JPS60135404A - Adsorptive polymer - Google Patents

Abstract

PURPOSE:An adsorptive polymer having a catechol skeleton and excellent chemical resistance, thermal resistance and selective adsorptivity for Group 3B elements, obtained by a reaction between a catechol and a styrene polymer, an addition polycondensation reaction between a catechol and formalin or a like reaction. CONSTITUTION:This adsorptive polymer has 0.5mmol/g or above of a catechol skeleton of the formula I . Examples of the polymer include one having polymer units of formula II and one having polymer units of formula III. The polymer having polymer units of formula II can be obtained by reacting a catechol with, for example, a polymer of a styrene derivative containing an aldehyde or hydroxyl group (e.g., formylstyrene). The polymer having polymer units of formula IIIcan be obtained by addition-polycondensing formalin with a catechol.

Description

[Detailed description of the invention] The present invention relates to novel adsorbent polymers.

Polymers having adsorption properties, such as ion exchange resins and chelate resins, are widely used in various separation industries, waste water treatment, and the like. However, the conventionally known compounds do not necessarily have poor chemical stability, and may have poor long-term stability depending on pH changes, or poor thermal stability.

Furthermore, the selectivity for various adsorbed substances was not sufficient.

From this point of view, the present inventors have conducted extensive studies and found that ν has a modern chemical structure, excellent chemical and thermal stability, and excellent selectivity for group 3B elements as adsorbed substances. They discovered an adsorbent polymer and completed the present invention.

The novel adsorptive polymer in the present invention is a polymer having a catechol skeleton. The catechol skeleton is represented by the following structural formula (■), and the four (7) hydrogen atoms attached to the so-called benzene skeleton of catechol can be substituted with any substituent, but one In order to form a polymer, the above must form the main chain of the polymer or be bonded to the main chain.

Although there are no particular limitations on the polymer and the bonding state, some preferred specific examples include those having polymerized units represented by the following formula (B).

4-('l(,-CH-)- R.

(1) R,, R11 are each hydrogen or carbon number 1 to 8
is a hydrocarbon group, R1 is hydrogen or a hydroxyl group.

Represents a hydrocarbon group having 1 to 8 carbon atoms or a catechol group.

Such a polymer can be produced by reacting a polymer of a styrene derivative having an aldehyde group or a hydroxyl group with catechols.

The second type is one having a polymerized unit represented by the following formula.

Such a polymer can be produced by an addition condensation reaction using catechols and formalin.

Preferably, the polymer of the present invention is three-dimensionally crosslinked.

In the case of having a polymer unit represented by 0), three-dimensional crosslinking can be achieved by including a polymer unit corresponding to a difunctional or polyfunctional monomer.

Examples of these polymerized units are divinylquinzene, divinyltoluene, divinylxylene, divinylethylbenzene, trihinylbenzene, divinyldiphenyl, divinyldiphenylmethane, divinyldibenzyl,
Divinyl phenyl ether, divinyl diphenyl sulfide, divinyl diphenylamine, divinyl sulfone,
Divinyl ketone, divinylpyridine, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl oxalate, diallyl adipate, diallyl henananosinate, diallylamine, triallylamine, N,N'-ethylene diacrylamide ,N.

N'-methylene diacrylamide, N,N'-methylene dimethacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate), 1,3-butylene glycol diacrylate, triallyl isocyanurate, triallyl citrate, trinori 1. It is a polymerized unit corresponding to triallyl tooate, triallyl cyanurate, etc.

Even if multiple types of these crosslinking units are included, no more than 11 of them can be used. These crosslinked polymer units preferably have a weight ratio of 1 to 50, more preferably a weight ratio of 1 to 30. Furthermore, there is no problem even if other polymer units are included as a third component in addition to these.

The third component of cholera is styrene, vinyltoluene,
Ethylstyrene, chloromethylstyrene, butadiene,
It may contain polymerized units corresponding to known monomers such as methacrylic acid, acrylic acid, methyl methacrylate, ethyleneimine, vinyl acetate, vinyl imitasol, vinyl pyridine, vinyl carnosol, and the like.

In the case where the polymer has a polymerized unit represented by 2), three-dimensional crosslinking can be achieved by including a trifunctional polymerized unit such as shown in 2).

The polymer of the present invention is an adsorbent polymer that has excellent selectivity for Group 3B elements as an adsorbed substance and also has excellent thermal and chemical stability. Preferably, it is contained. In quantitative terms, it is preferably 0.5 mm o 1711 or more, more preferably L 0 mmoA'/y or more.

The polymer of the present invention can be used as an adsorbent for metal ions, inorganic substances, and even organic substances. Adsorption refers to capture adsorption, physical adsorption, chemical affinity adsorption, etc. by so-called chelation. Among these, the polymer of the present invention showed extremely good selectivity to Group 3B elements.

Group 3B elements are B, A1. Ga, In,
It is Tl.

The state in which these Group 3B elements are separated and purified may be normally a solution state, and there are no particular restrictions on the bonding state.

Conventional and well-known methods can be used to use the substance of the present invention as an adsorbent. For example, the purpose can be achieved by contacting the substance with a liquid containing the ions in a linear or chromatographic manner. is possible.

Examples are shown below, but these are not intended to limit the scope of the present invention.

Reference Example 1 A mixed solution of commercially available 56 qb divinylbenzene log, y lolomethylstyrene (m form, p body mixture 19 og, and azobisin butyronitrile 1.0 g) was polymerized by a normal suspension polymerization method to produce a product. It was found from storage and elemental analysis that the entire amount of divinylbenzene and chloromethylstyrene had been polymerized.The entire amount of this material was added to acetic acid, and then sodium acetate was added and kept at 100°C for 15 hours. .

After filtering and washing the product, it was added to an aqueous solution of 6N hydroxide and kept at 90° C. for 4 hours. This product was thoroughly washed with 1N hydrochloric acid and water.

Reference Example 2 A mixed solution of 10 g of commercially available 56 divinylbenzene, 90 g of formylstyrene (m-form, p-form mixture), and 1.0 I of azobisin butyronitrile was polymerized by a normal suspension polymerization method to obtain a product. Obtained.

The yield and elemental analysis revealed that all of the divinylpenze/formylstyrene was polymerized.

Example 1 100 mg of 1N hydrochloric acid was placed in a 200-mm flask with a stirrer.
, polymer log obtained in Reference Example 1 and catechol 1
5 and 9 were added and heated to 90°C.

The reaction was continued at this temperature for 15 hours with stirring. The product thus obtained is filtered and thoroughly washed with water. The gold medal for the catechol skeleton of this product is that the adsorption amount of lead ion 6 was measured using the usual method and was 2.8 mmolJ/
It was I.

Example 2 30% Tj & acid 100m/, the polymer toy obtained in Reference Example 1, and catechol 1s9 were added to a 200rnI flask with a stirrer and heated to 90°C.

The reaction was continued at this temperature for 15 hours with stirring. The product thus obtained was filtered and thoroughly washed with water. The content of catechol skeleton was measured using the same method as in [Example] and found to be 3.3 mmoj! / It was 9. (This polymer is designated #o1.) Example 3 Volume @ 111. In a stainless steel autoclave container with a pressure resistance of 150 g/-, 300 m of 5-ethanol, 20 g of the polymer obtained in Reference Example 2, and sodium ethyl) 451%
and Catechol 509 were added and heated to 180°C. The reaction was continued at this temperature for 15 hours with stirring. The product obtained in the form of kernels was filtered and thoroughly washed with water. The term catechol backbone was 4.5 mmol/9.

(This polymer is referred to as #o2) Example 4 Into a 500-liter stirrer flask, add ethylene glycol 2
00m, sodium ethylate 45. j9, add 20 g of the polymer obtained in Reference Example 2 and 50 g of catechol to make 1
Heated to 50°C. The reaction was continued under stirring for 30 hours in this warm state. The product thus obtained was filtered and thoroughly washed with water.

The content of catechol skeleton was 4.2 nmol/7.

Example 5 200 mε of 10% sulfuric acid was added to a SOO flask equipped with a stirrer, and 22 g of catechol was dissolved therein.

While stirring at room temperature, 49 g of 37% formalin solution was added dropwise from the dropping funnel. The mixture was thoroughly stirred, the stirrer was removed, and the mixture was heated to 90°C.

The reaction continued at this temperature for 15 hours. After the reaction, the raw acid was in the form of a lump, which was pulverized using a mixer.

After thoroughly washing this product, the catechol skeleton steel was measured and found to be a, 7 mmol/7.

The infrared spectrum absorption of this product showed a characteristic absorption near 1290 cm.

(This polymer is called #03) Example 6 10% sulfuric acid 200rn! A product was obtained in the same manner as in Example 5, except that 6N sodium hydroxide 200% was used instead of . The content of catechol skeleton in this product was s, t mmol/g.

(This polymer is referred to as #04) Comparative Example 1 and Examples 7 to 10 Iminodiacetic acid type chelate resin synthesized by a known method and resins #01 to #04, 10g each of 10g of gallium 1
54P% aluminum 40,500F.

Sodium xo7. oooPt-containing sodium aluminate aqueous solution 100-, shaken for 2 hours, filtered, #Gallium I in the solution! II [was analyzed.

The results are summarized in Table 1.

J Fumiko fi: White Table 1

Claims (1)

[Claims] (Adsorptive polymer having 11 catechol skeleton (2) Adsorptive polymer according to claim 1) having catechol skeleton of O,'5 mrnol/11 or more