JPS587338B2 - New polymer-supported adsorbent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polymer-supported absorbent comprising a specific polymer derivative supported on an inorganic adsorbent.

Conventionally, inorganic adsorbents such as activated carbon, alumina, and asbestos are widely known as adsorbents, but their application range is limited due to their non-selective adsorption properties.

In addition, so-called polymer-supported adsorbents, such as silicic acid derivatives coated with polyamide resin and montmorillonite supported with vinyl polymers, have been used particularly for improving the quality of beverages with plant-based ingredients. It is still not sufficient to selectively adsorb only harmful substances such as polyphenols and protein-polyphenol aggregates contained in Currently, there is a desire for the development of

The present inventors conducted extensive studies on selective adsorption, which is a major drawback of such conventional adsorbents, and found that molecular groups of acid amide groups, tertiary amine groups, ether residues, and alcoholic hydroxyl groups We have discovered that these molecular groups have high affinity with each other, and that when these molecular groups exist in the same chain, even higher affinity is exhibited.

Furthermore, it has been found that an inorganic adsorbent that easily adsorbs a polymer having such a molecular group has extremely excellent saturation adsorption properties and economical efficiency, and the present invention has been achieved.

That is, in the present invention, a polyalkylene polyamine polyamide obtained by reacting a polyalkylene polyamine and a monoalkylene diamine with a saturated and unsaturated aliphatic dicarboxylic acid having 2 to 10 carbon atoms is further reacted with epichlorohydrin or a diglycidyl ether derivative, Activated carbon, alumina, zirconyl hydroxide, titanium hydroxide, phosphoric acid Zirconium, zirconium oxide, titanyl hydroxide, titanium phosphate, silicon oxide, diatomaceous earth, asbestos, montmorillonite,
This is a novel polymer-supported adsorbent for adsorbing and removing polyphenols contained in vegetable beverages, which is supported on one or more inorganic adsorbents selected from kaolin and their precursors.

Here, as the polyalkylene polyamine, diethylene triamine, triethylene tetraamine dipropylene triamine, tripropylene tetraamine, dibutylene triamine, etc. are used, but 20 to 90% of the polyalkylene polyamine is monoalkylene diamine such as ethylene diamine, propylene diamine, Substitution with hexamethylene diamine, pentamethylene diamine, diaminomethylbenzene, etc. is preferable because the resulting polymer tends to be water-insoluble.

As the aliphatic dicarboxylic acid, a saturated or unsaturated aliphatic dicarboxylic acid having 2 to 10 carbon atoms is used.

Examples include adipic acid, itaconic acid, maleic acid, sebacic acid, etc. However, since the polymer obtained from saturated aliphatic dicarboxylic acid alone is water-soluble, it is necessary to partially crosslink it to make it water-insoluble. It is preferable to partially substitute the group dicarboxylic acid.

Next, as diglycidyl ether derivatives, polyalkylene glycol diglycidyl ether derivatives and polyalkylene oxide diglycidyl ether derivatives are used, and examples include diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polyethylene oxide diglycidyl ether.

Furthermore, the inorganic adsorbent to be supported is one that easily adsorbs the polyalkylene polyamine polyamide derivative, and includes activated carbon, alumina, zirconyl hydroxide, silconium phosphate, zirconium oxide, titanium hydroxide, titanyl hydroxide, titanium phosphate, Silicon oxide, diatomaceous earth, asbestos, kaolin, and their precursors such as sodium silicate and zirconyl chloride are used.

Next, there are various methods for supporting the polyalkylene polyamine polyamide derivative on the inorganic adsorbent, but the simplest method is, for example, to impregnate the inorganic adsorbent with the polymer derivative and then heat-treating the polymer derivative.

In addition, when polyalkylene polyamine and aliphatic dicarboxylic acid are reacted, a predetermined amount of inorganic adsorbent is added to react, and after cooling, shrimp chlorohydrin or diglycidyl ether derivatives are added dropwise to a weak alkali to react. There is a method of heat treatment or heating again after adding a crosslinking agent as necessary. In this method 9, an inorganic adsorbent such as zircote hydroxide 5 is used to strongly fix the polyalkyne polyamine and aliphatic dicarboxylic acid on the surface. The reaction was carried out using crystalline alumina, etc. In this case, the reaction takes on the appearance of a solid phase polymerization reaction and a polymer with a high degree of polymerization is obtained, which is preferable since it is water-insoluble.

The ratio of the polymer derivative supported on the inorganic adsorbent varies depending on the inorganic adsorbent used, but is preferably about 5 to 50% by weight based on the inorganic adsorbent, and if it is less than 5%, the selective adsorption property is insufficient. , 750% or more is not advantageous in terms of manufacturing or economics.

Although the mechanism by which the novel adsorbent of the present invention exhibits excellent selective adsorption properties has not yet been fully elucidated, first, polyphenols are specifically transferred to the surface of the new adsorbent by the molecular groups possessed by the supported polymer derivative. It is believed that there is a chemical selection process followed by physical diffusion adsorption onto the inorganic adsorbent.

Therefore, it is thought that it exhibits excellent selective adsorption properties and a large amount of saturated adsorption.

The novel adsorbent of the present invention can adsorb and remove polyphenols by contacting it with a vegetable beverage in the following manner.

In other words, during the manufacturing process of beer, wine, fruit juice, etc. before bottling, for example, for beer, immediately after the main fermentation, during the post-fermentation process, etc., and for wine, immediately after the juice pressing process, in the intermediate production liquid such as after the storage process, etc. A method in which the novel adsorbent of the present invention is introduced and stirred and then filtered using a filter cloth or filter paper, or a method in which a column containing the adsorbent in a cylindrical tube is made and the solution is passed through the column. , furthermore, a method of filtering the intermediate manufacturing liquid of the beverage using a filter cloth or filter paper pre-coated with the adsorbent, furthermore, Japanese Patent Publication No. 46-6
Publication No. 111 or the patent application filed by the applicant in 1972
Any of the methods described in Japanese Patent No. 115227, in which polyamide microfibers, cellulose, etc. are mixed into a sheet and the solution is passed through the sheet, can be effectively used.

The present invention will be explained in more detail below using Examples.

Example 1 7 g (0.75 mol) of trietherenetetraamine, 93 g (0.25 mol) of propylene diamine, 116 g (0.8 mol) of adipic acid and 24.9 g (0.9 mol) of maleic acid.
A mixture of 200g of water and 200g of activated carbon was adsorbed or impregnated on 500g of activated carbon, and the resulting mud was uniformly stirred and reacted at 200°C for 2 hours.

After adding 100 g of water and cooling to 60°C, diethylene glycol diglycidyl ether 182.9 (0.5 mol) was added dropwise over 30 minutes with strong stirring using the dropwise method to react, and the temperature was raised to 160°C and the pressure was reduced to remove moisture. Excluded.

The obtained lump was pulverized, washed with water, washed with methanol, and dried to obtain a target product A having a polymer loading ratio of 42%.

Similarly, using r-crystalline alumina instead of activated carbon,
A target product B with a polymer support ratio of 24% was obtained.

1 each of these adsorbents and nylon 66 powder for comparison.
0.9 was mixed with 41 unbeaten pulp, and about 45cm
A circular sheet was created.

For convenience, each sheet is called "Sheet A", "Sheet B",
and "sheet comparison".

Load these sheets into the filter holder and pour commercially available beer 3.
Table 1 shows the results of quantifying the saturated adsorption amounts of polyphenols and anthocyanogens on each sheet by treating 0 liters with carbon dioxide gas at a rate of about 600 liters/m2·hr.

However, polyphenols and anthocyanogens were determined by Harris's method and Dadik's method, respectively.

It can be seen from Table 1 that the sheet according to the present invention has an extremely large saturated adsorption amount compared to the conventional sheet.

Example 2 Target A obtained in Example 1 (polymer support ratio 42%
activated charcoal) and activated charcoal for comparison with 1 liter of pressed red grape juice.
After adding 5 g of each to 1 ton of fermented beer and letting it stand for 1 hour,
Its decolorization property was observed.

Both of the beverages treated with activated carbon were decolorized, but Target A was hardly decolorized.

Furthermore, when we observed the occurrence of turbidity after being left for two weeks under sterile conditions, we found that a considerable amount of turbidity had occurred with the activated carbon treated product, whereas with Target A there was almost no turbidity. .

Thus, it can be seen that the adsorbent of the present invention specifically adsorbs cloudy components in vegetable fermented beverages.

As is clear from the above examples, the novel adsorbent of the present invention specifically adsorbs polyphenols, anthocyanogens, and cloudy components in vegetable drinks, and its saturated adsorption amount is higher than that of conventional adsorbents. It is extremely large and economically superior compared to conventional agents.

Claims (1)

[Claims] 1 A polyalkylene polyamine polyamide obtained by reacting a polyalkylene polyamine and a monoalkylene diamine with a saturated and unsaturated aliphatic dicarboxylic acid having 2 to 10 carbon atoms is further reacted with epichlorohydrin or a diglycidyl ether derivative to form a main chain. A polyalkylene polyamine polyamide derivative having an acid amide group and a tertiary amine group and having an ether residue or an alcoholic hydroxyl group introduced into the side chain can be used as activated carbon, alumina, zirconyl hydroxide, titanium hydroxide, zirconium phosphate, Adsorbs and removes polyphenols contained in vegetable beverages supported on one or more inorganic adsorbents selected from zirconium oxide, titanyl hydroxide, titanium phosphate, silicon oxide, diatomaceous earth, asbestos, montmorillonite, and kaolin. A novel polymer-supported adsorbent for