diallyldimethylammonium salt and diallyldiethylammonium salt; and dimethallyldialkylammonium salts such as dimethallyldimethylammonium salt. is there. A diallyldimethylammonium salt is preferred because it facilitates formation of a main chain with a repeating unit having a quaternary ammonium salt structure as a main component. These may be used alone or in combination of two or more.

The above diallylammonium group is incorporated into the molecule by 2
As the compound having one or more, the following formulas (1) to (10)
Compounds represented by are preferred.

[0038]

[Chemical 4]

Among the compounds represented by the above formulas (1) to (10), N, N, N ', N'-represented by the formula (10).
Further preferred is tetraallyl dipiperidyl propanium dichloride. The compounds having two or more diallylammonium groups in the molecule are represented by formulas (1) to (10)
In addition to the compound represented by, N, N'-dimethyl-N,
N, N ', N'-tetraallyl-2-butene-1,4-
Diammonium dichloride and compounds having two or more paravinylphenylmethylammonium groups and / or metavinylphenylmethylammonium groups in the molecule include N, N'-di (paravinylphenylmethyl) ethylenediammonium dichloride, N, N'-di (methavinylphenylmethyl) ethylene diammonium dichloride, N, N'-di (paravinylphenylmethyl) propylene diammonium dichloride, N, N'-di (methavinylphenylmethyl) propylene diammonium dichloride, etc. It is suitable. Those listed here are representative examples, and in addition to these, compounds synthesized with phenylenediamine or other diamines and allyl chloride or allyl acetate are preferable. These may be used alone or in combination of two or more. The counter anion contained in these compounds is not limited to the chloride type and may be another type.

In the production of the above crosslinked organic polymer, the copolymerization ratio of the ammonium compound and the compound having two or more diallylammonium groups in the molecule is 40 to 99.9 / 60 to 0.1 in terms of molar ratio. It is preferable that Further, compounds other than the above compounds may be appropriately polymerized. Furthermore, regarding the concentration of the compound in the aqueous solution, the concentration of the aqueous solution at the time of preparation is 30 to 8 in handling.
It is preferably 0% by mass, but it may be further concentrated by a dehydration operation before or during the initiation of polymerization.

Examples of the water-insoluble organic solvent used as the medium include toluene, xylene, benzene, n-hexane, cyclohexane, octane, mineral acid, mineral spirits, kerosene, 1,1,1-trichloroethane,
Bromination of 1,2-dichloropropane, tetrachloroethane, trichloropropane, tetrachloromethane, etc. and /
Alternatively, a chlorinated hydrocarbon or the like is suitable. These may be used alone or in combination of two or more. Among these, it is industrially preferable to use toluene or xylene.

The medium may contain a viscous fluid such as liquid paraffin and / or silicone oil. This makes it possible to suppress the cohesiveness of the generated spherical particles and the adhesion between the spherical particles to suppress the agglomeration of the crosslinked organic polymer. The content of such a viscous fluid in the medium is preferably 0.1 to 50 mass%. It is more preferably 1 to 40% by mass, and further preferably 5 to 30% by mass. Also,
The viscosity of the medium containing the viscous fluid only needs to increase before and after the addition of the viscous fluid.

The polymerization conditions in the above copolymerization, that is, the polymerization temperature, the polymerization time, the stirring conditions, the polymerization initiator used,
The additives and the like may be appropriately set depending on the size, performance, quality, etc. of the spherical particles to be produced, and the polymerization temperature is 20 to 20.
The temperature is preferably 150 ° C. More preferably 50
~ 120 ° C. Further, azeotropic dehydration may be used in combination with normal pressure or reduced pressure. The polymerization time may be appropriately set according to other conditions, and is preferably 4 to 50 hours. The stirring condition may be a stirring speed in ordinary polymerization. As the polymerization initiator to be used, a general peroxide type or azo type initiator can be used regardless of water solubility or oil solubility. As an additive, glycerol palmitate,
A general dispersion stabilizer such as ethyl cellulose, sorbitan monopalmitate, sorbitan monolaurate, sorbitan monostearate can be used.

As a typical example of the method for producing the crosslinked organic polymer, diallyldimethylammonium salt and N, N,
An aqueous solution of N ', N'-tetraallyldipiperidylpropanium dichloride and an aqueous solution of a polymerization initiator were mixed with toluene and liquid paraffin, and the mixture was added dropwise to a medium to which a dispersion stabilizer was added, followed by reverse phase suspension polymerization or The case where reverse phase emulsion polymerization is performed is shown in the following reaction formula (1).

[0045]

[Chemical 5]

In the above reaction formula (1), Y ⁻ represents a chloride ion of the counter anion. q and r represent the number of moles. The average particle size of the granular particles obtained by the above-mentioned reverse phase suspension polymerization or reverse phase emulsion polymerization is preferably set to 0.05 to 5 mm.

In the method for producing an N-hydroxyalkyl compound of the present invention, the amount of the ion exchange resin catalyst or the like used, the method of supplying it to the reaction apparatus, and the method for separating the ion exchange resin catalyst or the like from the reaction solution after the reaction are as follows. It may be appropriately set according to the mode in which the manufacturing method of the invention is performed. Also,
As the reaction conditions, the reaction temperature is preferably 50 to 180 ° C. If the temperature is lower than 50 ° C, the reaction rate may be slow and the yield per unit time may be low. 1
If it exceeds 80 ° C, the selectivity of the desired N-hydroxyalkyl compound, especially the triadduct, may be lowered. The temperature is more preferably 70 to 140 ° C, and further preferably 80 to 120 ° C. Reaction pressure is 0.1-3M
Pa is preferable. More preferably 0.15
˜2 MPa, more preferably 0.2 to 1 MPa
Is.

The method for producing the N-hydroxyalkyl compound of the present invention can be carried out in the presence of carbon dioxide or an inert gas such as nitrogen, argon or helium. Also,
When hydroxide ion is used for the counter anion,
In consideration of maintenance of catalytic activity and loss of anions during production, it is also possible to regenerate by treating with a basic solution having a hydroxyl group after completion of the reaction. In addition, as long as the effects of the present invention are exhibited, a compound having an epoxy compound as a reaction raw material and the above amide group or imide group, or other catalyst as a component other than the above catalyst is added as necessary. May be.

In the method for producing an N-hydroxyalkyl compound of the present invention, an epoxy compound is reacted with a compound having an amide group or an imide group in the presence of a catalyst (ion exchange resin catalyst). Since the catalyst has excellent catalytic activity, it suppresses coloring due to decomposition of the solvent, and has excellent heat resistance, so that impurities due to the catalyst can be suppressed, and moreover, the N-hydroxyalkyl compound High selectivity. The catalyst used here is
Depending on the liquid containing the solvent used, 0.1 to 2 at 50 to 180 ° C
Treatment for 4 hours is desirable. This treatment makes the product quality more stable. When recrystallization is necessary, it is possible to simplify the process by using a single reaction solvent and recrystallization solvent. Further, when the ion-exchange resin catalyst is formed into granular particles as described above, it becomes easy to separate the ion-exchange resin catalyst from the product, which is suitable as an industrial production method. Further, the reaction using the above catalyst can be carried out by using a stirred batch reactor, a fixed bed or a fluidized bed reactor, and the reaction system may be a batch system or a continuous system. Furthermore, it can be used for catalytic distillation and reactive distillation for efficiently purifying the reaction product obtained by the reaction, and the use method is not limited by the process.

By the above-mentioned production method, isocyanuric acid is used as a compound having an amide group or an imide group,
By using ethylene oxide as an epoxy compound and a reaction as shown in the following reaction formula (2), high-quality tris (2
-Hydroxyethyl) isocyanurate compositions are produced. Tris (2-
Hydroxyethyl) isocyanurate compositions are also part of this invention. Here, high heat resistance means that, when thermal analysis of the obtained product is carried out, the mass reduction at the time of reaching 300 ° C. is 55% or less, preferably 40% or less. It is more preferably 20% or less, and most preferably 10% or less.
The THEIC composition obtained by this method, when heated,
2-Oxazolidone is hardly generated, the viscosity after heating is low, and it is suitable because it is easy to handle when it is used in applications requiring heat resistance.

The composition of the present invention may contain a second component other than THEIC. The content of THEIC in the composition has a lower limit value of 10% or more, preferably 25%,
It is more preferably 50% or more, still more preferably 90% or more, and most preferably 95% or more. The second component may be, for example, a raw material / solvent used in the reaction, a reaction by-product, or a stabilizer added after the reaction. As the reaction by-products, ethylene oxide such as 1 adduct of isocyanuric acid with 1 mol of ethylene oxide, 2 adduct with 2 mol of the same, 4 adduct with 4 mol of the same, and 5 mol of the same with 5 mol. There are various adducts formed by the reaction, such as multimeric adducts, 2-oxazolidone formed by decomposition of THEIC, polymers formed by further reaction of 2-oxazolidone, and polyethylene oxide formed by ring-opening of ethylene oxide. . Compounds other than those mentioned here which are produced by the reaction are all second components.

The composition of the present invention includes, for example, a liquid obtained by removing the solid catalyst from the liquid after the reaction, a precipitate (crude product) obtained by removing the solvent after the reaction, and a recrystallization / extraction / drying of the crude product. The product (product) refined by the refining operation for increasing the purity. Further, the above crude product or product to which a diluent, a stabilizer or the like is added may be used. A slurry form having poor solubility in a solvent and producing a precipitate is also included in the composition. It is preferable that the product has a THEIC purity of 95% or more. More preferably, it is 98% or more. Since the catalyst used in the present invention has excellent activity, the reaction solvent can be freely selected, but after the solvent is removed from the reaction composition by making the reaction solvent and the recrystallization solvent the same, the recrystallization operation of the crude product is performed. As a reaction solvent, alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol, 2-propanol, and the like can be obtained by simply performing a drying operation. n-butanol, hexanol, cyclohexanol, glycol ethers having 3 to 6 carbon atoms, such as methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Ethers having 2 to 6 carbon atoms such as tetrahydrofuran and dioxane are preferable.

[0053]

[Chemical 6]

Since the above tris (2-hydroxyethyl) isocyanurate composition has high heat resistance and flame retardancy, it is used as an insulating varnish for electric wire varnish, a stabilizer for vinyl chloride resin, a raw material for various coating resins, and various It is a substance useful in various fields such as flame retardants for plastics.

[0055]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "%" in the specification means "mass%" unless otherwise specified.

Catalyst Preparation Method 1 In a 1 L separable flask equipped with an anchor type stirring blade, a reflux condenser, a thermometer, a nitrogen gas inlet tube and a dropping funnel,
350 mL of toluene and 50 mL of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd .; special grade) (12.5% by volume in the medium) were added, and sorbitan monopalmitate as a dispersion stabilizer was added.
071 g and 0.213 g of ethyl cellulose were added and dissolved. At this time, nitrogen gas was blown in to expel dissolved oxygen.

Separately, 41.80 g of an aqueous 65% diallyldimethylammonium chloride (DADMAC) solution, 8.26 g of N, N, N ', N'-tetraallyldipiperidylpropanium dichloride (TADPPC) and 5.36 g of water were mixed and dissolved. In addition, the polymerization initiator "V-50"
A solution obtained by mixing 0.319 g and 3.52 g of water was added (monomer concentration 59.8%, DADMAC / TADPP).
C = 90/10 mol%).

This mixed solution was added dropwise to the reaction vessel at room temperature over 30 minutes while stirring at 220 rpm, and after completion of the addition, 55 ° C. for 4 hours, 60 ° C. for 16 hours, and further 92-95 ° C.
And reacted for 6 hours. After 2 hours on the way, the stirring speed was increased from 220 rpm to 250 rpm, and 50 mL of liquid paraffin (22.2% by volume in the medium) was added dropwise. Also, when the temperature is raised from 55 ° C to 60 ° C, toluene 50
mL was added (concentration of liquid paraffin in the medium 20.0% by volume).

After the predetermined reaction time was completed, the reaction mixture was cooled and the produced particles were separated by filtration. Toluene 600m for the separated particles
L, washed with 800 mL of methanol three times, and dried under reduced pressure at 60 ° C. overnight to obtain 36.23 g of dried particles. The obtained dry particles were independent particles having a diameter of about 0.3 mm. The obtained counter anion was swollen with 30.0 g of a crosslinked product of chloride ion, and the counter anion was replaced with chloride ion from chloride ion by column method using 5 L of 2N sodium hydroxide aqueous solution. Then, by washing with the same amount of water, an ion exchanger having the structure represented by the above reaction formula (1) was obtained.

Example 1 Using the ion exchanger obtained in Catalyst Preparation Method 1, an addition reaction of ethylene oxide to isocyanuric acid was carried out. Specifically, the water swelling body 20 of the ion exchanger is placed in an autoclave container equipped with a thermometer, a pressure gauge, a stirrer, and the like.
mL (wet product which was weighed with a graduated cylinder, solvent-substituted with methyl cellosolve, and filtered under reduced pressure was used), isocyanuric acid 9.7 g, and methyl cellosolve 37.5 g were charged,
Under a nitrogen atmosphere, 9.9 g of ethylene oxide was continuously added over 1 hour at 90 ° C. Then, tris (2-hydroxyethyl) isocyanurate was synthesized by aging at 90 ° C. for 6 hours. In addition, methyl cellosolve was charged so that the total amount including methyl cellosolve contained in the ion exchanger was 37.5 g. After the ion exchanger was filtered off from the colorless transparent solution after completion of the reaction, the reaction filtrate was analyzed by high performance liquid chromatography to find that the conversion of isocyanuric acid was 94.3 mol% and that tris (2-hydroxyethyl) was present. ) The yield of isocyanurate is 7
It was 1.9 mol%. Methyl cellosolve was recovered from this solution, and when the solution was cooled, white solid crystals were precipitated. After filtering and drying, the obtained white solid crystals were
It was tris (2-hydroxyethyl) isocyanurate with a purity of 99.0%.

Example 2 The same experiment as in Example 1 was repeated using the ion exchanger filtered out in Example 1. After the ion exchanger was filtered off from the colorless transparent solution after completion of the reaction, the reaction filtrate was analyzed by high performance liquid chromatography to find that the conversion of isocyanuric acid was 99.0 mol% and tris (2-hydroxyethyl) was used. ) The yield of isocyanurate was 84.7 mol%, and the activity did not decrease due to repeated catalyst reaction. Methyl cellosolve was recovered from this solution, and when the solution was cooled, white solid crystals were precipitated. When it was separated by filtration and dried, the obtained white solid crystals were tris (2-hydroxyethyl) isocyanurate with a purity of 99.0%.

The obtained crystals were analyzed by a thermal analyzer (DTG-50, manufactured by Shimadzu Corporation). In a nitrogen gas flow rate atmosphere of 5 ml / min, the temperature rising program is 30
The temperature was raised to 200 ° C. at a rate of ° C./min and held for 10 minutes.
After that, the temperature is raised to 250 ° C. at 10 ° C./min, held for 10 minutes, and further raised to 350 ° C. at 10 ° C./min,
Hold for 5 minutes. Weight loss after holding at 250 ° C for 10 minutes is 0.9%, weight loss at 300 ° C is 1.7%
It was excellent in heat resistance.

Example 3 Using the cross-linked polymer filtered out in Example 2, repeated experiments were repeated 5 times in the same manner as in Example 2. After the cross-linked polymer was filtered off from the colorless transparent solution after the fifth reaction, the reaction filtrate was analyzed by high performance liquid chromatography to find that the conversion of isocyanuric acid was 99.0 mol%.
The yield of tris (2-hydroxyethyl) isocyanurate was 82.5 mol%. Methyl cellosolve was removed from this solution, and 24.0 g of the obtained crude product was charged with 24.0 g of ethanol for recrystallization. When the solution was cooled, white solid crystals were precipitated. When the precipitated solid was separated by filtration and dried, the white solid crystals obtained had a purity of 99.8.
% Tris (2-hydroxyethyl) isocyanurate.

Example 4 A reaction was performed in the same manner as in Example 1 except that the ion exchanger used in Example 1 was replaced with a commercially available heat-resistant anion exchange resin (“Diaion TSA1200”, trade name, manufactured by Mitsubishi Chemical Corporation). went. After the heat-resistant anion exchange resin was filtered off from the colorless transparent solution after completion of the reaction, the reaction filtrate was analyzed by high performance liquid chromatography to find that the conversion of isocyanuric acid was 100 mol% and tris (2-hydroxyethyl).
The yield of isocyanurate was 72.3 mol%. Methyl cellosolve was recovered from this solution, and when the solution was cooled, white solid crystals were precipitated. When it was separated by filtration and dried, the obtained white solid crystal was tris (2-hydroxyethyl) isocyanurate with a purity of 98.5%.

Example 5 Using the heat-resistant anion exchange resin filtered off in Example 4, repeated experiments were carried out in the same manner as in Example 4. After the reaction was completed, the heat-resistant anion exchange resin was filtered off, and the reaction filtrate was analyzed by high performance liquid chromatography to find that the conversion of isocyanuric acid was 97.5 mol% and that tris (2-hydroxyethyl) isocyanurate was present. The yield was 78.0 mol%. Recovering methyl cellosolve from this solution,
When the solution was cooled, white solid crystals were precipitated. Filtration,
When dried, the obtained white solid crystals had a purity of 99.
It was 0% tris (2-hydroxyethyl) isocyanurate. The obtained crystal was subjected to thermal analysis in the same manner as in Example 2. As a result, the mass reduction after holding at 250 ° C. for 10 minutes was 1.
The mass reduction when reaching 0% and 300 ° C. was 1.7%.

Comparative Example 1 Addition reaction of ethylene oxide to isocyanuric acid was carried out without using an ion exchanger. Specifically, a thermometer,
In an autoclave container equipped with a pressure gauge and a stirring device,
Isocyanuric acid (9.7 g) and N, N-dimethylformamide (37.5 g) were charged, and ethylene oxide (9.9 g) was continuously added over 1 hour at 120 ° C. under a nitrogen atmosphere.
Then, tris (2-hydroxyethyl) isocyanurate was synthesized by aging at 120 ° C. for 6 hours. When the pale yellow transparent solution after the end of the antisense was analyzed by high performance liquid chromatography, the conversion of isocyanuric acid was 88.4 mol% and the yield of tris (2-hydroxyethyl) isocyanurate was 72.9. It was mol%. N, N-dimethylformamide was recovered from this solution, and when the solution was cooled, white solid crystals were precipitated.
Since it was a yellow viscous solution and was difficult to filter out, recrystallization was carried out with ethanol. The crystals were separated by filtration and dried, and the obtained white solid crystals were tris (2-hydroxyethyl) isocyanurate with a purity of 98.0%. When thermal analysis was conducted in the same manner as in Example 2, it was 10 at 250 ° C. The weight loss after holding for 4 minutes was 49.5%, and the weight loss at the time of reaching 300 ° C was 67.5%, which is inferior to the method using an ion exchanger in yield, purity, and heat resistance. there were.

Comparative Example 2 As in Example 1 except that no ion exchanger was used,
The addition reaction of ethylene oxide to isocyanuric acid was performed at 90 ° C. After completion of the reaction, unreacted starting material isocyanuric acid was filtered off and the reaction filtrate was analyzed by high performance liquid chromatography to find that the yield of tris (2-hydroxyethyl) isocyanurate was 1.6 mol%.

Comparative Example 3 The addition reaction of ethylene oxide to isocyanuric acid was carried out in the same manner as in Comparative Example 2 except that the reaction temperature was 120 ° C. to compensate for the low activity. After completion of the reaction, unreacted starting material isocyanuric acid was filtered off and the reaction filtrate was analyzed by high performance liquid chromatography to find that the yield of tris (2-hydroxyethyl) isocyanurate was 26.9 mol%.

Catalyst Preparation Method 2 In a 1 L separable flask equipped with a stirrer, a reflux condenser, a water separation tube, a decompression constant device, a thermometer, a nitrogen gas inlet tube and a dropping funnel, 350 mL of toluene and 50 mL of liquid paraffin (in the medium) 12.5% by volume), 0.64 g of sorbitan monopalmitate as a dispersion stabilizer and 0.21 g of ethyl cellulose were added and dissolved at 40 ° C. At this time, nitrogen gas was blown in to expel dissolved oxygen.

Separately, in a 100 mL beaker, 65% diallyldimethylammonium chloride (DADMAC)
41.74 g of an aqueous solution and N, N, N ', N'-tetraallyldipiperidylpropanium dichloride (TADPP
C) 8.26 g and 20.78 g of water were mixed and dissolved, and further a solution of 0.32 g of the polymerization initiator "V-50" and 2.4 g of water was added (monomer concentration 48.2%, DAD).
MAC / TADPPC = 90/10 mol%).

This solution was added dropwise to the reaction vessel at 30 ° C. over 30 minutes, and after completion of the addition, the temperature was further raised at 55 ° C. for 4 hours,
The reaction was carried out at 75 ° C for 3 hours. After 2 hours on the way, increase the stirring speed from 220 rpm to 250 rpm,
50 mL of liquid paraffin (22.2% by volume in the medium)
Was dripped. When the temperature was raised from 55 ° C to 75 ° C, 50 mL of toluene (concentration of liquid paraffin in the medium was 20% by volume)
Was further added, and the pressure in the reaction system was reduced to polymerize while distilling water was separated.

After the reaction for a predetermined time, it was cooled and the produced particles were separated by vacuum filtration. 800m of methanol separated by filtration
It was washed with L for 3 times for 30 minutes and dried under reduced pressure at 60 ° C. overnight to obtain 32.9 g of dried particles. The dry particles obtained are
The particles were independent particles having a diameter of about 0.2 mm. The particles are ion exchangers having the structure represented by the above reaction formula (1).

Example 6 Using the ion exchanger obtained in Catalyst Preparation Method 2, an addition reaction of ethylene oxide to succinimide was carried out. Specifically, an autoclave container equipped with a thermometer, a pressure gauge, a stirrer, and the like was charged with 1.0 g of an ion exchanger, 7.5 g of succinimide, and 12.5 g of 1,4-dioxane, and under a nitrogen atmosphere, At 80 ° C., 3.4 g of ethylene oxide was added. Then, 2-hydroxyethyl succinimide was synthesized by aging at 80 ° C. for 3.5 hours. After the ion exchanger was filtered off from the colorless transparent solution after completion of the reaction, the reaction filtrate was analyzed by gas chromatography to find that the conversion of succinimide was 95.9 mol% and that 2-hydroxyethylsuccinic acid was present. The yield of imide was 90.6 mol%.

Example 7 Using the ion exchanger obtained in Catalyst Preparation Method 2
The addition reaction of ethylene oxide to pyrrolidone was performed. Specifically, in an autoclave container equipped with a thermometer, a pressure gauge, a stirrer, etc., 1.0 g of the ion exchanger, 2-
Pyrrolidone (20.0 g) was charged, and under a nitrogen atmosphere, 80 ° C
Then, 5.2 g of ethylene oxide was added. Then 80
2-Hydroxyethylpyrrolidone was synthesized by aging it at 2.5 ° C. for 2.5 hours. After the ion exchanger was filtered off from the colorless transparent solution after completion of the reaction, the reaction filtrate was analyzed by gas chromatography to find that the conversion rate of 2-hydroxyethylpyrrolidone was 57.3 mol% and 2-hydroxyethyl. The yield of pyrrolidone was 46.0 mol%.

[0075]

Since the method for producing an N-hydroxyalkyl compound of the present invention has the above-mentioned constitution, it is possible to suppress the coloring due to the decomposition of the solvent and the impurities due to the catalyst. In addition, since the production method has a high selectivity of the N-hydroxyalkyl compound, polyester resin, polyurethane resin, oxazolidone,
It is possible to produce N-hydroxyalkyl compounds that can be used in a wide range of applications as raw materials for fiber treatment agents, plasticizers, etc., and as solvents, etc. In particular, insulating varnishes such as wire varnishes and stabilizers for vinyl chloride resin. Tris (2-hydroxyethyl) isocyanurate, which can be used in various fields such as raw materials for various paint resins and flame retardants for various plastics, can be suitably produced. Further, it is possible to provide a high-quality tris (2-hydroxyethyl) isocyanurate composition which is useful in various fields and which is suppressed in coloring, has few impurities, and has high heat resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA02 AC41 BA72 BA81 BB14                       BB15 BB25 BC10 BC19 BN10                       BV34                 4H039 CA60 CF30

Claims (3)

[Claims] 1. By reacting a compound having an amide group or an imide group with an epoxy compound in the presence of a catalyst,
A method for producing an N-hydroxyalkyl compound, characterized in that the catalyst is a solid ion exchanger. 2. The solid ion exchanger comprises a main chain and / or
Alternatively, the organic polymer compound is essentially composed of an organic polymer compound having a hetero atom at the cross-linking site and not having a hydrogen atom bonded to the hetero atom, and the main chain of the organic polymer compound is cyclic 4 The method for producing an N-hydroxyalkyl compound according to claim 1, wherein the repeating unit having a primary ammonium salt structure is formed as a main component. 3. A tris (2-hydroxyethyl) isocyanurate composition produced by the method for producing an N-hydroxyalkyl compound according to claim 1 or 2.