JP2002212222A - Strongly basic crosslinked resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a strongly basic crosslinked resin having high ion exchange ability and catalytic ability as an ion-exchange resin, and a catalyst having a high diffusibility in a solvent, enhanced reactivity and applicable to various usage. SOLUTION: This strongly basic crosslinked resin has repeating units essentially having a cyclic amine structure, and the cyclic amine structure forms the main chain of the strongly basic crosslinked resin, and the repeating units having the cyclic amine structure has a substitute essentially having a hetero atom on the nitrogen atom in the cyclic amine structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a crosslinked product of a strongly basic resin.

[0002]

2. Description of the Related Art Strongly basic resins can exert ion-exchange ability and catalytic ability to activate active hydrogen. It is widely used in various industrial fields such as separation and purification, catalyst, metal recovery, iodine recovery, sugar solution recovery, sucrose decolorization, uranium purification, and formalin purification. As such a strongly basic resin, for example,
Styrene-based strongly basic ion exchange resins, such as copolymers of styrene and divinylbenzene, are generally known.

[0003] Styrene-based strongly basic ion exchange resins are:
Usually, styrene and divinylbenzene are spheroidized by suspension polymerization to synthesize a cross-linked poly-styrene-divinylbenzene, which is a cross-linked styrene-divinylbenzene copolymer, and then the cross-linked product is formed using a Lewis acid or the like. Is chloromethylated, followed by addition of a tertiary amine or the like to introduce an amine structure. Such a strongly basic ion exchange resin can be used in a wide range of fields because it can perform an ion exchange reaction in all pH ranges.

The strong basic ion exchange resin mainly contributes to the ion exchange ability and the catalytic ability by a nitrogen atom in an amine structure derived from a tertiary amine or the like introduced into the crosslinked product, ie, a tertiary amine. It is a site of a nitrogen atom in a quaternary ammonium salt (OH type) derived from the above. Therefore, in a strongly basic resin, increasing such sites, so-called active sites, is extremely important in improving the ion exchange capacity. International Publication No. 99/582
No. 42 discloses a crosslinked strong basic resin having a cyclic amine structure as a main chain, and the crosslinked strong basic resin has an ion exchange capacity of one which exhibits an ion exchange capacity and a catalytic capacity.
The neutral salt decomposition capacity of the water-swelled Cl-type resin as one index is less than 1.1 meq / mL, and there is room for contrivance to improve the neutral salt decomposition capacity in order to apply it to a wide variety of applications. there were.

One of the means for increasing the ion exchange capacity of a strongly basic ion exchange resin is to increase the degree of crosslinking. However, although the ion exchange capacity is improved by increasing the degree of crosslinking, the water content of the resin is reduced, and the reaction rate is decreased due to the slow diffusion rate of the resin in the aqueous solution. It will be. Therefore, a technique that can improve both ion exchange capacity and catalytic capacity and solution diffusivity has been desired.

JP-A-2-502923 discloses a cationic vinyl copolymer having a side chain, which can be diluted with water. This cationic vinyl copolymer has a linear basic skeleton in which networking is suppressed in a wide range, has a nitrogen atom serving as an active site in a main chain and a side chain, and has a property of polycation. Since it exhibits the properties of a polymer electrolyte, it is uniformly dispersed in water and exhibits high activity. However, this cationic vinyl copolymer has room for improvement to improve the ion exchange capacity, shorten the time required for ion exchange and catalytic reaction, and increase the throughput.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and as an ion-exchange resin or catalyst, has extremely high ion-exchange ability and catalytic ability, and realizes high solution diffusivity. It is an object of the present invention to provide a crosslinked product of a strongly basic resin which can improve the reaction rate by using the resin and can be widely applied to various uses.

[0008]

According to the present invention, there is provided a crosslinked strong basic resin in which a repeating unit having a cyclic amine structure is essential, wherein the cyclic amine structure forms a main chain, and which has the cyclic amine structure. The repeating unit is a crosslinked strong basic resin having a substituent essentially including a hetero atom at the nitrogen atom of the cyclic amine structure.

The present invention also provides a crosslinked strong basic resin in which a repeating unit having a cyclic amine structure is essential, wherein the cyclic amine structure forms a main chain. The water-swelled resin has a neutral salt decomposition capacity of 1.
It is a crosslinked strongly basic resin having a meq / mL or more.

The present inventors have conducted intensive studies after closely examining the problems with the crosslinked strongly basic resin, and as a result, in the crosslinked strongly basic resin described above, the cyclic amine structure contained a nitrogen atom. In addition to having a substituent which essentially requires a hetero atom in the nitrogen atom, and being a crosslinked product, these nitrogen atoms and hetero atoms become active sites, and the ion exchange capacity is increased due to the fact that the number of active sites can be increased. And the catalytic activity becomes extremely high, and furthermore, the water content of the strong basic resin can be increased due to the high proportion of nitrogen atoms,
Because high solution diffusivity can be achieved and the reaction rate can be improved, as an ion exchange resin or catalyst, it is possible to improve both the ion exchange capacity and the catalytic capacity and the reaction rate, and to improve such a strong base. The present invention has been achieved by encountering the fact that a dramatic effect that a crosslinked resinous resin can be applied to a wide variety of applications occurs. The crosslinked strongly basic resin in the present invention refers to a crosslinked resin which shows even a slight neutral salt decomposability, and may contain a weakly basic exchange group. Hereinafter, the present invention will be described in detail.

The crosslinked strongly basic resin of the present invention essentially requires a repeating unit having a cyclic amine structure, and the cyclic amine structure forms a main chain. In this specification, the cyclic amine structure means a cyclic amine structure and / or a cyclic ammonium salt structure. In the crosslinked strongly basic resin, the number of repeating units having a cyclic amine structure may be one, or two or more. Further, as long as the effects of the present invention are exhibited, one or more kinds of repeating units other than the essential repeating units (hereinafter, referred to as other repeating units) may be provided. When the crosslinked strongly basic resin has two or more types of repeating units, the form of copolymerization of those repeating units is not particularly limited, and examples thereof include forms such as random, alternating, and block.

In the above crosslinked strongly basic resin, the nitrogen atom of the cyclic amine structure forming the main chain can be an active site exhibiting ion exchange ability and catalytic ability. Further, it is generally known that the cyclic amine structure forms a main chain, so that the structure is less susceptible to oxidative decomposition than the aliphatic amine. The active sites are stably present due to the difficulty in decomposition, and the thermal decomposition resistance is improved. Therefore, it becomes possible to improve the thermal decomposition resistance while increasing the number of active sites exhibiting the ion exchange ability and the catalytic ability as the ion exchange resin or the catalyst.
"Thermal decomposition resistance" means the degree of the thermal decomposition temperature of the crosslinked strong basic resin, for example, high heat decomposition, or that has been improved, the crosslinked strong basic resin It means that the thermal decomposition temperature is higher or improved as compared with a conventional general crosslinked strong basic resin.

The cyclic amine structure is not particularly limited as long as the effects of the present invention are exhibited. Examples of the ring form include a three-membered ring, a four-membered ring, a five-membered ring, and a six-membered ring. Among them, considering the thermal decomposition resistance, etc.
It is preferably a membered ring. More preferably, it is a 5-membered ring. Further, it may have a hetero atom other than a nitrogen atom.

The repeating unit having a cyclic amine structure has a substituent which essentially requires a hetero atom at the nitrogen atom of the cyclic amine structure. By having a substituent on the nitrogen atom of the cyclic amine structure, it is easy to synthesize a crosslinked strong basic resin, and the production can be performed easily. Since the heteroatom exerts ion exchange ability and catalytic ability, the presence of the heteroatom in the substituent increases the active sites per unit volume of the crosslinked strongly basic resin. The number of hetero atoms in the above substituent is not particularly limited. The type of the hetero atom is not particularly limited as long as the function and effect of the present invention is exhibited, and examples thereof include a nitrogen atom, a sulfur atom, and a phosphorus atom. These may be one kind or two or more kinds. Among these, it is preferable to have a nitrogen atom as an essential component from the viewpoint that the water content of the crosslinked strong basic resin can be increased. More preferably,
It must have a cationized nitrogen atom as an essential component, that is, the substituent has a quaternary ammonium salt structure. As a result, the active sites per unit volume of the crosslinked strong basic resin can be increased, and the activity of the active sites can be extremely increased.

In the above crosslinked strong basic resin, the cyclic amine structure forms a main chain, whereby the thermal decomposition resistance of the active site of these structures is improved, and the active site is activated by a substituent having a hetero atom as an essential component. Since the number of points is increased and the activity of the active point is high, the ion exchange capacity and the catalytic activity can be significantly improved. In addition, since the proportion of hetero atoms such as nitrogen atoms is large, the compound has high solution diffusivity.

The repeating units having a cyclic amine structure include, among those having the structures described above, for example, the following general formula (1):

[0017]

Embedded image

[Wherein, R¹ And R^Two Are the same or different
To form a hydrogen atom, a halogen atom, a methyl group or an ethyl group
Represent. R^Three Has 1 to 1 carbon atoms which may have a hetero atom.
8 represents a divalent hydrocarbon group. R^Four , R^Five And R⁶ Is the same
One or different may have a hydrogen atom or a hetero atom
Represents a monovalent hydrocarbon group having 1 to 18 carbon atoms. Where R
^Four , R^Five And R⁶ Any two of them are connected to each other
May be. X^- Is a halide ion, an organic acid
Represents an anion or an anion of an inorganic acid. The ring represented by
A repeating unit having a tertiary amine structure, and / or
The following general formula (2);

[0019]

Embedded image

[Wherein R¹ And R^Two Are the same or different
To form a hydrogen atom, a halogen atom, a methyl group or an ethyl group
Represent. R^Three Are the same or different and have a heteroatom
Represents a divalent hydrocarbon group having 1 to 18 carbon atoms. R^Four ,
R^Five And R⁶ Are the same or different and represent a hydrogen atom or
A monovalent hydrocarbon group having 1 to 18 carbon atoms which may have a hydrogen atom
Represents Where R^Four , R^Five And R⁶ Any two of
One may be connected to each other. X^- Are the same or different
To form a halide ion, an anion of an organic acid or
Represents the anion of the acid. ] The cyclic quaternary ammonium represented by
It is preferable that the repeating unit has a salt structure.
No. In the general formulas (1) and (2), R¹ Passing
And R^Two Is preferably a hydrogen atom. R^Three 
Is, for example, -CH_Two -,-(CH_Two )_Two −, −
(CH_Two )_Three -,-(CH_Two )_Four -,-(CH) CH_Three 
-, -C (CH_Three )_Two -, -O-CH_Two -, -S-CH
_Two And the like, and among these,-(CH_Two )_Four In
Preferably, there is. R^Four , R^Five And R⁶ As an example
For example, methyl group, ethyl group, n-propyl group, n-butyl
Group, i-butyl group, t-butyl group, phenyl group, -C
OOH, -CH _Two OH, -CH_Two SH, -CH_Two NH_Two 
And the like. R^Four , R^Five And R⁶ Any two of
As a group formed when two are bonded, for example,
For example, piperidyl, pyrrolidinyl, pyridyl, pyra
Dinyl groups and salts thereof.
Preferably, it is a dinium salt. Halide ion
For example, chlorine ion, bromine ion, iodine ion
X etc.^- As a bromine ion
Is preferred.

The crosslinked product of the strongly basic resin is represented by the general formula (1)
Or a repeating unit having a cyclic tertiary ammonium salt structure represented by the general formula (2), or a cyclic tertiary compound represented by the general formula (1). In the case where one or both of the repeating unit having an amine structure and the repeating unit having a cyclic quaternary ammonium salt structure represented by the general formula (2) are two or more, in the substituents of the cyclic amine structure, , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.

The crosslinked strong basic resin has a crosslinked structure as an essential component, and such a crosslinked structure is not particularly limited as long as the effects of the present invention can be obtained. For example, the repeating unit having a cyclic amine structure is a repeating unit having a crosslinked structure. As the repeating unit having such a crosslinked structure, for example, a repeating unit having a crosslinked structure formed from a cyclic tertiary amine structure is preferable. In the repeating unit having a crosslinked structure formed from a cyclic tertiary amine structure, the tertiary amine structure forms a main chain.

The cross-linked structure formed from the cyclic tertiary amine structure is a structure formed by cross-linking within or between the molecules of the polymer forming the main chain. It refers to the combined structure of the located cyclic structure having a tertiary amine structure (heterocyclic ring having a nitrogen atom) and the structure connecting the cyclic structures at both ends. By having a cross-linked structure, the nitrogen atoms of the tertiary amine structures at both ends exert ion exchange ability and catalytic activity, and the tertiary amine structure forms a cross-linked structure to form a chemical structure. Since it has a structure that is not easily thermally decomposed, it is possible to form a crosslinked strong basic resin having excellent thermal decomposition resistance. Further, by having a repeating unit having a crosslinked structure, the strength of the crosslinked product of a strongly basic resin is improved.
The term “strength” means a crushing strength or a physical strength such that a crack does not occur due to a sudden solvent swelling or the like.

The repeating unit having a crosslinked structure formed from the tertiary amine structure is preferably, for example, one represented by the following general formula (3).

[0025]

Embedded image

In the general formula (3), R ¹ and R ² are the same as described above. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are each a hydrogen atom, a halogen atom,
Represents an alkyl group or a hydroxyl group, and is preferably a hydrogen atom. As the alkyl group having 1 to 10 carbon atoms,
Examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a pentyl group, a hexyl group, and the like. a and b are the same or different,
It is an integer of 0 to 10, and p is 0 or 1. However, a + b + p ≧ 1 is satisfied. Z represents an -NH- group, -N
(CH ₃ ) —, 1,4-piperazinylene, —NH—
(CH ₂ ) ₃ —NH— group, —NH— (CH ₂ ) ₄ —NH
— Group, —O— group, —O— (CH ₂ ) ₂ —O— group, —O—
CH ₂ —C (CH ₃ ) ₂ —CH ₂ —O— group, —O— (C
_{H 2) 2 - (O-} CH 2 -CH 2) n1, O- group, 3-methyl-2,6-pyridyl group, 4-methyl-2,6-pyridyl group, 2,6-pyridyl group, 2 , 5-pyridyl group or -CH (OH)-group. n1 is an integer of 0 or more. The 1,4-piperazinylene group is defined by the following formula (4)
And the 3-methyl-2,6-pyridyl group is a group represented by the following formula (5),
The 2,6-pyridyl group is a group represented by the following formula (6), and the 2,6-pyridyl group is a group represented by the following formula (7), and a 2,5-pyridyl group Is a group represented by the following formula (8).

[0027]

Embedded image

The repeating unit having a crosslinked structure represented by the general formula (3) can be formed, for example, by reacting a cyclic secondary amine structure with a crosslinking agent. The other repeating units of the crosslinked strong basic resin are not particularly limited, and include, for example, a repeating unit having a cyclic secondary amine structure, and the cyclic secondary amine structure forms a main chain. Is preferred.

The repeating unit constituting the crosslinked strong basic resin has a cyclic secondary amine structure, so that the nitrogen atom of the secondary amine structure exhibits ion exchange ability and catalytic activity, By forming the main chain of the crosslinked resin into a cyclic structure, the structure becomes difficult to thermally decompose chemically, so that a crosslinked strongly basic resin excellent in heat decomposition resistance can be formed.

Examples of the repeating unit having a cyclic secondary amine structure include the following general formula (9):

[0031]

Embedded image

Wherein R ¹ and R ² are the same as above. ] Is preferable.

In the above crosslinked strong basic resin, the molar ratio of the essential repeating unit to the other repeating unit is not particularly limited, and may be selected depending on the intended use of the crosslinked strong basic resin.
What is necessary is just to set suitably according to desired performance etc. For example,
S / T is preferably 100/0 to 1/99, where S is the number of moles of essential repeating units and T is the number of moles of other repeating units in the crosslinked strong basic resin. More preferably, it is 100/0 to 50/50, and further preferably, it is 100/0 to 70/30.
When the number of moles of the repeating unit having a crosslinked structure in the crosslinked strong basic resin is represented by t, S / t is 99/1 to 1
/ 99 is preferable. More preferably, 95 /
5/50/50, more preferably 90/10
70/30. In this case, in order to improve the strength of the crosslinked product of a strongly basic resin, S / t should be 95/5 to 0/1.
00 is preferred. More preferably, 90/1
0/50/50, more preferably 85 / 15-
70/30.

The molar ratio of the repeating unit having a cyclic tertiary amine structure represented by the general formula (1) to the repeating unit having a cyclic quaternary ammonium salt structure represented by the general formula (2) is not particularly limited. Instead, it may be appropriately set according to the desired performance and the like according to the purpose of use of the crosslinked strong basic resin. For example, when the number of moles of the repeating unit having a cyclic tertiary amine structure represented by the general formula (1) is m, the cyclic quaternary ammonium salt represented by the general formula (2) in the crosslinked product of a strongly basic resin Assuming that the number of moles of the repeating unit having a structure is n, m / n is preferably from 99/1 to 0/100. More preferably, 50/50 to 0/1.
00, more preferably 80/20 to 0/100.
It is.

The molecular weight of the crosslinked strong basic resin is not particularly limited, and may be appropriately set according to the desired performance and the like according to the purpose of use of the crosslinked strong basic resin. For example, the number average molecular weight is preferably from 500 to 1,000,000. If it is less than 500, the neutral salt decomposition capacity and strength may be insufficient. If it exceeds 1,000,000, it may be difficult to produce a crosslinked strongly basic resin. More preferably, it is 10,000 to 500,000, and still more preferably 50,000 to 200,000.

A repeating unit having a cyclic amine structure is essential, and the cyclic amine structure is a crosslinked strongly basic resin in which a main chain is formed.
Salt decomposition capacity of water swelling type resin is 1.1 meq / mL
The crosslinked strongly basic resin described above can be preferably used for various reactions because it can increase the ion exchange ability and the catalytic ability. Such a crosslinked strongly basic resin is also one aspect of the present invention. As such a crosslinked strong basic resin, for example, in the crosslinked strong basic resin described above, C
The water-swelled l-type resin has a neutral salt decomposition capacity of 1.1 meq / m
L or more, the molar ratio of the essential repeating unit in the crosslinked product of the strong basic resin to the other repeating unit, or the repeating unit having a cyclic tertiary amine structure represented by the general formula (1). It can be prepared by appropriately setting the molar ratio and the like to the repeating unit having a cyclic quaternary ammonium salt structure represented by the general formula (2).

In the present specification, the neutral salt decomposition capacity of the water-swelled Cl-type resin is a value measured by the following method. First, a water-swelled body of a crosslinked strong basic resin is measured with a 20 ml measuring cylinder, and packed into a column. Then 2N N
aOH 1500 ml is circulated at an SV of about 70, and pure water 150
Flow and wash 0 mL. 5% NaCl 500m
After flowing through l, the mixture is washed with 1500 ml of pure water to prepare a cross-linked strongly basic resin of Cl type. This is measured with a 10 ml graduated cylinder, packed in a column, and 2N NaOH
750 ml and pure water (1 L) through SV70 to make OH type. Next, 250 ml of a 5% NaCl solution is allowed to flow through SV70, and the volume is received in a 250 ml volumetric flask. A 50 ml portion thereof is taken and titrated with a 0.1 N HCl solution using a mixed indicator of methyl red and methylene blue, and the neutral salt decomposition capacity is calculated by the following equation. Neutral salt decomposition capacity (meq / ml) = ｛(0.1N-HC
1 titration ml) × (HCl titer) × 0.1 × 250/5
0｝ / 10

In the above crosslinked strongly basic resin, when the neutral salt decomposition capacity of the water-swelled Cl-type resin is 1.1 meq / mL or more, production of pure water, separation and purification of amino acids, catalyst,
In various industrial fields such as recovery of metals, recovery of iodine, recovery of sugar solution, decolorization of sucrose, purification of uranium, purification of formalin, etc. The amount can be increased, and the accuracy of ion exchange and catalytic reaction can be improved. Due to these functions and effects, high-quality products that could not be achieved with conventional strong basic ion exchange resins can be obtained, and manufacturing costs can be reduced. The body can be provided.

When the neutral salt decomposition capacity of the crosslinked strong basic resin in the form of a water-swelled Cl-type resin is less than 1.1 meq / mL,
Since the ion exchange capacity and the catalytic capacity are increased, it cannot be widely used for industrial applications. The neutral salt decomposition capacity of the water-swelled Cl-type resin is preferably 1.2 meq / mL or more. More preferably, 1.4 meq / m
L or more. In addition, it is preferable that it is the range of 3.0 meq / mL or less practically.

The crosslinked strong basic resin has a water content of 50%.
It is preferred that the content be at least 10% by weight. Such a crosslinked strong basic resin can improve the reaction rate due to the high diffusion rate of the resin in the aqueous solution.
Therefore, the ion exchange ability and the catalytic ability of the crosslinked strong base resin and the solution diffusibility can be simultaneously improved, and the crosslinked product can be widely applied to various uses. The water content is more preferably 55 to 80% by weight, and still more preferably 60 to 80% by weight.
As such a crosslinked strong basic resin, for example, the crosslinked strong basic resin described above has a water content of 50% by weight.
As described above, it can be prepared by appropriately setting the structure of the essential repeating unit of the crosslinked product of the strong basic resin, the molar ratio of the essential repeating unit and the other repeating units, and the like. .

In the present specification, the water content is a value measured by the following method. First, a crosslinked Cl-type strongly basic resin is prepared in the same manner as in the above-described method for measuring the neutral salt decomposition capacity of the water-swelled Cl-type resin. After measuring 10 ml of the water-swelled body of the crosslinked Cl-type strong basic resin, removing excess water by filtration, and drying overnight at 60 ° C. under reduced pressure,
The moisture content is calculated from the weight before and after drying according to the following equation. Water content (%) = (1−weight after drying / weight before drying) ×
100

The method for producing the crosslinked product of a strongly basic resin of the present invention is not particularly limited. For example, a repeating unit having a cyclic secondary amine structure is essential, and the cyclic secondary amine structure forms a main chain. A method of reacting a basic polymer (hereinafter, simply referred to as a basic polymer) with a haloalkylammonium halide under alkaline conditions is preferably used.

As the basic polymer, for example, diallylamine homopolymer, a copolymer of diallylamine and diallyldimethylammonium chloride, etc. are preferable, and one or more kinds can be used. The molecular weight of the basic polymer is not particularly limited, and for example, the number average molecular weight is preferably 500 or more. More preferably, it is 10,000 to 500,000, and still more preferably 50,000 to 200,000.

The method for producing the basic polymer is not particularly limited, and reaction conditions and the like may be appropriately set depending on the type of the monomer used and the like. For example, when using a diallylamine homopolymer, diallylamine hydrochloride (DAA
An aqueous solution of HC) is prepared, polymerized, and then neutralized with an alkali to prepare an aqueous solution.

By reacting the basic polymer with a haloalkylammonium halide under alkaline conditions, a hydrogen atom on the nitrogen atom of the cyclic secondary amine structure of the basic polymer is substituted with an alkylammonium halide, When one alkylammonium halide is bonded to the nitrogen atom, a cyclic tertiary amine structure represented by the general formula (1) is generated. When such a cyclic tertiary amine structure is further reacted with a haloalkylammonium halide under alkaline conditions, another alkylammonium halide is bonded to the nitrogen atom of the cyclic tertiary amine structure, whereby a compound represented by the general formula (2) is obtained. A cyclic quaternary ammonium salt structure as shown is generated. As a reaction formula in such a case, in a cyclic secondary amine structure represented by the general formula (9), a basic polymer having a repeating unit having a cyclic secondary amine structure in which R ¹ and R ² are hydrogen atoms is essential. The case of using the union is shown in the following reaction scheme. In this case, the alkylammonium halide is gradually substituted on the nitrogen atom of the cyclic secondary amine structure of the basic polymer.
Two alkylammonium halides may be substituted simultaneously.

[0046]

Embedded image

In the above reaction formula, the formula (10) is a repeating unit having a cyclic secondary amine structure. General formula (11)
Is a haloalkylammonium halide. The general formula (12) is a repeating unit having a cyclic tertiary amine structure, and the nitrogen atom of the cyclic tertiary amine structure has a substituent that essentially requires a hetero atom. General formula (13)
Is a repeating unit having a cyclic quaternary ammonium salt structure, and the nitrogen atom of the cyclic quaternary ammonium salt structure has a substituent that essentially requires a hetero atom. General formulas (11), (12) and (13) in the above reaction scheme
In the formula, R ¹¹ , R ¹² and R ¹³ represent R ⁴ , R ⁵ and R ⁶
Is the same as A haloalkylammonium halide represented by the general formula (11), a repeating unit having a cyclic tertiary amine structure represented by the general formula (12), and a compound represented by the general formula (1)
The repeating unit having a cyclic quaternary ammonium salt structure represented by 3) may be one type or two or more types.

The reaction conditions for reacting the above-mentioned basic polymer with the haloalkylammonium halide are not particularly limited. For example, an alkaline compound is added to the reaction solution containing the basic polymer, if necessary, by adding a compound exhibiting alkalinity to the reaction solution containing the basic polymer. And it is preferable to react with a haloalkyl ammonium halide. The compound exhibiting such alkalinity is not particularly limited, and examples thereof include sodium hydroxide. The reaction temperature in this case is 20 ° C.
The reaction solution is preferably at a temperature of from 90 to 90 ° C., and the pH of the reaction solution is preferably from 8 to 13.

In the above reaction, the concentration of the basic polymer in the reaction solution is preferably, for example, 10 to 70% by weight. The molar ratio of the basic polymer to the haloalkylammonium halide in the reaction solution (the number of moles of the basic polymer / the number of moles of the haloalkylammonium halide) depends on, for example, the purpose of use of the crosslinked strong basic resin. It may be set appropriately depending on the desired performance and the like.

The method for producing the crosslinked product of the strongly basic resin is not particularly limited. For example, (1) a method of reacting a basic polymer with a haloalkylammonium halide and a crosslinking agent simultaneously or stepwise [Production] Method (A)]
(2) a method of reacting a haloalkylammonium halide with a crosslinking agent simultaneously or stepwise during the polymerization of a basic monomer [Production method (B)]; Is reacted and then polymerized with a crosslinking agent [Production method (C)].
In these production methods, in the production method (A), a haloalkylammonium halide is preferably reacted after a crosslinked product is obtained by reacting a reaction solution containing a basic polymer with a crosslinking agent to form a crosslinked product. (B)
Then, it is preferable to react a haloalkylammonium halide after obtaining a crosslinked body by polymerizing the monomer component in a reaction solution containing a basic monomer and a monomer component having a crosslinker as an essential component. Further, in the production method (C), a basic monomer having a side chain having a hetero atom is obtained by reacting a basic monomer with a haloalkylammonium halide, and then the side chain having the hetero atom is removed. It is preferable to polymerize a monomer composition having a basic monomer and a crosslinking agent. In the above production method, as the crosslinking agent, in the production method (A), it is preferable to use a compound having a bifunctional or more reactive point capable of forming a crosslinked structure, and the production method (B) and the production method In (C), a monomer capable of forming a repeating unit having a crosslinked structure, for example, a monomer having a crosslinked structure and a tertiary amine structure located at both ends of the crosslinked structure as described below is used. Is preferred.

As a series of reactions in the case of producing a crosslinked product of a strongly basic resin by the above production method (A), the following general formula (9)
Using a basic polymer having a repeating unit having a cyclic secondary amine structure in which R ¹ and R ² are hydrogen atoms in the cyclic secondary amine structure represented by the following formula, and using epichlorohydrin as a crosslinking agent. An example of reacting a haloalkylammonium chloride after obtaining a crosslinked product is summarized in the following reaction scheme.

[0052]

Embedded image

In the above reaction scheme, the formula (10), the general formulas (11), (12) and (13) are the same as described above. Formula (14) is a repeating unit having a crosslinked structure. The basic polymer which requires the repeating unit represented by the formula (10) is the basic polymer, and the repeating unit represented by the formula (10) and the repeating unit represented by the formula (14) are required. What is the above-mentioned crosslinked body. R ¹¹ , R ¹² and R ¹³ are the same as described above. M0 and M1 represent the molar ratio of the repeating unit having a cyclic secondary amine structure in the basic polymer or the crosslinked product, and are positive numbers. M2 and M
3 represents the molar ratio of the repeating unit having a cyclic secondary amine structure in the crosslinked strong basic resin, which is the same or different and is 0 or more. t represents a molar ratio of a repeating unit having a crosslinked structure in a crosslinked product or a strongly basic resin crosslinked product, and is 0 or more. m1 represents a molar ratio of the repeating unit having a cyclic tertiary amine structure in the crosslinked strong basic resin, and is a positive number. m2 represents the molar ratio of the repeating unit having a cyclic tertiary amine structure in the crosslinked strong basic resin, and is a number of 0 or more. n represents the molar ratio of the cyclic quaternary ammonium salt structure in the crosslinked strong basic resin, and is 0 or more. However, m2 and n are not simultaneously 0. Therefore, in the crosslinked strongly basic resin produced by the production method described above, the general formula (12) and / or
Or (13) and (14) as essential repeating units, and having formula (10) as necessary,
The molar ratio of these repeating units will be appropriately adjusted depending on the reaction conditions and the like.

As the basic polymer used in the production method (A), for example, the above-mentioned diallylamine homopolymer, a copolymer of diallylamine and diallyldimethylammonium chloride and the like are preferably used. As a specific method for obtaining a crosslinked product in the above production method (A), for example, a reaction solution containing a basic polymer is prepared, and the reaction solution is suspended in an inert organic solvent. It is preferable to form particles and then crosslink the basic copolymer using a crosslinking agent.

The reaction solution containing the basic polymer can be prepared, for example, by dispersing and dissolving the basic polymer in a solvent. As the solvent, it is possible to dissolve the basic polymer, and the reaction solution in which the basic polymer is dissolved does not mix with the inert organic solvent, that is, the reaction solution in the inert organic solvent Is not particularly limited as long as it satisfies the condition that is present as suspended particles. For example, water; an aqueous solution containing sodium hydroxide or the like; a mixed solvent in which water contains a water-miscible organic solvent such as methyl alcohol And the like. For example, in the case of a diallylamine homopolymer, the above-described DAA
An aqueous solution obtained by preparing an aqueous solution of HC, polymerizing, and neutralizing with alkali can be used as the reaction solution.

In the above-mentioned production method (A), the concentration of the basic polymer in the reaction solution is not particularly limited as long as the effects of the present invention are exhibited. For example, the concentration of the basic polymer in the reaction solution is not limited. Considering that the higher the value, the higher the strength and the more the crosslinked product having excellent performance can be obtained, the content is preferably 5 to 90% by weight. 5% by weight
If the amount is less than the above, the strength, ion exchange ability and catalytic ability of the crosslinked strongly basic resin may be insufficient. If it exceeds 90% by weight, the crosslinked product may not be easily granulated. More preferably, it is 20 to 60% by weight, and still more preferably, 30 to 50% by weight.

As a method of suspending the above reaction solution in an inert organic solvent to form suspended particles, it is preferable to carry out, for example, in the presence of a suspending agent. The inert organic solvent is not particularly limited, and includes, for example, pentane, n-hexane,
Saturated hydrocarbons such as heptane; alicyclic hydrocarbons such as ligroin and cyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. These may be used alone or in combination of two or more. Among these, toluene is preferred.

The suspending agent is not particularly restricted but includes, for example, glycerol palmitate, glycerol (mono)
Carboxylic acid glycerides represented by fatty acid glycerides such as stearate, glycerol oleate and glycerol linoleate; sorbitan esters such as sorbitan monopalmitate, sorbitan monostearate and sorbitan monooleate; These may be used alone or in combination of two or more.

To keep the suspended particles of the reaction solution stable in an inert organic solvent, it is preferable to use a precipitation inhibitor. The precipitation inhibitor is not particularly limited, and includes, for example, starch; gelatin; cellulose derivatives such as ethyl cellulose; and well-known precipitation inhibitors used in reversed-phase suspension polymerization such as polyvinyl alcohol. These may be used alone or in combination of two or more. Among these, ethyl cellulose and polyvinyl alcohol are preferred.

The crosslinking agent used in the above production method (A) is 2
It is not particularly limited as long as it has a functional point of functional or higher, that is, it has two or more sites capable of reacting with the basic polymer. The nitrogen atom constituting the secondary amine structure and / or the carbon atom directly or indirectly bonded to the nitrogen atom is used as at least one of the crosslinking points to contribute to the formation of the crosslinked structure.

Specific examples of the crosslinking agent include epoxy compounds such as epichlorohydrin and various diepoxy compounds; dichloro compounds such as 1,4-dichlorobutane and 1,2-bis (2-chloroethoxy) ethane; Dibromo compounds such as 1,2-dibromobutane and 1,4-dichlorobutane; and dialdehyde compounds such as glyoxal and glutaraldehyde. These may be used alone or in combination of two or more. Among these, epichlorohydrin is preferable, and a preferable crosslinked structure can be formed.

In the above-mentioned production method (A), the amounts of the cross-linking agent, inert organic solvent, suspending agent, precipitation inhibitor and the like are not particularly limited, and may be set as appropriate. The reaction conditions such as the reaction temperature in the cross-linking reaction are not particularly limited, and may be appropriately set depending on the type of the cross-linking agent, the properties of the basic polymer to be cross-linked, and the like.

In the above production method (B), as the basic monomer, for example, those having a structure represented by the following general formula (15) are preferable. Incidentally, the basic monomer,
At the time of polymerization, a salt of hydrohalic acid, inorganic acid, or organic acid is used.

[0064]

Embedded image

In the general formula (15), R ¹⁴ and R ¹⁵ are
Same as R ¹ and R ² . Further, as the cross-linking agent, for example, those having a structure represented by the following general formula (16) are preferable.

[0066]

Embedded image

In the general formula (16), R¹⁶, R¹⁷, R¹⁸
And R¹⁹Is R⁷ , R⁸ , R⁹ And R ^TenIs the same as
R²⁰, R^{twenty one}, R^{twenty two}And R^{twenty three}Is R¹ And R^Two Same as
You. R^{twenty four}And R^{twenty five}Are the same or different and are a hydrogen atom or
Represents an alkyl group having 1 to 18 carbon atoms. Where R^{twenty four}as well as
R^{twenty five}Is the R^{twenty four}And the R^{twenty five}Is connected to the nitrogen atom
It may be bonded to any of the carbon atoms that are combined.
c and d are the same or different and are integers from 0 to 10
And preferably 0 to 2. q is 0 or 1
You. However, c + d + q ≧ 1 is satisfied. W is the same as Z
It is. In the above general formula (16), X^- Are the same or different
Thus, halide ions, anions of organic acids or inorganic
It is an anion of an acid. Salt represented by the above general formula (15)
The basic monomer and the crosslinking agent represented by the general formula (16) are
Each may be used alone, or two or more kinds may be used in combination.
No.

A series of reactions in the case of producing a crosslinked product of a strongly basic resin by the above production method (B) is represented by the general formula (1)
In 5), a basic monomer in which R ¹⁴ and R ¹⁵ are hydrogen atoms is used, and R ¹⁶ , R ¹⁷ , R ¹⁸ ,
R ¹⁹ , R ²⁴ and R ²⁵ are hydrogen atoms, c and d are 1, W is —CH (OH) —, q is 1, X is Cl
An example of reacting a haloalkylammonium chloride after obtaining a crosslinked product using the crosslinking agent is summarized in the following reaction scheme.

[0069]

Embedded image

In the above reaction scheme, the formula (10), the general formulas (11), (12), (13) and the formula (14) are the same as described above. Formula (17) is a basic monomer, and Formula (18) is a crosslinking agent. The basic polymer which requires the repeating unit represented by the formula (10) is the basic polymer, and the repeating unit represented by the formula (10) and the formula (14)
The above-mentioned crosslinked product is required for the repeating unit represented by the following formula. R ¹¹ , R ¹² and R ¹³ are the same as described above.
M0, M1, M2, M3, t, m1, m2 and n are the same as above. Therefore, in the crosslinked strongly basic resin produced by the production method described above, the general formula (12) and / or
Or (13) and (14) as essential repeating units, and having formula (10) as necessary,
The molar ratio of these repeating units will be appropriately adjusted depending on the reaction conditions and the like.

In the above-mentioned monomer component, in addition to the basic monomer and the crosslinking agent, a polymerizable monomer copolymerizable with these essential monomers is contained as long as the effects of the present invention are exhibited. You may go out. Examples of such a polymerizable monomer include styrene, ethylene, and vinyl ether. These may be used alone or in combination of two or more.

The molar ratio of the basic monomer represented by the general formula (15) and the crosslinking agent represented by the general formula (16) in the monomer component, the basic unit in the monomer component and The molar ratio between the monomer and the crosslinking agent (the number of moles of the basic monomer / the number of moles of the crosslinking agent) is not particularly limited as long as the action and effect of the present invention are exhibited.
What is necessary is just to set suitably according to the desired performance etc. according to the use purpose of a strong basic resin crosslinked body.

In the above production method (B), the higher the concentration of the monomer component in the reaction solution, the higher the strength and the higher the performance of the crosslinked product can be obtained.
For example, the content is preferably 5 to 90% by weight. If the amount is less than 5% by weight, the strength, ion exchange ability and catalytic ability of the crosslinked strongly basic resin may be insufficient. 90% by weight
When it exceeds, the crosslinked product may not be easily granulated.
More preferably, it is 40 to 80% by weight, still more preferably 50 to 70% by weight.

When the above monomer components are polymerized, a polymerization initiator is usually used. The polymerization initiator is not particularly limited and includes, for example, peroxide initiators such as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2 ′
Azo compounds (azo initiators) such as azobis (2-amidinopropane) dihydrochloride; radical polymerization initiators such as ammonium persulfate, sodium persulfate, potassium persulfate and other persulfates (persulfate initiator) And the like. These may be used alone or in combination of two or more.
Among these, it is preferable to carry out the polymerization reaction using an azo-based initiator since there is no sulfur remaining which may act as a catalyst poison depending on the reaction. The amount used is not particularly limited. Further, instead of using the polymerization initiator, the polymerization may be started by irradiating radiation, an electron beam, ultraviolet light, or the like, or the polymerization initiator may be used in combination with the irradiation of radiation, an electron beam, ultraviolet light, or the like. Good.

The reaction conditions for carrying out the above polymerization reaction are not particularly limited. For example, the reaction temperature may be appropriately set according to the type of the monomer component and the dispersion medium. The reaction time may be appropriately set according to the reaction temperature, the composition of the monomer components, the type and combination of the polymerization initiator and the dispersion medium, the amount used, and the like so that the polymerization reaction is completed. Further, the reaction pressure may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

As a method for polymerizing the above monomer component,
For example, it is preferable to carry out by suspension polymerization or the like. Suspension polymerization of the above monomer components in a reaction solution provides excellent thermal decomposition resistance, exhibits high processing ability as a strongly basic ion exchange resin or resin catalyst, and has a spherical (pearl-like) shape with a desired particle size. )) Can be obtained.

The dispersion medium (solvent) used for the reaction solution in the above suspension polymerization is not particularly limited.
Examples include toluene and cyclohexane. These may be used alone or in combination of two or more. The use amount of the dispersion medium is not particularly limited.

In carrying out the above suspension polymerization, it is preferable to use a suspending agent. Such a suspending agent is not particularly limited, and examples thereof include sorbitan esters.
The amount used is not particularly limited.
Further, in order to stably maintain the suspension state of the monomer component in the reaction solution, a precipitation inhibitor or the like may be used. Such a precipitation inhibitor is not particularly limited, and examples thereof include gelatin, dextrin, and polyvinyl alcohol. These may be used alone or in combination of two or more.

A series of reactions for producing a crosslinked product of a strongly basic resin by the above production method (C) is represented by the general formula (1)
In 5), a basic monomer in which R ¹⁴ and R ¹⁵ are hydrogen atoms is reacted with a haloalkylammonium halide to obtain a basic monomer (19) and / or (20) having a side chain having a hetero atom. After that, polymerization and cross-linking are performed using a monomer composition containing the basic monomer (19) and / or (20) having a side chain having a hetero atom as an essential component in the following reaction scheme. Are shown together. In the following reaction scheme, the crosslinking agent represented by the formula (18) is represented by the general formula (1)
In 6), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁴ and R ²⁵ are hydrogen atoms, c and d are 1, W is —CH (O
H)-, wherein q is 1 and X is Cl.

[0080]

Embedded image

In the above reaction scheme, the general formula (10)
(11), (12), (13), (14), (17) and (18) are the same as above. The general formulas (19) and (20) are basic monomers having a side chain having a hetero atom. M3, t, m2 and n are the same as above. Therefore, in the strongly basic resin crosslinked product produced by the production method described above, the general formula (12) and / or (1)
3) and (14) as essential repeating units,
The compound has the formula (10) as needed, and the molar ratio of these repeating units is appropriately adjusted depending on reaction conditions and the like.

The monomer composition containing the basic monomer (19) and / or (20) having a side chain having a hetero atom as the essential component comprises a haloalkylammonium halide and an unreacted basic monomer. It may contain a polymerizable monomer copolymerizable with these essential monomers as long as the effects of the present invention can be achieved. Examples of such a polymerizable monomer include those described in the above-mentioned production method (B).

In the above production method (C), the amounts of the basic monomer, haloalkylammonium halide and crosslinking agent used are not particularly limited, and may be appropriately set.
The method of polymerizing the monomer composition and the reaction temperature in the crosslinking reaction are not particularly limited, and may be set as appropriate.

The crosslinked strongly basic resin produced by the above-mentioned production method can be used as it is as a strongly basic ion exchange resin or the like, but may be washed with a polar solvent in which an inorganic salt is soluble. . This makes it possible to obtain a crosslinked strongly basic resin having higher ion exchange ability, catalytic ability, and strength. The above-mentioned inorganic salt means, for example, an inorganic salt formed by alkali-neutralizing the diallylamine hydrochloride portion contained in the diallylamine homopolymer. For example, when the alkali neutralization is performed using NaOH, the inorganic salt means NaCl.

The polar solvent varies depending on the type of the inorganic salt, but is generally water; hydrophilic alcohols such as methyl alcohol and glycerin; dimethylformamide; dimethylacetamide; dimethylsulfoxide;
-Methylpyrrolidone and the like. These may be used alone or in combination of two or more. For example, when the inorganic salt is NaCl, the polar solvent is preferably water, glycerin, methyl alcohol or the like, and water is most preferable from the viewpoint of solubility.

The use of the crosslinked product of the strongly basic resin is not particularly limited. For example, a resin catalyst used as a strongly basic ion exchange resin used for an ion exchange reaction, or used for a reaction for activating active hydrogen, etc. Production of pure water, separation and purification of amino acids, recovery of catalyst and metal, recovery of iodine, recovery of sugar solution, decolorization of sucrose, purification of uranium,
It can be suitably applied in various industrial fields such as formalin purification. In such a use, the strongly basic resin crosslinked product of the present invention has an extremely large ion exchange ability and catalytic ability such that the neutral salt decomposition capacity of the water-swelled Cl-type resin is 1.1 meq / mL or more. It can be used in the field in which is required or the field in which high solution diffusivity is required. That is, in the crosslinked product of the strongly basic resin of the present invention, as an ion exchange resin or a catalyst, the ion exchange ability and the catalytic ability are extremely high, and further, a high solution diffusion property can be realized, and the reaction rate can be improved. The use can be greatly expanded.

The above-mentioned ion exchange reaction more specifically means an anion exchange reaction. In the crosslinked strongly basic resin of the present invention, a nitrogen atom derived from a quaternary ammonium salt structure and / or a tertiary amine structure present in the molecule,
Further, the hetero atom of the above-described substituent functions as an ion-exchange group, and the hydroxide ion, halide ion, and anion of an organic acid or an inorganic acid that these ion-exchange groups have may form another anion. Exchanged for ions.

The reaction for activating the active hydrogen is defined as the reaction of the active hydrogen with a nitrogen atom derived from the tertiary amine structure or quaternary ammonium salt structure of the crosslinked strong basic resin, a hetero atom in the substituent, or the like. It means that active hydrogen is extracted or more easily dissociated from a compound having the compound, that is, activation of the active hydrogen of the compound is meant. The crosslinked product of the strongly basic resin is a reaction for nucleophilic addition by extracting active hydrogen from a compound having active hydrogen, or by making active hydrogen more easily dissociated, that is, various reactions involving activation of active hydrogen. It can be suitably used for the reaction.

The above-mentioned active hydrogen means a hydrogen atom involved in a desired reaction among all the hydrogen atoms of the compound. Such active hydrogen is not particularly limited, and is preferably, for example, a hydrogen atom having a higher reactivity than a hydrogen atom directly bonded to a carbon atom in an organic compound having no hetero atom. There are no particular restrictions regarding the aforementioned hydrogen atoms, for example, -NH ₂ group, -CONH group, -OH group, -
A hydrogen atom directly bonded to a hetero atom such as an SH group; a hydrogen atom bonded to a carbon adjacent to an electron-withdrawing group such as a hydrogen atom at the α-position of a carbonyl compound (α-hydrogen atom); a hydrogen atom constituting a substituted aromatic A hydrogen atom constituting a functional group such as an aldehyde and a carboxylic acid;

Among the compounds having active hydrogen to which the crosslinked strong basic resin obtained by the present invention is applied, unsaturated carboxylic acids are preferable, and (meth) acrylic acid is most preferable. The compound having active hydrogen may have a plurality of active hydrogens. In this case, the bonding forms of these active hydrogens may be the same or different.

The reaction for activating activated hydrogen using the crosslinked strongly basic resin as a resin catalyst is not particularly limited, and can be suitably used, for example, in the following reactions.

The reaction involving a hydrogen atom directly bonded to a hetero atom includes, for example, the following reaction examples (1) to (14). Incidentally, reactions involving a hydrogen atom directly bonded to a hetero atom are not limited to only these reactions.

(1) Addition reaction of a cyclic hetero compound (eg, ethylene oxide, ethylene imine, ethylene sulfide, etc.) to an amine (primary amine or secondary amine). (2) Conversion reaction of amines (primary amines or secondary amines) to amides. (3) Hydrolysis reaction of amides. (4) An addition reaction of a cyclic hetero compound to an amide, for example, an addition reaction of ethylene oxide to pyrrolidone or isocyanuric acid. (5) Addition reaction of cyclic hetero compound to thioamides.

(6) Addition reaction of a cyclic hetero compound to water or alcohols (primary, secondary or tertiary alcohols), for example, water, methanol,
Addition reaction of oxirane compounds such as ethylene oxide and propylene oxide to ethanol, propanol or butanol. (7) Reaction of alcohols (primary alcohol, secondary alcohol or tertiary alcohol) with hydrogen halide, for example, reaction of synthesizing isopropyl bromide from isopropyl alcohol and concentrated hydrogen bromide. (8) An ester synthesis reaction using an alcohol (a primary alcohol, a secondary alcohol, or a tertiary alcohol). (9) Oxidation reaction of alcohols (primary alcohol, secondary alcohol or tertiary alcohol). (10) Addition reaction of a cyclic hetero compound to phenols (for example, phenol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, BHPF (bishydroxyphenylfluorene), dihydroxydiphenylmethane, etc.).

(11) Reaction for synthesizing ethers from phenols and alkyl halides (Williamson synthesis reaction), for example, p-nitrobenzyl-p from p-cresol and p-nitrobenzyl bromide The following reaction for synthesizing tolyl ether: (12) Ester synthesis reaction using phenols, for example, p-nitrophenol and acetic anhydride to give p-acetic acid
A reaction for synthesizing nitrophenyl or a reaction for synthesizing o-bromophenyl-p-toluenesulfonic acid from o-bromophenol and p-toluenesulfonyl chloride. (13) Addition reaction of a cyclic hetero compound to thiols (first thiols, second thiols, or third thiols). (14) Addition reaction of a cyclic hetero compound to thiophenols.

Examples of the reaction involving a hydrogen atom bonded to a carbon atom adjacent to the electron-withdrawing group include the following reaction examples (1) to (8). still,
Reactions involving a hydrogen atom bonded to a carbon atom adjacent to the electron withdrawing group are not limited to only these reactions.

(1) A ketone halogenation reaction, for example, a reaction of introducing a bromine atom into cyclohexanone. (2) Aldol condensation reaction, for example, a reaction for synthesizing 3-hydroxybutanal from acetaldehyde or a reaction for synthesizing diacetone alcohol from acetone. (3) Perkin condensation reaction. (4) Knoevenagel condensation reaction.

(5) Cope reaction. (6) Various nucleophilic addition reactions to carbonyl compounds (ketones) such as the Wittig reaction. (7) Nucleophilic acyl substitution reaction to ketones such as Claisen condensation reaction. (8) Addition reaction (Michael addition reaction) to α, β-unsaturated carbonyl compound (ketones).

Examples of the reaction involving a hydrogen atom constituting the substituted aromatic include the following reaction examples (1) and (2). It should be noted that reactions involving hydrogen atoms constituting the substituted aromatic are not limited only to these reactions. (1) Reimer-Tiem
nn) reaction. (2) Friedel-Crafts
ts) acylation reaction.

Examples of the reaction involving a hydrogen atom constituting a functional group such as an aldehyde or a carboxylic acid include the following reaction examples (1) to (4).
In addition, reactions involving a hydrogen atom constituting a functional group such as aldehyde and carboxylic acid are not limited to these reactions.

(1) Addition reaction of a cyclic hetero compound (eg, ethylene oxide, propion oxide, etc.) to a carboxylic acid (eg, acrylic acid, methacrylic acid, acetic acid, propionic acid, etc.), for example, an industrially important reaction A reaction for synthesizing (meth) acrylic acid hydroxyethyl ester from (meth) acrylic acid and ethylene oxide, and a reaction for synthesizing (meth) acrylic acid hydroxypropyl ester, known as methacrylic acid and ethylene oxide. (2) Addition reaction of a cyclic hetero compound to thiocarboxylic acids.

(3) Addition reaction of alcohol to aldehydes. (4) Cannizzaro reaction,
More specifically, a reaction for producing trimethylolpropane by subjecting formaldehyde to aldol condensation twice with n-butylformaldehyde and then performing a Cannizzaro reaction.

The above-mentioned crosslinked strongly basic resin can be used for phenols, amides, alcohols, carboxylic acids, malonic acid, cyanoacetic acid and esters thereof among the reactions involving activation of active hydrogen in these active hydrogen-containing compounds. A reaction of adding a cyclic hetero compound (preferably an oxirane compound, more preferably ethylene oxide or propylene oxide) or an aldehyde to one or more active hydrogen-containing compounds selected from the group consisting of: a Mannich reaction; Alkylation reaction of compounds;
It can be more suitably used for hydroxyalkyl esterification of (meth) acrylic acid described in JP-A-13019, cyanohydrin formation reaction, cyanoethylation reaction and the like. Among these, phenols, amides,
Active hydrogen-containing compounds selected from the group consisting of alcohols, carboxylic acids, malonic acid, cyanoacetic acid and esters thereof (more preferably carboxylic acids and esters, particularly preferably (meth) acrylic acid)) It is particularly preferably used for the reaction of adding an oxirane compound or an aldehyde (more preferably, an oxirane compound).

[0104]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Preparation of Cross-linked Poly (diallylamine) A homopolymer of diallylamine hydrochloride and a linear polymer having a molecular weight of about 150,000 was converted to a solid content of 44%
90.9 g of the resulting aqueous solution was mixed with 42.4 g of an 8.5% aqueous NaOH solution to prepare an aqueous polymer compound solution. Subsequently, a container 1L equipped with a thermometer and an irrigating stirrer
Was charged with 500 ml of toluene as a dispersion medium (inert organic solvent), 0.67 g of sorbitan monopalmitate and 0.67 g of ethyl cellulose as suspending agents. And the stirring blade is 25
While rotating at 0 rpm, the above polymer compound aqueous solution is gently mixed and suspended (dispersed) in a dispersion medium.
Hold for hours. Subsequently, 4.15 g of epichlorohydrin as a cross-linking agent was added dropwise over 1 hour, and the temperature was raised to 80 ° C. and the reaction was carried out for 4 hours. After cooling the reaction solution in the vessel, a crosslinked polymer was obtained by filtration. The crosslinked polymer was washed with 600 ml of toluene and then placed in 600 ml of pure water to obtain a water-expanded body. Then, 13.1 g of a 48% aqueous NaOH solution was added dropwise with stirring, and after maintaining for 30 minutes, the crosslinked polymer was washed with water until the washing water became neutral. The crosslinked polymer was dried under reduced pressure at 60 ° C. overnight, and 29.2 g of the obtained dried product was obtained as a crosslinked polymer A.

Example 2 Preparation of bromobutyltrimethylammonium bromide (BBA) Tetrahydrofuran (THF) 6 was added to a 2 L four-necked flask.
00 ml and 1,8.0 g of 1,4-dibromobutane were charged and cooled. At 0 ° C., 32.5 g of trimethylamine dissolved in 250 ml of THF was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 1.5 days to complete the reaction. The precipitated crystals were filtered by suction and washed with 700 ml of THF. Crystals at room temperature
It was dried under reduced pressure overnight to obtain 106.0 g of BBA. H ¹ NMR
As a result, the ratio of trimethylamine 1 adduct was 95 mol%.
Met.

Example 3 Addition reaction of BBA 9.38 g of the BBA obtained in Example 2 was placed in a four-necked flask, dissolved in 37.6 g of pure water, and 3.0 g of the crosslinked polymer obtained in Example 1 was added. Was added. By appropriately adding NaOH, the pH of the reaction solution was kept at 7 to 11 and kept at 50 ° C for 15 days. Subsequently, the crosslinked polymer was washed three times with 400 ml of pure water and dried under reduced pressure at 60 ° C. overnight to obtain BBA.
Was added to obtain 12.00 g of a crosslinked polymer B. As a result of elemental analysis, the number of added BBA was 1.5 per N atom of the crosslinked polymer A. The neutral salt decomposition capacity of the Cl-type water-swelled body was 1.5 meq / ml, and the water content was 62% by weight.

Example 4 Synthesis of bromobutylpyridinium bromide (BBP) 100 ml of benzene was placed in a 500 ml separable flask.
And 108.0 g of 1,4-dibromobutane were charged and heated to reflux with stirring. Then pyridine 1
3.2 g was added dropwise over 15 hours, and reflux was further applied for 3 hours. After the reaction was completed, the temperature was returned to room temperature, and the precipitate was taken out by filtration and washed with 80 ml of acetone. This at room temperature
It was dried under reduced pressure overnight to obtain 35.9 g of powder. As a result of H ¹ NMR, the ratio of the pyridine 1 adduct was 74 mol%.

Example 5 Addition reaction of BBP 24.3 g of the BBP obtained in Example 4 was placed in a four-necked flask, dissolved in 36.6 g of pure water, and 3.0 g of the crosslinked polymer A obtained in Example 1 was obtained. Was added. By appropriately adding NaOH, the pH of the reaction solution is maintained at 7 to 11, and
It was kept at 150C for 15 days. Subsequently, the crosslinked polymer was 400 m
of pure water three times, and dried under reduced pressure at 60 ° C. overnight.
10.5 g of a crosslinked polymer C to which BP was added was obtained. As a result of elemental analysis, the number of added BBA was 1.2 per N atom of the crosslinked polymer A. The neutral salt decomposition capacity of the Cl-type water-swelled body was 1.4 meq / ml, and the water content was 58% by weight.

Example 6 Using the crosslinked polymer B obtained in Example 3, a hydroxypropylation reaction of acrylic acid was carried out as an addition reaction of a cyclic hetero compound to a carboxylic acid. That is, acrylic acid and propylene oxide were charged into a reaction vessel equipped with a thermometer, a stirrer, and the like so that the molar ratio of propylene oxide to acrylic acid was 1.2 times, to obtain a reaction solution. Next, Example 3 was added to the reaction solution.
Was added in an amount of 15% by weight based on acrylic acid. Thereafter, the reaction solution was reacted at 70 ° C. for 4 hours while stirring to carry out hydroxypropylation of acrylic acid. After completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by GC. As a result, the conversion of acrylic acid was 66.6%, the selectivity of an adduct (reaction product) obtained by adding one molecule of propylene oxide to acrylic acid was 87.5%, and the propylene oxide was converted to acrylic acid. The selectivity of the adduct (reaction by-product) with two molecules added was 11.7%. From this, it was found that the crosslinked polymer B obtained in Example 1 acts as a catalyst for the hydroxypropylene pyration reaction of acrylic acid, which is a cyclic heteroaddition reaction to carboxylic acids.

Example 7 In the same manner as in Example 6, using the crosslinked polymer C obtained in Example 5, hydroxypropylene was converted to acrylic acid. As a result, the conversion of acrylic acid was 68.0.
%, And the selectivity of an adduct of one molecule of propylene oxide added to acrylic acid (reaction product) is 88.1%, and an adduct of two molecules of propylene oxide added to acrylic acid (reaction by-product) Was 10.5%. Thus, the crosslinked polymer C obtained in Example 6 is an addition reaction of a cyclic hetero compound to carboxylic acids. It was found to act as a catalyst for the hydroxypropylation reaction of acrylic acid.

[0112]

The crosslinked product of a strongly basic resin according to the present invention has the above-mentioned structure, and therefore has an extremely high ion exchange capacity and catalytic capacity as an ion exchange resin or catalyst, and also realizes a high solution diffusion property. As it can improve the reaction rate, as a strong basic ion exchange resin or resin catalyst,
Production of pure water, separation and purification of amino acids, recovery of catalysts and metals,
Widely used in various industrial fields such as recovery of iodine, recovery of sugar solution, decolorization of sucrose, purification of uranium, purification of formalin, etc., where improvement of ion exchange capacity and catalytic capacity and improvement of solution diffusivity are required. can do.

Claims (4)

[Claims] 1. A repeating unit having a cyclic amine structure, wherein the repeating unit having a cyclic amine structure is essential, and the cyclic amine structure is a crosslinked product of a strong basic resin in which a main chain is formed. A crosslinked product of a strongly basic resin, characterized in that the nitrogen atom has a substituent that essentially requires a hetero atom. 2. A repeating unit having a cyclic amine structure.
The position is represented by the following general formula (1):[Wherein, R¹ And R^Two Are the same or different
, A halogen atom, a methyl group or an ethyl group. R^Three 
Is a divalent carbon having 1 to 18 carbon atoms which may have a hetero atom
Represents a hydride group. R^Four , R^Five And R⁶ Are the same or different
Thus, a carbon atom which may have a hydrogen atom or a hetero atom
-18 represents a monovalent hydrocarbon group. Where R ^Four , R^Five Passing
And R⁶ Any two of may be bonded to each other
No. X^- Is a halide ion, an anion of an organic acid or
Represents an anion of an inorganic acid. A tertiary cyclic amine represented by the formula
And / or a repeating unit having the following general formula:
(2);[Wherein, R¹ And R^Two Are the same or different
, A halogen atom, a methyl group or an ethyl group. R^Three 
Are the same or different and may have a heteroatom
Represents a divalent hydrocarbon group represented by Formulas 1 to 18. R^Four , R^Five And R
⁶ Are the same or different and have a hydrogen atom or a hetero atom.
Represents a monovalent hydrocarbon group having 1 to 18 carbon atoms which may be used. Was
But R^Four , R^Five And R⁶ Any two of them are
May be bonded to X^- Are the same or different
Logenide ion, anion of organic acid or ani of inorganic acid
Indicates ON. And a cyclic quaternary ammonium salt structure represented by the formula:
2. A repeating unit having the formula:
The crosslinked strongly basic resin according to the above. 3. A strongly basic crosslinked resin in which a repeating unit having a cyclic amine structure is essential and the cyclic amine structure forms a main chain, wherein the strongly basic crosslinked resin is a water-swelled Cl-type resin. A crosslinked product of a strongly basic resin, having a neutral salt decomposition capacity of 1.1 meq / mL or more. 4. The crosslinked product of a strongly basic resin has a water content of 5%.
4. The crosslinked strongly basic resin according to claim 3, wherein the content is 0% by weight or more.