JPS59155404A - Polymer having basic functional group and its production - Google Patents

Abstract

PURPOSE:An anion exchange resin being excellent in heat resistance and chemical resistance and showing no lowering in exchange capacity after a long-time use, comprising a three-demensional crosslinked copolymer consisting of specified polymer units. CONSTITUTION:A three-dimensional crosslinked copolymer consisting of the polymer units of formulas I , II, III, IV, and V (wherein R1, R2, R3, and R4 are each H or a 1-4C hydrocarbon, X is a halogen, and the position of the substituent, in each formula, to the benzene sleletone or the pyridine skelton is arbitrary), wherein the polymer units of formulas I , II, III, IV, and V are present in amounts of 2-50mol%, 0-50mol%, 10-98mol%, 0-30mol%, and 0-30mol%, respectively. This copolymer can be prepared by reacting an alpha-picolinic acid of formula VI with a three-dimensional crosslinked copolymer having polymer units of formulas I and IV and, optionally, a polymer unit of formula II and, if necessary, subjecting the product to alkali treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel basic three-dimensional crosslinked copolymer and a method for producing the same.

Currently, anion exchange resins with a chloromethylstyrene skeleton aminated with dimethylamine, trimethylamine, etc. are used, but these resins have poor heat resistance and chemical resistance, and as they are used, they deteriorate. A decrease in exchange capacity will occur.

The present inventors have conducted intensive studies to find an anion exchange malleable resin that can replace this, and as a result, have come up with the present invention.

That is, the copolymer of the present invention has the following structural formulas (1) and (II).
, (1), (Ill,
(1), (IV) and (11(n) (1)
(IV) (V) (2 to 30 molar units, θ to jθ molar ratio, 70 to 70 molar units, respectively)
It is a copolymer containing 9♂ mol, θ to 3θ mol, and θ to 30 mol.

(However, R, , R, , R3, R4 represent hydrogen or a hydrocarbon group of carbon number/group, and X represents a halogen. Also, the position of the substituent on the benzene skeleton and the pyridine skeleton may be any position.) The above structure Formula (1) corresponds to divinylpenyne and its derivatives, and preferred examples include those in which R1 is hydrogen or a methyl group. (11 is a mole ratio of 0 to 5'θ, preferably 2 to 3 mols).

Structural formula (n) is a polymerized unit corresponding to styrene and its derivatives. A plurality of units of formula (If) with different R2 may be contained in the polymer. (It) is θ~
jθ morch. Structural formula (1) is a polymerized unit having a heterocycle containing a nitrogen atom, and exhibits basicity as an ion exchange resin. (1) is a molar ratio of /θ to ri♂, preferably a molar ratio of λθ to 7θ. Structural formula (rvl has a halogenoacetyl group, and X represents fluorine, chlorine, bromine, or iodine.

surface and (■ is 2 to 30 molar ratio, preferably θ to
/j I'm in charge of the moles. Structural formulas (1), (lv), (V1 odor) can use a plurality of units with different R3. In addition, the structural formula (group, (V)) can also contain a plurality of different units with R4. Structural formula ( The polymerized units represented by It), Double) and (V) may not be included in the polymer.

Furthermore, the present invention provides a three-dimensional crosslinked copolymer (hereinafter referred to as raw material polymer) containing polymerized units represented by structural formulas (1) and (IV) and, if necessary, structural formula (n), and a basic tertiary This invention relates to a method for producing an original crosslinked copolymer.

(R4 is the same as above. Any position of R4 may be used.) The raw material polymer can be synthesized by several methods. First of all, it can be obtained by copolymerizing (1) and (IV) and, if necessary, a heptamer corresponding to the structural formula of (n). Structural formula (n) and (
There is no problem in using a plurality of monomers having different R2 and R3 as the monomer corresponding to IV).

For polymerization, ordinary suspension polymerization or emulsion polymerization techniques can be employed. Second, Y -C0-CH2-
It can be obtained by subjecting a halogenoacetyl halide represented by X (Y represents halogen) to a Friedel-Crafts reaction. Furthermore, a three-dimensional crosslinked polymer consisting of polymerized units (11 and (n)) is subjected to a Friedel-Crafts reaction with acetyl halide or acetic anhydride represented by YCOCHs, and then methylated with X in the presence of a catalyst if necessary. It can also be obtained by directly converting groups into halides.The composition of each component of the raw material polymer having polymerized units represented by structural formulas (1), (It), and (lead) is as follows:
50 moles 91! , , (Ill is 0 to 10 mol%, (
The concavity is /θ~9♂ molar ratio. R1, R2, R3 and R
4 is hydrogen or a hydrocarbon group with a carbon number of 1 to 3,
In a preferred embodiment, R1 is hydrogen, methyl group, etc., R2 and R3 are hydrogen, methyl group, ethyl group, etc., and R4 is preferably hydrogen, methyl group, ethyl group, etc. Moreover, it is preferable that X is Ct or Br.

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 the polymerized unit represented by the structural formula (m) in the raw material polymer, and is preferably equal to or more than two times the number of moles.

When carrying out this reaction, the reaction may be carried out in the presence or 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 /~3
0θ? /1 is preferred. Specific examples of inert liquids include:
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, alcohols such as methanol, ethanol, propatool, phthanol, and phenol, diethyl ether , dibutyl ether,
Ethers such as 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. Examples of basic substances include alkali metal salts such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and alkali metal alcoholades such as sodium ethylate and sodium butylade.

The reaction temperature is not particularly limited, but is preferably 2θ to 200°C, more preferably 20 to 750°C. There is no particular restriction on the reaction time, but it is usually 0, . 31 hours to 7
A reaction time of 0.00 hours is employed.

Next, the method of alkali treatment will be described. In the present invention, the alkali treatment refers to reacting a reaction product of α,-picolines and a raw material polymer with a basic water bath liquid. 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. It is something. For this water removal, it is possible to add a small amount of water such as alcohol and a small amount of organic components. The degree a of these basic substances is usually θ, θ/
It is used at a concentration of ~0. The amount of the basic aqueous solution is 7 to 30% as the slurry concentration to the raw material polymer.
0 f/ is the degree. Although there is no particular restriction on the reaction time, about 7 to jθ hours are used. There is no particular restriction on the reaction temperature, but a temperature of about λθ to /koθ°C is used.

When producing the polymer of the present invention, when performing alkali treatment after the reaction with α-picolines, add the salt basic substance directly to the reaction solution with α-picophosphorus. It is also possible to perform so-called "one-pot synthesis" by reacting.

Next, specific embodiments of the present invention will be shown.

First, the desired product can be obtained by treating the raw material polymer with α-picolines and, if necessary, with alkali.

The novel copolymer of the present invention may contain other polymer units as long as the properties of the copolymer are not changed.

The novel copolymers of the present invention can be used as ion exchange resins.

Examples are listed below.

A/~A shown in Table 1 by ordinary suspension polymerization from haloacetylstyrenes, styrenes and divinylbenzenes.
7 raw material polymers were synthesized.

Table 7 1) DVB Nidivinylbenzene 2) St: Styrene 3'l BAS Near" lomoacetylsterene 4)
1i8: Ethyl styrene 5) CAS: Chloroacetylstyrene 6) DV
T Nidivinyltoluene 7) VT: Vinyltoluene Example/First surface/Raw material polymer/3. jθ4t gr and α
- Pifrin7. 2 gt (79.7 mmol) of water was mixed with stone-aged water/jθ-, and the mixture was reacted at 0° C. for 3 hours with stirring in a nitrogen atmosphere. Sodium hydrogen carbonate, 7θgr-(79.7 mol) was added to the reaction mixture, and the mixture was reacted at 1θθ°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 /¥, 3/2gx. The main peaks of the infrared absorption spectrum were as follows.

29/θ, /Otsu70, /Otsuθθ, /G2θ, /Guguj,
/3 Otsu 0. /, 29θ, //7ta, //θθ, ♂30.
The results of elemental analysis at 7θθ, 7θθ (cm-”) were as follows.

C: 7♂, /31-1: Otsu, θ Yu N;
3. θ0CL: 2. / 47 Br;
/ 0.6g (%) When the ion exchange capacity was measured, it was found to be of the HCt type (including 0 strong base portions). From these results, it is clear that (
The molar percentages of the components of 11, (II), (group), (IV), and (Vl) are /7.θ, 33.2, and 25.
It was found that 9%, //3%, /λ, were small.

Examples λ to j Table 2 shows the results of reactions carried out in the same manner as in Example/.

(Margin below)

Claims (1)

[Claims] (1) The following structural formulas (I), (II), (III),
A three-dimensional crosslinked copolymer composed of polymer units represented by (IV) and (V), comprising (I), (II), and (I).
II), (IV) and (V) each have 2 to 2 polymerized units.
50 moles, 0 to 50 moles, /θ~9 moles, θ~
A copolymer characterized by containing a 3θ molar ratio and a θ to 3θ molar ratio (where R1=R2, R3, and R4 represent hydrogen or a hydrocarbon group having 7 to 7 carbon atoms, and X represents a halogen. (The position of the substituent on the pyridine skeleton and the pyridine skeleton may be any position.) (2) Each of R2 and R3 in the copolymer according to claim 1, wherein R is hydrogen or a methyl group. copolymer (4) according to claim 7 or 2, wherein X is hydrogen, methyl group or ethyl group; Any of item 3 (copolymer (5) according to one description) The polymerized units represented by the following structural formulas (1), (ill and (1)) are respectively λ~taθ molar ratio, θ~jθ
The following structural formulas (1), (11), (I), (relation and (V)
A three-dimensional crosslinked copolymer composed of polymerized units represented by (1), (...), (1), (IV) and (V
A method for producing a copolymer containing 2 to jθ mol units, θ to j 0 mol%, 10 to 98 mol%, θ to 3θ mol units, and θ to 30 mol units, respectively (with the exception that R1, R2, R3
, R4 is hydrogen or a hydrocarbon group with a carbon number/from
represents halogen. Further, the positions of the substituents on the benzene skeleton and the pyridine skeleton may be any position. )