JPS6088041A - Chelating resin - Google Patents

Abstract

PURPOSE:A chelating resin excellent in heavy metal scavengeability and high in adsorption rate, prepared by incorporating an amidoxime group-containing fine- particulate polymer in a hydrophilic and water-insoluble organic polymer gel. CONSTITUTION:A chelating resin is formed by dispersing and incorporating an amidoxime group-containing fine-particulate polymer (e.g., Diaion CR50, a product of Mitsubishi Chemical Products Industry Co., Ltd.) ground to a particle diameter <= about 50mu) in a hydrophilic and water-insoluble organic polymer gel (dialdehyde-crosslinked polyvinyl alcohol). The mixing ratio of the fine-particulate polymer to the organic polymer gel is preferably within the range of 1:10-10:1 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION The non-promoting invention relates to a chelate resin with a 7' absorption reaction rate. For more information, please visit /topromotion.

- It contains an amidoxime group as the 11th group for the capture of mouse metals, and the adsorption speed is as fast as 1 minute.

R, 'M:J Fat can selectively adsorb specific metals for removal, separation, etc. due to the chelate-forming ability of a certain cylindrical group chemically bonded in the resin. It is used. A polymer having an amidoxime group as a functional group is, for example, r'PREPARAT-'IVE METaoD.
sOF POLYMERCHEMISTRY, W, R,
5orsonson T, W, Campbell co-author;
INTER5crENcE Publishing NEWYORK / 7
It is known that heavy metal ions present in polyacrylonitrile (obtained by reacting with hydroxylamine) can be selectively adsorbed and captured as described in ``Page 1''.

However, the chelate value of the amidoxime group gM is 71.
In this case, the reaction rate of chelate formation between the crosslinking group fixed in the resin and the heavy metal ion is slow, or the diffusion of the vital metal in the resin particles is slow, so that In short-term contact at , the utilization of exchange groups in the resin is generally low.

The present inventors have made extensive efforts to improve the reaction rate of heavy metal capture by impairing the utilization rate of exchange groups in chelate resins, and as a result, we have succeeded in dispersing and incorporating fine-grained chelate resins into a disintegrating polymer gel for water cultivation. The reaction rate of heavy metal capture was improved by 7'
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According to the present invention, this object is easily achieved by incorporating a finely divided polymer containing amidoxime groups into a hydrophilic and water-insoluble organic polymer gel.

The present invention will be explained in detail below.

Polymers containing amidoxime groups used in the present invention are prepared by reacting polymers containing nitrile groups with hydroxylamine. As polymers containing nitrile groups, for example, nitrile = 'k monomers. A homopolymer of monomers having a nitrile group, a copolymer of monomers having a nitrile group, or a copolymer of a monomer having a nitrile group and another monomer copolymerizable with the nitrile group may be used.

Examples of monomers having a nitrile group include acrylonitrile, methacrylonitrile, chloracrylonitrile-vinylidene cyanide%] α-substituted acrylonitrile, crotonide IJ/l/, cocyanoethyl acrylate, cocyanoethyl methacrylate, etc. These may be used alone or in combination of two or more. Usually acrylonitrile or methacrylonitrile is used.

Other monomers that can be copolymerized include the above-mentioned nitrile
All aliphatic and aromatic compounds that can be copolymerized with the monomers having ljJ may be used, such as ethylene, propylene, butylene, acrylic acid, methacrylic acid, and their esters. Field, vinyl halides, vinyl esters,
Vinyl alcohol-vinyl ether, aliphatic monovinyl compounds such as hynylidene halides, styrene, aromatic monovinyl compounds such as vinyltoluene, divinylbenzene,
Polyvinyl compounds such as diallyl phthalate, diacrylic acid or dimethacrylate, ethylene glycol or glycerin dimethacrylate are used.

Examples of polymers having a nitrile group include those mentioned above, such as cyanether (B cellulose, cyanethylated polyvinyl alcohol, etc.); polyvinyl alcohol hv< even if it is treated with iminodiacetonitrile to form a nitrile group; furthermore, aromatic or Oxybenzonitrile etc.
A condensate as a component may also be used.

Inverse ratio of nitrile polymer and hydroxylamine: v1. It is carried out according to any method, preferably a methanol or ethanol bath solution of hydroxylamine,
Alternatively, use a methanol or ethanol bath solution of hydroxylamine sulfate or hydrochloride and add 65% of alkali such as sodium hydroxide or potassium hydroxide AQ'j+ to neutralize all or part of the salt. -9 to 100°C), and this reaction mainly converts the nitrile group into an amidoxime group rL.

The fine particulate polymer containing an amidoxime group used in the present invention has a particle size of 50 μm or less, preferably 10 μm or less.

Hydrophilic and water-insoluble polymer gels include linear polymers having anionic functional groups, such as polystyrene sulfonic acid, polyacrylates, etc., and star-shaped polymers having cationic functional groups 2, such as polyvinyl Ion complex consisting of a combination of penzyltrimethylammonium hydroxide, polyethyleneimine, polyethylenepiperazine, etc., polycohydroxyethyl methacrylate, polyethylene glycol mono(meth)
Divinylbenzene, polyethylene glycol di(meth)acrylate, polyglycerin di(
Gels copolymerized with cross-linking monomers such as meth)acrylate, or gels prepared by single use of hydrophilic cross-linking monomers such as polyethylene glycol di(meth)acrylate and polyglycerin di(meth)acrylate, starches, and Starch derivatives, polysaccharides such as cellulose and cellulose derivatives, oligomers such as pullulan, polyvinyl alcohol, etc. are cross-linked with dialdehydes such as glyochinal, malonaldehyde, succinaldehyde, and phthalaldehyde, and are insoluble in water. Used are gels made of polyacrylic acid, polyacrylamide or polyacrylamide dihydrazine, and the like.

The quantitative ratio of the amidoxime group-containing fine particulate polymer used in the chelate side fat of the present invention and the hydrophilic organic polymer gel depends on the properties and characteristics of the hydrophilic 4J war molecular gel.
4, which cannot be uniformly determined and must be optimized), or Jli1' trial weight vertical standard /: 10 to 10
:/-preferably in the range of /:5 to 3:/ 3. A method for dispersing and incorporating an amidoxime group-containing polymer into a hydrophilic organic polymer gel is suitable for use in sushi, water-based polymer gels, etc. Various methods are used depending on the properties of the gel, but usually, a polymer with a normal particle size (several U μm) containing an amidoxime group is pulverized, atomized, and then crushed into a hydrophilic polymer. It can be dispersed and included in the gel. - 10,000, the above-mentioned nitrile group-containing qMj fat matrix of normal particle size is pulverized to obtain a fine-grained matrix polymer, or the monomer having a nitrile group is subjected to known A-end emulsion polymerization or other polymerization method. A method is also used in which finely granular polymers are produced, these polymers are dispersed and included in a hydrophilic polymer gel, and then 2) IJ groups are converted into amidoximes.

For example, when using an ionic complex consisting of a linear polymer having an anionic functional group and a linear polymer having a cationic functional group as a hydrophilic KH machine molecular gel, first the streaked polymer is partially 1-IK which produces a bonded ion complex, and adds and mixes f'LVc, a fine particulate polymer containing an amidoxime group, or a fine particulate matrix polymer containing the above-mentioned nitrile group (hereinafter referred to as the fine particulate polymer δ). A method can be used to promote the formation of an ion complex, to form a water-insoluble gel, and, if necessary, to amidoxime.

In addition, when using a crosslinked polymer of a hydrophilic 1↓ linear polymer such as a polycyclic polymer or polyvinyl alcohol as a hydrophilic polymer gel, the hydrophilic edge polymer is partially crosslinked in advance. After adding fine particulate polymer to this and mixing L1, the fanning reaction is promoted to form a water-insoluble gel.
A method in which a water-insoluble gel is produced by performing seven cross-linking reactions in one step in the presence of a hydrophilic glandular polymer and a finely divided polymer is used. The resulting product, which requires 4L, is subjected to an amide-thousimization reaction.Also, it is used to synthesize two aqueous monomers such as polyacrylamide or polyenalene glycol dimethacrylate gel.
When using the proboscis as a hydrophilic gel, a method is used in which a fine particulate polymer is dispersed in advance in a monomer containing a crosslinking agent monomer, and then a water-insoluble gel is produced by the polymerization method. The refined gel is pulled and subjected to an amidoximation reaction, if necessary.

The chelate resin of the present invention, in which the fine 4i-like polymer having an amidoxime group is dispersed and included in a residual aqueous organic polymer gel, has a high adsorption reaction rate for Kokinu ions, so that it can be used in dilute solutions containing one heavy metal. It is extremely useful for adsorbing and separating heavy metals.

Next, the present invention will be explained in detail with reference to examples, but the invention is not limited to the following examples unless it goes beyond the gist thereof.

Example/ A slurry of uniform fine granular resin of Ichi MM's amidoxime group-containing chelate & (Jlii) was obtained. Applicable to this:
of water was added to obtain a 41I fat suspension with a solid content of 10%.

Then - 100 ml of an aqueous solution of borivinylbenzyltrimethelammonium hydroxide of 0.2 eq/l of n, molecular weight - 10,000, respectively. 2 eq/l of polystyrene sulfone was mixed with water f4/00 me'g and further diluted with methyl alcohol f00 rrdl'f (additionally diluting it to produce a slurry-like polyion complex.

100 rnl of suspension of the above-mentioned amidoxime group-containing fine granular resin in the conoslurry! , and stirred until the slurry became uniform. The obtained 2' slurry liquid was left under heating and reduced pressure to evaporate the soybean component, resulting in a lumpy solution) -', fIj fat 2'1.7 94
Gay()ta.

The above chelate; IMj fat was classified into crushed bodies 2o to SO Metsuyu/1.01 chelate resin jf&? ? It's 6.

Example Copolyvinyl alcohol (manufactured by Nihon Kansan (1 (Ten), Gohsenol NL-θS, degree of saponification 7g 5%) a.

1 was added to an emulsion containing polyacrylonitrile having a particle diameter of less than /μ/g', Q jil-, and the mixture was heated at 15°C for 1 hour.

After cooling to the above slurry liquid, 2S% glutaraldehyde gd
A water-insoluble gel was obtained when a -1 normality salt θrrt was added and a crosslinking reaction was carried out for 6θCλ hours. After crushing and classifying this gel, 3% hydroxylamine was dissolved in methanol M3o.

◇Example 3 Polyacrylamide dog 1 with molecular ia
It was dissolved in 1rt water to obtain a 2%M water bath solution. Add 1 part of hydrazine hydride to this water bath solution, and add 1 part to it at 60°C.
A white opaque slurry was obtained by carrying out the crosslinking reaction for 0 hours. To this slurry liquid, the amide quince-containing imitative granular tree used in Example 1 was added and mixed until a uniform slurry was formed. The resulting slurry wsoc is dried with air for 3 days to form a water-insoluble lumpy resin 3.
I got J.

After crushing the above lump resin, it was classified into 20-30 meshes and 53
! A chelate resin of / was obtained.

LOL Example Example/, Kiri-1, Resinbo M and Niichi 1 obtained in 2.3
Temporary amidoxime-type fat Diaion cR5゜ (Mitsubishi Kasei L-strip (blank)) in a humidity 4 threshold condition 3rnl (r konalyo': +E and p1iz3,005mol/1m M4'
2i+'1lIj bathing (-"1 wave-1#'!: T.
1ml of anti-sodium solution) / 00; Add 11 pieces to the Erlenmeyer flask containing ne・Wj Jk above
In a warm Erlenmeyer flask containing water at s°C, shake width x o o
n No Furi S? Shake A4H at 741 m JI*
The absorption of D%il ions was measured using the M'g E D T A method over time to investigate the increase in the rate of layer formation on the functional groups in the resin. The results are shown in Figure 1. Shown below.

Fig. 1 is a graph showing the change over time in the stratification rate of another ion due to the chelate Tochi IIσ of the present invention.

The vertical axis represents the layering rate of copper ions on the chelate resin (j4: the amount of absorbed M divided by the average of the adsorption amounts), and the -Ajq axis represents the adsorption time.

In the figure, solid lines (a) to (c) l'i, respectively thick hl
! iExample 1, Su.

30 The broken line (d) shows the chelate value collapse of the present invention. This is the result using io.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent Patent Attorney Submissive Use - (7 others)

Claims (1)

[Claims] (1) A fine particulate polymer containing an amidoxime group,
A chelate tree characterized in that a fraction thereof is incorporated into a water-cultivable and water-insoluble organic molecular gel. (2) The chelate resin according to paragraph a4 of the patent claim, characterized in that W containing an amidoxime group is used as a particulate polymer with a particle size of 50 μm or less. (3) The ratio by weight of the fine particulate polymer and the hydrophilic water-insoluble organic polymer gel is /: 10 × 1 O: 1
The chelate 4d fat according to claim 1, wherein the chelate 4d fat is within the range of . (4) A polyion complex consisting of a linear polymer having an anionic functional group and a linear polymer having a cationic functional group is used as the polymer gel. The chelate resin described in items nf)'- of Items to Box 3. (b) The monomer polymer gel is characterized by using a dialdehyde crosslinker of polyvinyl alcohol.
! The chelate resin according to any one of fri'F discovery ranges 1 to 3. (6) The polymer gel is characterized in that the 4'-acrylic acid-hydracic acid chain is present in the body of the 4'-
F. The chelate resin according to any one of Item 7, No. 3 of Claim jjg Surrounding Board.