JPH0469171B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel basic ion exchange resin and a method for producing the same. Currently, anion exchange resins are made by aminating a copolymer with a chloromethylstyrene skeleton by reacting dimethylamine, trimethylamine, etc., but these resins lack durability and chemical resistance. Unfortunately, as it is used, the exchange capacity decreases. 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 present invention provides structural formulas (), (), (),
A three-dimensional crosslinked copolymer consisting of polymerized units represented by () and (), containing 2 to 50 mol% of polymerized units represented by () (0 to 50 mol% of polymerized units represented by parentheses) () It is an ion exchange resin containing 10 to 98 mol% of polymerized units represented by () and 0 to 30 mol% of polymerized units represented by ().

【formula】

【formula】

【formula】

【formula】

[Formula] (However, R ₁ , R ₂ and R ₃ are hydrogen or carbon number 1
R ₄ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. The position of the substituent on the benzene 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. Preferred embodiments of R ₂ include hydrogen, methyl group, and ethyl group. In (), a plurality of units with different R ₂ can be contained in the polymer. () is 0 to 50 mol%. Structural formula () has an imidazole skeleton and exhibits basicity in the present ion exchange resin. Structural formula () has a cyano group, and is 0 to 30 mol%, preferably 0 to 10%
It is. In the structural formulas (), (), and (), a plurality of units with different R ₃ may be used. Further, structural formulas () and () can also contain a plurality of units with different R ₄ . Structural formula(),()
The polymerized units represented by and () may not be included in the polymer. Furthermore, the production method of the present invention has structural formulas () and ()
Furthermore, if necessary, a three-dimensional crosslinked copolymer containing polymerized units represented by the structural formula () (hereinafter referred to as raw material polymer) is reacted with an ethylenediamine represented by the structural formula (a). This is a method for producing the ion exchange resin of the present invention. _H2N - _CH2 - _CH2 - _NHR4 (a) ( _R4 is the same as above.) 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. The second method is to introduce a cyano group into a three-dimensional crosslinked polymer consisting of polymerized units () and (). Methods for introducing cyano groups include direct introduction using hydrogen cyanide, copper cyanide, etc.
Furthermore, there is a method of reacting a formyl group with hydroxylamine. The composition of each component of the raw material polymer having polymerized units represented by structural formulas (), () and () is as follows:
() is 2 to 50 mol%, () is 0 to 50 mol%,
() is 10 to 98 mol%. R ₁ , R ₂ , R ₃ and
R ₄ is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and in preferred embodiments, R ₁ is hydrogen, a methyl group, etc., and R ₂ and R ₃ are hydrogen, a methyl group,
Examples include ethyl group, and R ₄ is preferably hydrogen, methyl group, ethyl group, benzyl group, or the like. Next, a method for reacting raw material polymer and ethylenediamines will be described. The ethylenediamines in the present invention are represented by the above structural formula (A), and specific examples include ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, and N-benzylethylenediamine. The amount of ethylenediamines is preferably equal to or more than the moles of polymerized units represented by () in the raw material polymer, more preferably 1 to 1.
It is 10 times more molar. The reaction may be carried out in the presence of an inert liquid. The inert liquid refers to a liquid that is inert to the raw material polymer and ethylenediamine. There is no particular limit to the amount of this inert liquid used, but the slurry concentration relative to the raw material polymer is 1
~300g/ is preferred. 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, methanol, ethanol, propanol, butanol, and phenol. alcohols such as diethyl ether, dibutyl ether, diphenyl ether, ethers such as tetrahydrofuran, esters such as methyl formate, ethyl acetate, methyl butyrate, aromatic substituted derivatives such as nitrobenzene and chlorobenzene, acedeamide, dimethyl Amides such as formamide and dimethylacetamide, dimethyl sulfoxide, water, and the like can be used. When producing the ion exchange resin of the present invention, it is preferable to coexist with an auxiliary agent that promotes the reaction. Specific examples include metal chlorides such as copper chloride, iron chloride, and zinc chloride, hydrogen peroxide, and sulfur. The amount of this auxiliary agent is preferably about 1 to 5 moles relative to the polymerized units represented by () in the raw material polymer. The reaction temperature is not particularly limited, but is preferably 20 to 300°C, more preferably 60 to 200°C.
Although there is no particular restriction on the reaction time, a reaction time of 1 hour to 100 hours is usually employed. When attempting to produce the ion exchange resin of the present invention in which R ₄ in the polymerized units represented by () and () is other than hydrogen, first
After producing a copolymer in which R ₄ is hydrogen, a method may be adopted in which a corresponding alkyl group is subsequently introduced. Specifically, this is a method in which the raw material polymer and ethylenediamine are first reacted by the method described above, and then reacted with R ₄ X (X is halogen). The amount of R ₄ There are no particular restrictions on the temperature and time of the reaction, but a temperature of 20 to 100°C and about 1 to 50 hours is usually employed. The reaction may be carried out in the presence of an inert liquid. Additionally, in this reaction, it may be advantageous to add a basic substance. Basic substances include alkali metal salts such as potassium hydroxide, sodium hydroxide, and sodium carbonate, and alkali metal alcoholates such as sodium ethylate. Next, specific embodiments of the present invention will be shown. First, the raw material polymer, ethylenediamines, and if necessary an inert liquid and a reaction accelerating agent are mixed, the reaction is carried out at a predetermined temperature for a predetermined time, and the polymer is recovered by filtration to obtain the desired product. can. 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 imidazole ring structure, it has anion exchange ability due to its basicity, and is useful as an anion exchange resin that is stable due to the chemical and thermal stability of the imidazole ring. Examples are shown below. By copolymerizing cyanostyrenes, divinylbenzenes, and styrenes, Table 1 No. 1 to No.
The raw material polymer shown in 7 was synthesized.

【table】

[Table] Example 1 9.68gr. of raw material polymer of No. 1 in Table 1, 11.97gr. of ethylenediamine, 100ml of diphenyl ether
and 2.5 g of sulfur powder were thoroughly stirred and mixed, and reacted at 150°C for 20 hours. The reaction product was thoroughly washed successively with carbon disulfide, acetone and water to obtain a product. The yield was 11.32gr. The results of elemental analysis and measurement of exchange capacity are shown below. C; 83.49 H; 6.65 N; 9.86 (%) Exchange capacity; 3.12 meq/g In addition, the main peaks (cm ^-1 ) of the infrared spectrum are as follows. 3000, 1610, 1585, 1490, 1450, 1290, 1110,
700 and others 1000cm ^-1 which is one of the characteristic absorption of imidazoline
No absorption of nitrile or nitrile was observed. This result (), (), (), () and ()
The mole percentage in the polymer is 17.0%, respectively.
It was found to be 33.2%, 49.8%, 0% and 0%. Example 2 10.35 gr. of the raw material polymer No. 2 in Table 1, 20.43 gr. of ethylene diamine, 3.3 gr. of sulfur powder, and 150 ml of diphenyl ether were mixed and reacted at 200° C. for 20 hours. The same treatment as in Example 1 yielded 13.14 gr. of product. The exchange capacity of this product was 4.84 meq/g, and the results of elemental analysis are as follows. C: 79.36, H: 6.14, N: 14.50 (%) Further, as a result of the infrared spectrum, no absorption of nitrile or imidazoline was observed. From this, the mol% of (), (), (), () and () in the polymer is 15
%, 0%, 85%, 0% and 0%. Example 3 Using the raw material polymer No. 3 in Table 1, a reaction was carried out under the same molar ratio conditions as in Example 2, and as a result, the following products were obtained. Exchange capacity: 1.77meq/g From the results of infrared spectrum and elemental analysis, the mole percentages of (), (), (), () and () in the polymer are 32%, 41.5%, 26.5%, respectively.
It was found that 0% and 0%. Example 4 10.43gr. of raw material polymer No. 4 in Table 1, 34.19gr. N-benzylethylenediamine, 2.91g sulfur powder
r. and 150 ml of dimethylformamide were mixed and refluxed for 40 hours with stirring. The reaction product, carbon disulfide, acetone, and water were thoroughly washed to obtain 16.40 g of product. The exchange capacity of this product was 2.52 meq/g, and the elemental analysis was as follows. C; 85.26, H; 6.97, N; 7.77 (%) From this, (), (),
The mol% of (), () and () is 5% each,
They were 38.1%, 56.9%, 0% and 0%. Example 5 12.25 gr. of the raw material polymer No. 5 in Table 1, 15.12 gr. of N-methylethylenediamine, and 100 ml of diphenyl ether were mixed and reacted at 100°C for 30 hours. The reaction product was thoroughly washed with acetone and water. The product was 13.98 gr. Elemental analysis is as follows. C: 80.08, H: 6.90, N: 13.02 (%) Also, the exchange capacity was 3.80 meq/g. From the absorption intensity of nitrile at 2200 cm ^-1 in the infrared spectrum, the absorption intensity of imidazoline at 1000 cm ^-1 and the results of elemental analysis, it was found that (),
The mole percentages of (), (), () and () were found to be 15%, 0%, 61%, 8% and 16%, respectively. Example 6 10.37gr. of the raw material polymer No. 6 in Table 1, 17.93gr. ethylenediamine, 3.82gr. sulfur powder, and 100ml diphenyl ether were reacted at 180°C for 25 hours. The product was isolated and analyzed in the same manner as in Example 1, and (),
Products were obtained in which the mole percentages of (), (), () and () were 14.4%, 11%, 74.6%, 0% and 0%, respectively. Example 7 9.04gr. of the raw material polymer No. 7 in Table 1, 20.19gr. ethylenediamine, 4.30gr. sulfur powder, and 150ml diphenyl ether were mixed and reacted at 150°C for 8 hours. A product was obtained in the same manner as in Example 1. The exchange capacity was 4.71meq/g. The results of elemental analysis (%) were C: 77.93, H: 6.15, and N: 15.92. The component () was quantified from the absorption of imidazoline in the infrared spectrum. From these results, () in the polymer,
The mole percentages of (), (), () and () were found to be 4%, 0%, 81.0%, 0% and 15.0%, respectively. Example 8 13.14gr. of the product obtained in Example 2 was mixed with 150ml of ethanol and 4.62gr. of sodium ethylate, and while stirring at 60°C, methyl iodide was added.
19.31gr. was added dropwise. The reaction was continued for 4 hours while stirring. The product was thoroughly washed with acetone and water and then dried. Further, this product and 200g of imidazole were mixed and reacted at 200°C for 20 hours. The product was thoroughly washed with acetone and water. Weight increase from raw materials is 0.95gr.
The exchange capacity was 4.53meq/g. As a result, a product in which R ₄ was a methyl group was obtained.

Claims (1)

[Claims] 1 Structural formula (), (), (), () and ()
A three-dimensional crosslinked copolymer consisting of the polymerized units shown in parentheses, 2 to 50 mol% of the polymerized units shown in parentheses, and 0 to 50 mol% of the polymerized units shown in parentheses. An ion exchange resin characterized by containing 0 to 30 mol% of polymerized units represented by 10 to 98 mol% () and 0 to 30 mol% of polymerized units represented by (). [Formula] [Formula] [Formula] [Formula] [Formula] (However, R ₁ , R ₂ and R ₃ are hydrogen or have a carbon number of 1
R ₄ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. The position of the substituent on the benzene skeleton may be any position. ) 2 A three-dimensional crosslinked polymer containing 2 to 50 mol%, 0 to 50 mol%, and 10 to 98 mol% of polymerized units represented by structural formulas (), (), and (), respectively, is reacted with ethylenediamines. A three-dimensional crosslinked copolymer consisting of polymerized units represented by the structural formulas (), (), (), (), and (), characterized in that it contains 2 to 50 mol% of the polymerized units represented by (). 0 to 50 mol% of the polymerized units shown in parentheses (10 to 98 mol% of the polymerized units shown in parentheses) 0 to 30 mol% of the polymerized units shown in parentheses (0 to 30 mol% of the polymerized units shown in parentheses) Method of manufacturing ion exchange resin containing mol%. [Formula] [Formula] [Formula] [Formula] [Formula] (However, R ₁ , R ₂ and R ₃ are hydrogen or have a carbon number of 1
R ₄ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. The position of the substituent on the benzene skeleton may be any position. )