JPH01245003A - Metallic phthalocyanine octacarboxylic acid polystyrene - Google Patents

Abstract

PURPOSE:To obtain a compound having excellently catalyzing action in using as a deodorant by bonding a metallic phthalocyanine derivative of a metallic complex having oxidation-reduction ability to a polymer substance. CONSTITUTION:A metallic phthalocyanine octacarboxylic acid polystyrene shown by formula I or formula II (M is metallic atom and polymerization degree of polystyrene unit x+y=300-4,000). The polystyrene, for example, is dissolved or dispersed into water or an organic liquid, adsorbed on a solid having adsorbing ability such as active carbon, sawdust or zeolite or chemically bonded to pumice or foamed concrete and used as a deodorant. In decomposing substances of bad smell into odorless substances, the polystyrene has high reaction rate, high decomposition ratio, long catalytic life and extremely high catalytic efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal phthalocyanine octacarboxylic acid polystyrene in which a polymeric metal complex, particularly a metal phthalocyanine octacarboxylic acid, is bonded to polystyrene.

In recent years, the factors that generate bad odors have become more complex year by year, but the technology to deal with them is extremely inadequate, so the current situation is that there is no sign that bad odor pollution will improve.

Conventional methods for deodorizing bad odors include activated carbon adsorption, catalytic combustion, ozone or chemical oxidation, neutralization, bacterial decomposition, and enzymatic methods, but all of them have high running costs. It has many drawbacks, such as being expensive, difficult to manage, lacking in sustainability, and having relatively low deodorizing efficiency.

In particular, among these known deodorizing treatment methods, the method of decomposing malodorous gases using oxidizing agents is the most effective, but since potassium dichromate, sulfuric acid, etc. are generally used as agents, care must be taken when handling them. This treatment method is not preferred for general use because there is a risk of secondary contamination due to chemicals and the reaction temperature is high.

As a result of research into deodorants that are free from the above-mentioned drawbacks and exhibit excellent effects, the present inventors found that by bonding a metal phthalocyanine derivative, which is a metal complex with redox ability, to a polymeric substance, particularly excellent performance was achieved. I found giving. In other words, metal phthalocyanine derivatives have a high reaction rate and high decomposition rate when decomposing malodorous substances to make them odorless, the reaction proceeds at room temperature, the reaction can be carried out in an aqueous system, and the oxygen in the air is effectively used. What you can do,
Although it has extremely advantageous properties as a deodorant, such as a long catalyst life in cycle reactions, it has been found that the catalyst efficiency can be significantly increased by bonding it to a polymer compound.

As described above, the polymer metal complex of the present invention is a compound having excellent catalytic activity.

A substituent of a metal phthalocyanine derivative of the following formula: (wherein, M is a metal atom with redox ability, and at least one Y is a substituent and the rest are hydrogen atoms) is bonded to a polymer compound. This is what I did.

Examples of M in the basic skeleton include calcium, barium, tin, chromium, iron, cobalt, nickel, copper, manganese, osmium, titanium, beryllium, molybdenum, and tungsten. Among these metals, manganese, cobalt, nickel, and iron are preferably used from the viewpoint of deodorizing effect.

The W1 substituent Y used in the metal phthalocyanine derivative includes an alkyl group, a substituted alkyl group, a /-logen group, a nitro group, an amino group, an azo group, a thiocyanate group, a carboxyl group, a carbonyl chloride group, a carboxylamide group, and an aldehyde group. , nitrile group, hydroxyl group, alkoxyl group, phenoxydyl group, sulfonic acid group, sulfonyl chloride group, sulfonamide group, thiol group, chloromethyl group, alkyl silicon group, vinyl group, as well as alkali salts of carboxyl group and sulfone m group. and so on. Particularly preferred is a case in which 8 of Y are carboxyl groups and the rest are unsubstituted -H.

Examples of polymer compounds to be chemically bonded include natural polymers and their derivatives such as cellulose, starch, gelatin, casein, and guar gum, polyvinyl alcohol, polyacrylic acid or polymethacrylic acid, and metal salts or alkyl esters thereof, polyacrylic or polymethacrylamide, mono- or dialkylaminoacrylate or methacrylate, polyhydroxyalkyl acrylate or methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinylsulfonic acid or its metal salts, polyvinyl ester, polystyrene,
Polyvinyl acetal, polyester, polyamide, amine resin, alkyd resin, etc., and copolymers thereof are used, and those that react with and bond to the substituents of phthalocyanine are selected, and preferably polystyrene is used. Polystyrene has a polymerization degree of 300-40
00 commercially available products can be used.

A particularly preferred combination of a metal phthalocyanine derivative and a polymer compound that reacts therewith is a combination of a metal phthalocyanine octacarboxylic acid in which 8 of the substituents Y are carboxyl groups, and polystyrene.

That is, the chemical formula of the polymer metal complex of the present invention is as follows, and the degree of polymerization of polystyrene units is X+yl-30
It is 0-4000.

Furthermore, since metal phthalocyanine octacarboxylic acid has a plurality of functional groups (carboxyl groups), polystyrene molecules may be crosslinked. In that case, the chemical formula of the polymer metal complex of the present invention is as follows.

In order to obtain the catalytic effect of the polymeric metal complex of the present invention, it is sufficient that the metal phthalocyanine octacarboxylic acid is bonded to about 0.1z of all the phenyl groups in polystyrene, but the metal phthalocyanine octacarboxylic acid is bonded to about 60z of all the phenyl groups in polystyrene. Octacarboxylic acid does not bind.

The polymeric metal complex of the present invention may be used by being dissolved or dispersed in water or an organic liquid, or adsorbed onto a solid having adsorption ability such as activated carbon, sawdust, or zeolite.
It is used by adhering or chemically bonding to pumice, foamed concrete, various fibers, leather, rubber, plastics, paper, pulp, etc. It may also be used by molding itself.

Next, a concrete explanation will be given with reference to examples.

Nitrobenzene 1501 was placed in a three-bottle flask equipped with a stirrer and a reflux condenser, and 114 g of pyromellitic anhydride, 300 g of urea, and 1 ammonium molybdate were added.
Add Og and 18.3 g of ferric chloride anhydride and stir.
The mixture was heated at 180-170° C. for 3 hours under reflux.

After cooling, the precipitate was filtered, washed in the order of methanol, dilute hydrochloric acid, and water, and then placed in a three-bottle flask equipped with the same equipment as above, together with 30% caustic potassium aqueous solution 141, and stirred at 100°C. The mixture was reacted and hydrolyzed under reflux, and after cooling, hydrochloric acid was added to acidify the mixture to obtain iron phthalocyanine octacarboxylic acid.

10 benzene in a three-loaf flask equipped with the same equipment as above.
Add 0 ml of iron phthalocyanine octacarboxylic acid.
og and thionyl chloride 301. Add 0.51 pyridine,
The reaction mixture was stirred and heated under reflux for 10 hours to form iron phthalocyanine having carbonyl chloride groups.

Add 5 g of the carbonyl chloride group-containing iron phthalocyanine obtained above to a solution of 30 g of polystyrene in nitrobenzene 3001, stir and dissolve until homogeneous. Next, cool to 10°C or less in a water bath and then anhydrous chlorination. 10 g of aluminum was added, and the mixture was left to stand for 10 hours while stirring to obtain a gel-like reaction product. This was poured into water and nitrobenzene was removed by steam distillation, and after drying, the product was washed with methanol, then with an alkaline solution, then with dilute hydrochloric acid, and then thoroughly washed with water. When the infrared absorption spectrum of this product was examined, it was found that the absorption of the 1000H group in iron phthalocyanine octacarboxylic acid weakened, and a shifted absorption of the 100 group appeared.

Claims (1)

[Claims] 1. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M is a metal atom, and the degree of polymerization of polystyrene units x + y
=300-4000] metal phthalocyanine octacarboxylic acid polystyrene. 2. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M is a metal atom, and the degree of polymerization of polystyrene units x + y
=300-4000] metal phthalocyanine octacarboxylic acid polystyrene.