JPH0469167B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel ion exchange resin having basic functional groups and a method for producing the same. Currently, anion exchange resins in which the chloromethylstyrene skeleton is aminated with dimethylamine, trimethylamine, etc. are used.
These resins have poor heat resistance and chemical resistance, and their exchange capacity decreases as they are used. The present inventors have made intensive studies to find an alternative anion exchange resin, and as a result, have completed the present invention. That is, the ion exchange resin of the present invention is a three-dimensional crosslinked copolymer composed of polymerized units represented by the following structural formulas (), (), (), (), and (). (),()as well as

【formula】

【formula】

【formula】

【formula】

[Formula] 2 to 50 mol% of polymerized units in (), 0 to 50 mol%, respectively
50 mol%, 10-98 mol%, 0-30 mol% and 0-
It is a copolymer containing 30 mol%. (However, R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and X represents a halogen. Furthermore, the position of the substituent on the benzene skeleton and the pyridine skeleton may be any position. ) The above structural formula () corresponds to divinylbenzene and its derivatives, and preferred examples include those in which R ₁ is hydrogen or a methyl group. () is 2 to 50 mol%, preferably 2 to 35 mol%. Structural formula () is a polymerized unit corresponding to styrene and its derivatives. A plurality of units with different R ₂ of formula () can be contained in the polymer. () is 0 to 50 mol%. Structural formula()
is a polymerized unit having a heterocycle containing a nitrogen atom, and exhibits basicity as an ion exchange resin. () is 10 to 98 mol%, preferably 20 to 70 mol%. Structural formula () has a halogenoacetyl group, and X represents fluorine, chlorine, bromine, or iodine. () and () are 2
-30 mol%, preferably 0-15 mol%. In structural formulas (), (), and (), a plurality of different units of R ₃ can be used. Also, the structural formula (),
() can also contain a plurality of units with different R ₄ . The polymerized units represented by structural formulas (), (), and () may not be included in the polymer. Further, the present invention provides a three-dimensional crosslinked copolymer (hereinafter referred to as raw material polymer) containing polymerized units represented by the structural formulas () and () and, if necessary, the structural formula (), and the following structural formula ( The present invention relates to a method for producing an ion exchange resin having a basic functional group, which comprises reacting the α-picoline shown in (a) and then subjecting it to an alkali treatment if necessary. (R ₄ is the same as above. Any position of R ₄ is acceptable.) The raw material polymer can be synthesized by several methods. First of all, () and ()
Furthermore, if necessary, it can be obtained by copolymerizing a monomer corresponding to the structural formula (). There is no problem in using a plurality of monomers having different R ₂ and R ₃ as the monomers corresponding to the structural formulas () and (). For polymerization, ordinary suspension polymerization or emulsion polymerization techniques can be employed. Second, Y-CO-CH ₂ -X (Y
represents a halogen) by subjecting a halogenoacetyl halide to a Friedel-Crafts reaction. Furthermore, () and ()
A three-dimensional crosslinked polymer consisting of polymerized units of
It can also be obtained by subjecting acetyl halide or acetic anhydride represented by YCOCH ₃ to a Friedel-Crafts reaction, and then directly converting the methyl group into a halide with X in the presence of a catalyst if necessary. The composition of each component of the raw material polymer having polymerized units represented by structural formulas (), (), and () is ()
is 2 to 50 mol%, () is 0 to 50 mol%, () is
It is 10-98 mol%. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and in a preferred embodiment, R ₁ is hydrogen, a methyl group, etc., and R ₂ and R ₃ are hydrogen, Methyl group, ethyl group, etc., and _R4 is hydrogen, methyl group,
An ethyl group is preferred. Also, X is Cl or Br
It is preferable that Next, a method for reacting the raw material polymer with α-picolines will be described. The amount of α-picolines is preferably equal to or more than the number of moles of polymerized units represented by the structural formula () in the raw material polymer,
More preferably, it is 1 to 5 times the mole amount. When carrying out this reaction, the reaction may be carried out in the presence of an inert liquid. The amount of this inert liquid used is not particularly limited, but the slurry concentration relative to the raw material polymer is preferably 1 to 300 g. Specific examples of inert liquids include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;
Aliphatic hydrocarbons such as hexane, heptane, octane, nonane, and decane; alcohols such as methanol, ethanol, propanol, butanol, and phenol; ethers such as diethyl ether, dibutyl ether, and tetrahydrofuran;
Esters such as methyl formate, ethyl acetate, and methyl butyrate, aromatic substituted derivatives such as nitrobenzene and chlorobenzene, amides such as acetamide, dimethylformamide, and dimethylacetamide, dimethyl sulfoxide, and water can be used. When carrying out the reaction with α-picolines, it may be preferable to add a basic substance. Basic substances include sodium hydroxide, potassium hydroxide,
These include alkali metal salts such as sodium carbonate, and alkali metal alcoholates such as sodium ethylate and sodium butylate. The reaction temperature is not particularly limited, but is preferably 20 to 200°C, more preferably 20 to 150°C.
There is no particular restriction on the reaction time, but a reaction time of 0.5 to 100 hours is usually employed. Next, the method of alkali treatment will be described. The alkali treatment in the present invention refers to reacting a reaction product of α-picolines and a raw material polymer with a basic aqueous solution. Substances that exhibit basicity include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and alkali metal alcoholates such as sodium methylate and sodium ethylate dissolved in water. be. At this time, a small amount of water-soluble organic components such as alcohol may be added to the water. The concentration of these basic substances is usually about 0.01 to 5 M/L. The amount of the basic aqueous solution is approximately 1 to 300 g per slurry concentration relative to the raw material polymer.
There is no particular restriction on the reaction time, but about 1 to 50 hours is used. Although there is no particular restriction on the reaction temperature, a temperature of about 20 to 120°C is used. When producing the polymer of the present invention, α
- When carrying out alkali treatment after the reaction with picolines, it is also possible to carry out so-called one-pot synthesis, in which the salt basic substance is directly added to the reaction solution with α-picolines and reacted. Next, specific embodiments of the present invention will be shown. First, the raw material polymer, α-picolines, and if necessary, an inert liquid and a basic substance are mixed, and then a reaction is carried out at a specified temperature for a specified period of time, followed by alkali treatment as necessary to obtain the desired product. I can do it. The novel ion exchange resin of the present invention may contain other polymerized units to the extent that the properties of the ion exchange resin are not changed. Since the novel ion exchange resin of the present invention has an indolizine ring structure, it has anion exchange ability due to its basicity and is useful as a thermally and chemically stable anion exchange resin. Examples are shown below. Raw material polymers No. 1 to No. 7 shown in Table 1 were synthesized from haloacetylstyrenes, styrenes, and divinylbenzenes by conventional suspension polymerization.

[Table] Example 1 13.504gr. of raw material polymer No. 1 in Table 1 and α-
Water in which 7.42gr. (79.7mmol) of picoline is dissolved
150 ml of the mixture was mixed and reacted at 80° C. for 3 hours under stirring in a nitrogen atmosphere. Add 6.70gr. (79.7mol) of sodium bicarbonate to the reaction mixture,
The reaction was further continued at 100° C. for 3 hours with stirring in a nitrogen atmosphere. The product was thoroughly washed with acetone and water. The yield of free product was 14.312 gr.
The main peaks of the infrared absorption spectrum were as follows. 2910, 1670, 1600, 1490, 1445, 1360, 1290,
1175, 1100, 830, 760, 700 (cm ^-1 ) The results of elemental analysis were as follows. C; 78.13 H; 6.05 N; 3.00 Cl; 2.14 Br; 10.68 (%) In addition, when the ion exchange capacity was measured, it was 2.09meq/
gHCl type (including 0.68 meq of strong base portion).
From these results, (), (),
The molar percentages of each component (), (), and () were found to be 17.0%, 33.2%, 25.9%, 11.5%, and 12.4%, respectively. Examples 2 to 5 Table 2 shows the results of reactions conducted in substantially the same manner as in Example 1.

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Claims (1)

[Claims] 1. A three-dimensional crosslinked copolymer constructed from polymerized units represented by the following structural formulas (), (), (), () and () [Formula] [Formula] [Formula] [ Formula】【Formula】 and (), (), (), () and ()
An ion exchange resin containing 2 to 50 mol%, 0 to 50 mol%, 10 to 98 mol%, 0 to 30 mol%, and 0 to 30 mol% of polymerized units, respectively. (However, R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and X represents a halogen. Furthermore, the substituents may be placed in any position on the benzene skeleton and the pyridine skeleton. .) 2 The ion exchange resin according to claim 1, wherein R ₁ is hydrogen or a methyl group. 3. Claim 1 or 2, wherein each of R ₂ and R ₃ is hydrogen, a methyl group, or an ethyl group.
The ion exchange resin described in Section. 4 Claim 1 in which X is Cl or Br
2. The ion exchange resin according to any one of Items 2 and 3. 5 α-picolines are added to a three-dimensional crosslinked copolymer containing 2 to 50 mol%, 0 to 50 mol%, and 10 to 98 mol% of polymerized units represented by the following structural formulas (), (), and (), respectively. A three-dimensional crosslinked copolymer structured from polymerized units represented by the following structural formulas (), (), (), () and (), characterized by reacting with [Formula][ Formula] [Formula] [Formula] [Formula] The polymerized units of (), (), (), () and () are respectively 2 to 50 mol%, 0 to 50 mol%, 10 to
A method for producing an ion exchange resin containing 98 mol%, 0 to 30 mol%, and 0 to 30 mol%. (However, R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and X represents a halogen. Furthermore, the substituents may be placed in any position on the benzene skeleton and the pyridine skeleton. .)