JPS60135420A - Production of chelating resin - Google Patents

Abstract

PURPOSE:To obtain an easily regeneratable chelating resin having an exchange capacity and an excellent effect of scavenging metal ions, boron, and arsenic, by polycondensing a specified aromatic amine with a polyhydroxyalkylaldehyde in two stages. CONSTITUTION:An aromatic amine of formula I or II (wherein R is H or a 1- 4C alkyl) is partially condensed with a polyhydroxyalkylaldehyde of formula III(wherein n is 2-6) in a molar ratio of 3:1-1:2 and 30-70 deg.C for 3-30hr in the presence of an acid catalyst. While the reaction product mixture still retains flowability, an additional aldehyde is dissolved in the mixture in such an amount that the molar ratio of the total amount of the aldehyde to the amine is 1:1-5. The resulting mixture is dispersed in an organic solvent such as o-dichlorobenzene, and subjected to pearl polymerization at 70-120 deg.C for 3-30hr in the presence of an acid catalyst such as boric acid until the reaction is completed.

Description

[Detailed Description of the Invention] The present invention relates to a method for producing a chelate resin,
In particular, the present invention relates to an improved method for producing a new chelate resin that increases its exchange capacity.

Chelate resins selectively adsorb specific metals due to the chelate-forming ability of certain functional groups chemically bonded in the resin, and are used in a wide range of applications such as removal, separation, and recovery. .

The present inventors previously proposed a new chelate resin consisting of a crosslinking condensation product of an aromatic amine and a polyhydroquine alkyl aldehyde represented by the following general formula (1) (Japanese Patent Application Sho sg-/lI !i'lOk issue), and as a result of subsequent studies, it was discovered that the exchange capacity could be improved by carrying out the condensation reaction in two stages, leading to the completion of the present invention.

H-C! (-0HOH+nH...9(I)1 (In the formula, n represents an integer from λ to B.) Hereinafter, the present invention will be described in detail.

The chelate resin of the present invention comprises an aromatic amine and the general formula (
Examples of the aromatic amine which is a cross-linked condensation product with polyno-idroxyalkyl ryotehyde shown in 1) and used as a raw material include aniline, 0-toluidine, m-)Jreizine, p-toluidine, . 7. , S
-- Monoaminobenzenes optionally substituted with alkyl groups such as dimethylanilino, l-amine naphthalene,
No aminonaphthalene. Aromatic monoamines such as fused polycyclic aromatic monoamines such as l-aminoanthracene and co-aminoanthracene; or O-phenylenediamine, m-phenylenediamine, p-phenylenediamine, y, y
-7 aminoto JIene, 3. S-diaminotoluene, 2
．． Diaminobenzenes optionally substituted with alkyl groups such as 3-sia ζ metoluene % /,! 72 g of i-diaminonaphthalene, 3-diaminonaphthalene, /, S-diaminonaphthalene, λ,
Aromatic diamino such as combined polycyclic aromatic diamines such as 3-diaminoanthracene and 71g-diaminoanthracene are used, and preferably aniline, 0-phenylenediamine, m-phenylenediamine, and p-phenylenediamine are used.

Examples of the polyhydroxyalkyl aldehyde of the general formula (1) used in the reaction include glyceraldehyde, erythrose, arabinose, xylose, monoquinose, glucose, mannose, galacto-
etc. are used.

At that time, the reaction is carried out in two steps / 11! It is necessary to do i'.

That is, an acid serving as a polymerization catalyst is added to an aqueous solution of an aromatic amine and a partial amount of polyhydroxyalkyl aldehyde represented by the general formula (1), and the pH of the reaction solution is made acidic, followed by a polycondensation reaction. This first stage condensation reaction is stopped while the generated polycondensation reaction liquid maintains fluidity,
Further, an additional amount of polyhydroquine alkyl aldehyde represented by the general formula (1) is added to complete the second stage polycondensation reaction. In the present invention, a state in which fluidity is maintained means a state in which the reaction liquid is in a solution state and no gel-like substance is generated. If the fluidity of the first stage polycondensation reaction solution is not maintained, when an additional amount of polyhydroquine alkyl aldehyde is added and reacted, the second stage reaction will not be carried out homogeneously, which is not preferable.

The reaction conditions are based on the aromatic amine used and the general formula (1
) It depends on the type of borino-idroquine alkyl ryoltehyde and the type of acid catalyst used, and it cannot be uniformly determined, but the presence of an acid is usually used as the first reaction condition. Below, under conditions where the aqueous solution is acidic, the aromatic amine used in this reaction and the general formula (1)
Considering the total amount of polyhydroxyalkyl aldehyde used, the charge ratio of aromatic amine and polyhydroxyalkyl aldehyde, based on the number of moles, is from 3:l to l:
, 2, preferably in the range 2:1 to 0:1.

In this case, the reaction temperature is 30° C. to 70° C., and the reaction time is 3 hours to 30 hours.

In addition, in the second stage polycondensation reaction, the aromatic amine and an additional amount of polyhydroquine alkyl aldehyde are reacted, but in that case, the aromatic amine and the general formula (1)
The ratio of u to polyhydroquine alkyl aldehyde,
The ratio of the total amount used in this reaction, including the raw materials used in the i-s reaction, is preferably from 1:1 to 1:3-1, preferably from /:/ to /:, ? selected within the range. The condensation reaction is carried out at a reaction temperature of 70''C to isooC until the reaction is completed.

Examples of condensation catalysts used in this reaction include mineral acids such as boric acid, hydrochloric acid, and sulfuric acid, and organic acids such as formic acid, phosphoric acid, trichloroacetic acid, dichloroacetic acid, and monochloroacetic acid.

In particular, it is preferable to use boric acid as the acid catalyst in the two-stage merging reaction of the method of the present invention, since it is possible to further improve the exchange capacity of the chelate resin.

The chelate resin obtained by the method of the present invention may be in any form such as beads, powder, plate, film, or thread, but bead-like resins are generally used.

When the purpose is to produce a bead-shaped chelate resin, an additional amount of the general formula After adding and dissolving the polyhydroxyalkyl aldehyde represented by (1), dispersing it in an organic medium,
A method is used in which the second stage reaction is completed by a conventional bar polycondensation reaction method. In this case, any medium can be used as long as it is inert to the polycondensation reaction, but examples include carbon tetrachloride, chloroborum, trichlorethylene, perchlorethylene, and dichloroethylene. , dichloroethane, /, halogenated aliphatic hydrocarbons such as λ-dichloropropane, chlorobenzene, 0-dichlorobenzene, p −'; halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzene, be/ Zen, toluene, p-xylene, m-
Xylene nanoaromatic hydrocarbons, decane, dodecane,
Aliphatic hydrocarbons such as undecane, cyclohexane,
Examples include alicyclic hydrocarbons such as cyclopropane, and LM alcohols such as cyclohexanol and cyclopentanol.

The chelate resin d obtained by the method of the present invention has a scavenging effect on metal ions, boron, and arsenic, but has an excellent scavenging effect on boric acid of 7+, as is clear from the following examples. It is extremely useful for selectively adsorbing and removing boric acid in a solution.

Next, the present invention will be explained in more detail with reference to Examples and Test Examples, but the present invention is not limited to the Examples below unless it exceeds the gist thereof.

Example 1 After adding m-phenylenediamine 10fjK30 weight ratio D-glucose aqueous solution y o &, 97 esters of sulfuric acid I was gradually added so as not to generate heat to obtain a homogeneous aqueous solution.

For the first stage polycondensation reaction, the above aqueous solution is heated at a reaction temperature of k 0
The reaction was carried out under stirring for a period of time at C to obtain a water-soluble polycondensate.

- While the polycondensate produced in the above reaction maintains fluidity, add an additional amount of SO Kurumadoshi's D-glucose water bath solution lIo.
g to form a uniform aqueous solution/ζ. As the second stage polycondensation reaction, this aqueous solution is dispersed in 0--7 chlorobenzene at a reaction temperature of q! ``Nide/!Pearl polycondensation was performed for i hours.

The resulting resin was filtered, washed several times with acetone, treated with a normal aqueous solution of caustic soda, and further washed with water until the phenolphthalein became colorless. The volume of the obtained fat in a wet state is 1 d q
b me, and its water-containing layer is 3.2. g '16. Elemental analysis value of dry resin (0:2.g0%, N'
: b, y a%) m-phenylenediamine and D
- The molar ratio of glucose was 1-i/:co, 37.

EXAMPLE A chelate resin was manufactured in the same manner as in Example 1 except that 70 hours was used as the first stage polycondensation reaction time.

The volume of the obtained resin in a wet state is q/ml,
Its water content was 5/2%. Elemental analysis values of dry resin (0: j/, ff&%, N: sq%)! 7m
-phephenylenediamine-glucose molar ratio was 27.

Example 3 A chelate resin was produced in the same manner as in Example 1, except that 20 hours was used as the convenient reaction time for the first stage.

The volume of the obtained resin in a wet state is gqml, its water-containing layer is qq, g%, and the elemental analysis value of the dry resin (
0:! ; 2. 2θ relation, N: Otsu, guar), the molar ratio of m-phenylenediamine and D-glucose /:, 2. J
It was J.

Comparative example / m-phenylenediamine 10jJ so heavy % (7)D
- After adding the aqueous ggog of curcose, 97% Wt acid lI& was gradually added so as not to generate heat to obtain a homogeneous aqueous solution. This water bath liquid was dispersed in 0 to dichlorobenzene, and bar polycondensation was performed at a reaction temperature of 95° C. for 1S time. The obtained resin was filtered for 1', washed several times with acetone, treated with a co-normal caustic soda water bath, and further washed thoroughly with water until phenolphthalein became colorless. The volume of the obtained resin in the wet state is qom
The water-containing layer was SO.O.%. Elemental analysis values of dry resin (C: hs, oo4, N: 6.lI-,
, 7%), the molar ratio of m-phenylenediamine to D-glucose was 1-J/:λ, and it was guar.

Test Example: Using the wet chelate resins obtained in Examples No., No. 3, and Comparative Example No. 3, 70 ml of each of these resins was subjected to normality Q,
/ , boric acid aqueous solution 10θ adjusted to pH'/ 0.3
mlVC was immersed at room temperature, and the concentration of boric acid remaining in the solution to be treated after being left for 3 days was adjusted to pHVs, and then titrated using mannitol to determine the amount of adsorption to the resin.

The results are shown in Table 7.

Example 1 10 J/m of aniline and Jθ weight m. After adding the shadow D-glucose aqueous solution G0I, 97% sulfuric acid qy was gradually added so as not to generate heat to obtain a uniform aqueous solution.

For the first stage polycondensation reaction, the above aqueous solution is heated at a reaction temperature of Sθ℃.
The mixture was reacted with stirring for 10 hours to obtain a water-soluble military condensate.

While the polycondensate produced in the above reaction maintains fluidity, add 1 of the D-glucose aqueous solution O1 by weight of SO.
was added to make a uniform aqueous solution.

As the second step condensation reaction, this aqueous solution was dispersed in a mixed solution of real benzene and carbon tetrachloride (weight ratio 3:3), and bar polycondensation was performed at a reaction temperature of 30° C. for 20 hours.

The obtained resin was filtered through f'5, washed several times with acetone, treated with a co-normal caseinoda aqueous solution, and further washed thoroughly with water until phenolphthalein became colorless.

The volume of the obtained resin in a wet state is /Jθml,
The water-containing coal was Gug, Q-jin. Elemental analysis value of dry resin <c'', s, 2.oo%, N:, 2.7.ycI)
), the molar ratio of aniline and D-glucose is / : ,
It was 2.7/.

Comparative Example After adding D-glucose aqueous solution ioog of coaniline logKs07jEbt%, 97% sulfuric acid qy was gradually added so as not to generate heat to obtain a homogeneous aqueous solution. This water bath solution was mixed with chlorobenzene and carbon tetrachloride (weight ratio 3:/
) and subjected to bar pongeeing at a reaction temperature of gθ°C for 10 hours.

The resulting resin was filtered, washed several times with acetone, and then treated with a normal Caseinoda water bath.

The volume of the obtained resin in the wet state is i, 2 g m1
! And the hydrous coal is tig,! i%. Elemental analysis value of dry resin (0:5O, 2/%, 14:Co, 7
From Section 3), the molar ratio of aniline and D-glucose is /:
x,! ;g.

Using the wet chelate resins obtained in Test Example 1, Example 3, and Comparative Example, the boric acid adsorption amount of each resin was determined in the same manner as in Test Example.

The results are shown in Table 1.

pH10,! ;

Claims (1)

[Scope of Claims] A method for producing a chelate resin, which comprises carrying out a crosslinking condensation polymerization reaction in the presence of a medium to preliminarily cause a condensation reaction with a chelate, and then adding a human under reaction conditions to carry out the condensation reaction. H-0+0HOH-)nH pa--... (1) 1 degree of 〇 aldehyde is subjected to a condensation reaction in advance so that the total amount of polyblown hydroxyalkyl aldehyde used in the main reaction is /near~/:S The special alkyl aldehyde is characterized in that it is selected so that it is in the range of (mol) from 30 to 70.
The manufacturing capacity doroquin according to claim 1 or claim 1, characterized in that the condensation reaction is carried out at a temperature of ゛°C and a temperature of 3~/Uθ°C for a time sufficient to complete the reaction. Claims 1 to 5 are characterized in that a spherical chelate resin is obtained by adding and dissolving the alkyl aldehyde, dispersing it in an organic solvent, and performing bar polycondensation for 3 to 30 hours. The manufacturing method according to any one of Item 3. (5) The manufacturing method according to any one of claims 1 to 9, wherein the aromatic amine is an aromatic monoamine represented by the following general formula (If). (In the formula, R represents hydrogen or an alkyl group with a carbon number of up to 1, and may be the same or different.) (6) The aromatic amine is an aromatic diamine represented by the following general formula (Ill). The manufacturing method according to any one of claims 7 to 3, characterized in that: (In the formula, R represents hydrogen or an alkyl group with a carbon number of /~g.)