JPS62104807A - Macromolecular metal complex - Google Patents

Abstract

PURPOSE:To obtain the titled metal complex of high odor-decomposition rate also with outstanding persistency when used as a deodorant, by bonding to macromolecular compound a metal phthalocyanine derivative as an oxidative and reductive metal complex. CONSTITUTION:The objective metal complex can be obtained by bonding to a macromolecular compound (e.g., polystyrene, polyvinyl alcohol) a metal phthalocyanine derivative of formula (M is oxidative and reductive metal atom; for Ys, at least one is substituent, the rest being H) (pref. M is Mn, Co, Ni or Fe, the substituent for Ys being carbonyl chloride, acetaldehyde). USE:Usable by dissolving or dispersing in water or organic liquid, or by adsorption to zeolite, etc., or by attaching to or chemical bond formation with pumice, paper, rubber, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polymeric gold F? & complexes, particularly polymer metal complexes in which a metal phthalocyanine derivative is bonded to a polymer compound.

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 enzyme methods, but all of them have high running costs. It has many drawbacks, such as high deodorization, difficulty in management, poor sustainability, and relatively low deodorizing efficiency.

In particular, among these known deodorizing treatment methods, the method of decomposing malodorous gas using an oxidizing agent is the most effective, but it generally uses dichromic potassium, sulfuric acid, etc., so be careful when handling it. This treatment method is not preferred for general use because of the high reaction temperature, the risk of secondary contamination due to chemicals, and the high reaction temperature.

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 of a metal complex with fiI reduction ability to a polymeric substance, particularly excellent performance was obtained. I found that it gives 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. Although it has extremely advantageous properties as a deodorant, such as long catalyst life in cycle reactions, it has been found that catalytic 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 action, and has the following formula: A metal phthalocyanine derivative (where the remainder is a hydrogen atom) is bonded to a polymer compound.

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

The substituent Y used in the metal phthalocyanine derivative of the present invention includes an alkyl group, a substituted alkyl group, a halogen group, a nitro group, an amino groups, nitrile groups, hydroxyl groups, alkoxyl groups, phenoxydyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, chloromethyl groups, alkyl silicon groups, vinyl groups, as well as alkali groups such as carboxyl groups and sulfonic acid groups. There are various salts, among which lj types or two or more types are used, and among them, a carbonyl chloride group or an aldehyde group is preferably used.

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, polymethacrylic acid and their metal salts or alkyl esters, 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, amino resin, alkyd resin, etc., and copolymers thereof are used, and these are selected from those that react and bond with the Fa substituents of phthalocyanine, but preferably polystyrene, polyvinyl alcohol, Polyacrylic esters, polymethacrylic esters, and polyvinylamines are used, particularly preferably polystyrene and polyvinyl alcohol.

〔Production method〕

The polymeric metal complex of the present invention can 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.
Pumice 1 It is used by adhering or chemically bonding to foamed concrete, various fibers, leather violet, rubber, plastics, paper, pulp, etc.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the same extent by these Examples.

Example 1 Into a three-loaf flask equipped with a stirrer and a reflux condenser, 150 μl of nitrobenzene was charged, and 100 g of trimellitic anhydride, 300 g of urea, 10 g of ammonium molybdate, and 3 g of ferric chloride anhydride IEi were added. The mixture was stirred and heated under reflux at 160 to 170°C for 3 hours. After cooling, the precipitate was filtered and washed in the order of methanol, dilute hydrochloric acid, and water to obtain iron phthalocyanine tetracarboxylic acid amide. Aqueous solution 1! ; Stir with L, react and hydrolyze while refluxing at 100°C, and after cooling, add hydrochloric acid to make it resistant and prepare iron phthalocyanine tetracarboxylic acid (fl).

Next, put benzene 1001 in a three-bottle flask equipped with a stirrer and a rapid flow condenser, and add 10 g of iron phthalocyanine tetracarboxylic acid obtained above and thionyl chloride 301,
Add 0.51 liters of pyridine, stir and heat to reflux.
The reaction was allowed to proceed for 0 hours to form iron phthalocyanine with a carbonyl chloride base.

Add 5 g of the carbonyl chloride group-containing iron phthalocyanine obtained above to a solution of 30 g of polystyrene in 300 liters of nitrobenzene, stir to dissolve until homogeneous, cool to below 10°C in a water bath, and then anhydride. 10g of aluminum chloride was added and left to stand for 10 hours while stirring W1 to obtain a gel-like reaction product.Next, this was poured into water and nitrobenzene was removed by steam distillation.After drying, the product was diluted with methanol and a dilute alkaline solution. The polystyrene was washed in the following order and further washed with dilute hydrochloric acid to obtain polystyrene having iron phthalocyanine in the side chain.

Elemental analysis of this revealed that N was 0.62% by weight and F
e was 0.30% by weight. Calculated from the amount of N, iron phthalocyanine is 4 per monomer unit of polystyrene.
．． 12No1% combined, calculated from the amount of Fe, the same (
This means that 4,0ONo1% is combined, and the values of both names almost match. In addition, the infrared absorption spectrum of this item is 1700 cm for iron phthalocyanine tetracarboxylic acid.
-'(>C-O bond of carboxyl group) has an absorption, while at 1700cm-1 and 16800C[
1 (>C=0 bond of ketone group) also has absorption.

Example 2 105 g of iron phthalocyanine having a carbonyl chloride group obtained in Example 1 and 12 g of barium palladium sulfate,
400 ml of xylene was placed in each flask equipped with a stirrer, and hydrogen was blown into the flasks to perform Rosenmund reduction to obtain iron phthalocyanine having an aldehyde group.

1100 ml of 10% polyvinyl alcohol aqueous solution and 30
% sulfuric acid and heated to 40°C, to which was added the iron phthalocyanine 51 having an aldehyde group obtained above.
The viscosity of the zero reaction system gradually increased, and when it reached just before gelatinization, it was cooled and 10%
After neutralizing with aqueous ammonia, methanol was added to precipitate and dry. Polyvinyl alcohol bound to iron phthalocyanine was obtained.

Poetry Applicant Homa Yamai Nippon Carbide Industries Co., Ltd. Nippon Carbide Industries Co., Ltd. Earthclean Co., Ltd.

Claims (1)

[Claims] 1. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M is a metal atom, at least one Y represents a substituent, and the rest represent hydrogen atoms] A polymer metal complex in which a metal phthalocyanine derivative is bonded to a polymer compound. 2. The polymeric metal complex according to claim 1, wherein at least one of said Y is a carbonyl halide group or an aldehyde group, and the remainder are hydrogen atoms. 3. The polymer metal complex according to claim 1 or 2, wherein the polymer compound is polystyrene or polyvinyl alcohol.