JPH02102733A - Porous fine particles having deodorizing function - Google Patents

Abstract

PURPOSE:To obtain porous fine particles having superior deodorizing performance by supporting a metal complex having oxidizing-reducing ability on porous fine org. particles having innumerable fine through holes in the entire particles. CONSTITUTION:Porous fine particles of methyl methacrylate, etc., synthesized by suspension polymn. or other method are immersed in an aq. soln. of a metal complex such as iron phthalocyanine.polycarboxylic acid to support the metal complex by >=0.01wt.%. One or more kinds ot metal complexes selected among metal porphyrin, metal porphyrazine, derivs. ot them and polymer-metal complexes may be used. By the interaction between the metal complex and the porous tine particles, the supported metal complex is not easily separated by washing and dehydration and the deodorizing activity is maintained over a long period of time.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to porous fine particles having a deodorizing function, and in particular to porous fine particles having continuous pores on which metal complexes having a redox catalytic function are supported. This relates to Jf fine particles.

(Prior art) For example, bad odor due to decomposition of hydrogen sulfide, ammonia, etc.
Many methods have been known to remove bad odors, reducing odor components, and harmful gases caused by incomplete combustion.
Representative examples include the following.

(a) Combustion method: Also called direct combustion method or afterburning method, this method uses flame to burn malodorous components at high temperatures of around 650 to 800°C, and oxidizes and decomposes them into odorless and harmless substances such as water vapor and carbon dioxide gas. .

(b) Catalytic oxidation method: Also called catalytic combustion method, this method uses a catalyst to oxidize malodorous components at 250 to 350°C.

(c) Adsorption method: A method in which malodorous components are adsorbed onto porous materials with adsorption capacity, such as activated carbon, zeolite, and silica gel.

(d) Ozone oxidation method A method of oxidizing malodorous components using the oxidizing power of niosin.

(e) Chemical cleaning method: A method of absorbing or cleaning odor components with acid or alkaline solution.

(f) Masking method: A method of dissipating a fragrance that is stronger than the bad odor.

An appropriate method is selected from among the above methods based on conditions such as the state of the odor source and the environment.

However, since the combustion method (a) and the catalytic oxidation method (b) require large equipment and high running costs, they are only applied to industrial applications for deodorizing large-scale, foul-smelling exhaust gas. In addition, the ozone oxidation method (2) requires an ozone generator, and the chemical cleaning method (e) requires
It lacks versatility, such as the inability to remove malodorous components that are difficult to neutralize with acid or alkaline solutions.

On the other hand, the adsorption method (c) is a method that has been used for a long time, is versatile, and has relatively low running costs, so it is currently widely used in various fields and has penetrated into ordinary households. For example, the refrigerator, toilet,
It is often used to deodorize small spaces such as closets.

However, the diffusion of bad odor into the adsorbent becomes rate-limiting.
Adsorbents are unsuitable for wide area deodorization, require a long time to reach adsorption equilibrium, and are not necessarily easy to reduce the concentration below the malodor threshold due to the equilibrium system. has drawbacks such as not having activity against all types of malodors.

In addition, in the method using an adsorbent, the deodorizing effect decreases over time, so that the adsorbent must be periodically replaced with a new adsorbent.

In recent years, the development of deodorizing technology that utilizes the oxidation catalytic function of metal complexes has been progressing, and specific examples include U.S. Pat.
No. 0180 and JP-A-55-32519.

According to JP-A No. 55-32519, some biological oxidases, especially certain metal-containing enzymes, have the ability to oxidize and decompose ammonia, amines, hydrogen sulfide, mercaptans, indoles, carbonyl compounds, etc. Furthermore, the oxygen reaction itself has favorable conditions for decomposing malodorous substances, and therefore metal complexes that exhibit reaction behavior similar to biological oxidases are effective in oxidatively decomposing malodorous components. is taught.

In particular, metal porphyrins, metal porphyrazines,
The derivative has (1) a fast reaction rate and good decomposition efficiency;
(2) The reaction proceeds at room temperature, (3) There is no risk of environmental pollution because it is a water-based reaction, and (4) The catalyst has a long life because it is a cycle reaction. It is stated that the conditions are met. moreover,
The publication describes that these metal complexes can be supported on activated carbon, zeolite, fiber, paper, plastic, etc. and used.

(Problem to be solved by the invention) As mentioned above, deodorizing technology that uses metal complexes such as metal porphyrin and metal porphyrazine as an oxidation catalyst is already known, but the technology according to the above US patent is This process involves the removal of mercaptans from petroleum, and the elimination process consists of two phases: an oil phase and an aqueous phase containing a large amount of alkali.
It is carried out by a phase method, and the catalyst itself is mainly supported on a solid surface such as activated carbon, which is unsatisfactory for general odor removal.

On the other hand, the deodorant described in JP-A No. 55-32519 has the advantages of excellent long-lasting odor removal action, low running costs, and the ability to be used by supporting various substances with adsorption ability. have.

However, in order to support a substance with adsorption ability on a substance such as zeolite or activated carbon, for example, immersion in an aqueous solution of 10% metal phthalocyanine (metal porphyrazine) and then dehydration drying is performed. can be,
Due to its low affinity with metal phthalocyanines, metal phthalocyanine often separates from the carrier during dehydration, and the amount of metal phthalocyanine attached to the dried substance is extremely small.

In addition, most bad odors are generally in the gaseous state,
When deodorizing, it is necessary to bring the deodorant into contact with the bad odor effectively and in a short time.Regarding this requirement, porous fine particles having continuous pores as a carrier have a very large specific surface area. The metal complex having redox ability is easily brought into contact with the gas component. It is also considered to be an advantageous material because it is easy to change the hydrophilic/hydrophobic balance by selecting raw materials when synthesizing porous fine particles, and the affinity with metal phthalocyanines can be freely controlled. In addition, because porous fine particles are synthesized from organic substances, unlike zeolites and activated carbon, they have a high affinity with metal complexes that have a deodorizing function, so they can be used as deodorizers during dehydration and drying after soaking. Another relatively advantageous advantage is that the desorption is extremely small.

(Means for Solving the Problems) The present inventors investigated the deodorizing function of various organic porous fine particles by carrying metal complexes having redox ability, and found that fine penetrating particles were formed throughout the entire body. It has been found that porous fine particles having countless pores have a superior ability to support metal complexes compared to other carriers, and the above-mentioned difficulties of conventionally known deodorants can be solved.

The porous fine particles having a deodorizing function according to the present invention are characterized in that particles having innumerable fine through holes throughout the particles support 0.01% by weight or more of a metal complex having redox ability. .

The porous particles having countless fine through holes used in the present invention are synthesized, for example, as follows.

That is, radically polymerizable monomers such as styrene,
Styrene derivatives such as methylstyrene and chlorostyrene,
Acrylic acid esters such as acrylonitrile, methacrylaterile, methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; fatty acid vinyls such as vinyl acetate and vinyl propionate; allyl acetate; Various allyl esters such as allyl propionate; vinyl ethers such as isobutyl vinyl ether and phenyl vinyl ether; polyethylene glycol monovinyl ethers such as ethylene glycol monovinyl ether and diethylene glycol monovinyl ether; Vinyl or allyl ethers of polyalkylene gelcols such as alcoholic acid ethers, maleic diesters such as dimethyl maleate and diethyl maleate, fumaric diesters such as diethyl fumarate and dipropyl fumarate, dimethyl itaconate, Itaconate diesters such as diethyl itaconate, mesaconate diesters, thiol fatty acid vinyl esters, alkyl vinyl sulfides, vinyl ketones, acrylamides, vinylamides, vinyl carbazole derivatives, various diene derivatives, allyl compounds, In addition, various monomers having radical single or radical copolymerization reactivity, crosslinkable heptamers having two or more radically polymerizable unsaturated double bond groups in a predetermined amount, and evagivinyl ether, Diacrylates of polyethylene glycols such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dimethacrylates, diacrylates of polypropylene glycols, or polyalkylene gels such as dimethacrylates. Recall diacrylates or dimethacrylates, other polyacrylates or polymethacrylates of various polyhydric alcohols, fumaric acid, maleic acid, itaconic acid, mesaconic acid, succinic acid, adipic acid, phthalic acid. , esters of alcohols having an unsaturated double bond group such as divinyl or diallyl esters of aliphatic or aromatic di- or tricarboxylic acids such as isophthalic acid and terephthalic acid and having radical crosslinking properties; a predetermined amount of a radical polymerization initiator, such as benzoyl peroxide, tert-butyl hydroperoxide,
Organic peroxides such as diisopropyl peroxycarbonate, cumene hydroperoxide, and dicumyl peroxide, and an azo radical polymerization initiator such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile are added, and an appropriate solvent is added. For example, add an aromatic organic solvent such as benzene, toluene, or xylene, or an organic solvent commonly used as a radical polymerization solvent such as trichloroethane, tetrachloroethylene, or hexachloroethane, and which is insoluble in water, in an amount equal to that of the monomers. Mix thoroughly to prepare monomer oil.

On the other hand, in water, well-known water-soluble polymers such as polyvinyl alcohol, sodium polyacrylate, and polyvinylpyrrolidone, which are widely used as thickeners in suspension polymerization and emulsion polymerization, or as dispersion stabilizers, are suitable. The mixture of monomer oils prepared above is added to the evaporated mixture, stirred at high speed to sufficiently uniformly disperse the monomer oil in water, and heated as it is for polymerization to synthesize fine particles. After the polymerization is complete, fine particles are isolated by filtration, washed with water to completely remove water-soluble polymers, and then treated with an alcohol such as methanol or ethanol or an organic solvent with a relatively low boiling point such as acetone or chloroform. The immersion and filtration are repeated many times to completely replace and remove the organic solvent used in polymerization, and finally drying is performed under reduced pressure to obtain porous fine particles.

The porous fine particles synthesized in this manner are loaded with a metal complex having a deodorizing function as shown below. Metal porphyrin and its derivatives are represented by the structural formula shown below, and also represented by the structural formula shown for metal porphyrazine.

In both formulas, M is Fe, Co, Mn, Ti,
Examples include metal ions such as NiN15CuSZnS%W.

Among these metal ions, iron and cobalt are preferred from the viewpoint of deodorizing effect. In both formulas, X represents hydrogen or a substituent. As a substituent, an alkyl group, a substituted alkyl group (
For example, chloroalkyl group), halogen group, nitro group, amino group, azo group, thiocyanate group, carboxyl group,
In addition to carbonyl chloride groups, carboxylamide groups, nitrile groups, hydroxyl groups, alkoxyl groups, phenoxydyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, alkyl silicon groups, vinyl groups, etc.
Alkali salts of carboxyl groups and sulfonic acid groups are used. These may be used alone or in combination of two or more.

Among these, carboxyl groups, sulfonic acid groups, alkali salts thereof, amino groups, halogen groups, hydroxyl groups, and the like are preferably used.

In addition, a polymer metal complex is one in which a metal complex is composed of polymer ligands or coordinating oligomers localized in a small part of the chain or dispersed throughout the chain, or a metal complex composed of a polymer ligand or a coordinating oligomer. A complex formed from a metal ion and a metal ion, but has a high molecular weight (usually, the molecular weight is about -10,000 or more). Examples of polymeric metal complexes include intramolecular chelate complexes of polyvinyl alcohol and copper ions, complexes of polyvinylamine and iron ions, and metalloenzymes (eg, catalase, peroxidase, peptidase, etc.). The above metal complexes may be used alone or in combination of two or more.

The required amount of metal complex supported varies depending on the type of metal complex, but is generally 0.01% by weight or more. If the supported amount is small, the desired level of deodorizing activity cannot be obtained, and the sustainability of the deodorizing activity is also poor. The preferred amount supported is in the range of 0.01 to 5% by weight.

In order to support metal complexes on organic porous fine particles, the porous fine particles are immersed in an aqueous solution of the metal complexes mentioned above or in an appropriate organic solvent and treated under pressure or reduced pressure to sufficiently adsorb the metal complexes. Good.

(Function) The deodorizing activity of the metal complex used in the present invention is thought to be based on the oxygen oxidation effect shown below.

The metal coordinated with porphyrin and porphyrazine becomes an active center and the oxidation reaction proceeds. For example, taking the oxidation of mercaptan as an example, the oxidation is shown by the following chemical reaction formula.

2R-SH+ 2011-→2R-S-+ 211□0
(1) 2R-3-+ 28tO+ 0□→R-S-S-
R+)l! 0! +2011- (21The thiolate anion produced in the reaction of formula (1) coordinates with oxygen to porphyrin and porphyrazine to become an active species which is a ternary complex, and the thiolate anion coordinated to this active species is It is converted into a disulfide via a thiyl radical.

This reaction is very similar to in vivo enzymatic oxidation reactions, and several examples of similar aerobic oxidation reactions are known. In addition, other known malodorous components such as amines and aldehydes undergo oxidation reactions with metal complexes and are decomposed into harmless and odorless components, so it is effective against many malodorous components. Furthermore, the oxidation reaction by the metal complex proceeds at room temperature or lower in the presence of a small amount of moisture, and the reaction rate is fast and the reaction rate is high.

It does not seem that the metal complexes are supported on the porous particles only by physical adsorption. In particular, when monomers having OH groups or hydrophilic functional groups are used, almost no elution of metal complexes is observed. It is thought that strong adsorption occurs due to the interaction between the two.

(Effect of the invention) Due to the interaction between the metal complex and the porous fine particles, the supported metal complex does not easily come off by washing with water or dehydration, and can be supported in a larger amount than zeolite or activated carbon. The deodorizing activity lasts for a long time. Furthermore, since it is a cyclic reaction, the catalyst has a long life and running costs are low.

Furthermore, supporting the metal complex on the organic porous fm particles can make it difficult to form an inactive dimer structure, and the metal complex can be supported while maintaining its high activity. By supporting the metal complex on porous fine particles, the metal complex is supported in a highly active state.

In addition, the porous particles that have a deodorizing function can be easily incinerated after use, and since they are a fine powder, they can be used in the same way as various powders, and because they have a deodorizing function, they are widely used in the deodorizing field. can be used.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Porous N fine particles were synthesized using a suspension polymerization method that has been widely used in the past. That is, methyl methacrylate 5
0 parts by weight, 50 parts by weight of ethylene glycol dimethacrylate, 1.5 parts by weight of benzoyl peroxide, and 80 parts by weight of toluene were thoroughly mixed to obtain a monomer oil, and partially saponified polyvinyl alcohol (degree of saponification 95%) was dissolved in water. 500 parts by weight of a 0.3% by weight aqueous solution, the monomer oil prepared earlier was added to this, the monomer oil was sufficiently dispersed in water using a high-speed stirrer, and the mixture was heated to 80°C.
Polymerized for hours.

After the polymerization is completed, the fine particles are separated from the polyvinyl alcohol aqueous solution by filtration, and the fine particles are repeatedly washed with pure water.
Immerse in methanol to replace toluene with methanol,
Drying under reduced pressure was performed to obtain methyl methacrylate-based porous fine particles.

The fine particles were immersed in an aqueous solution of iron phthalocyanine polycarboxylic acid (aqueous solution concentration 3 g/It, pH 12),
Dehydrated and dried. The thus obtained porous fine particles with a deodorizing function contain iron phthalocyanine per 3 g of fine particles.
About 0.06 g of polycarboxylic acid was supported.

The deodorizing activity of the obtained porous fine particles was tested using the method shown below. That is, 50 g of hydrogen sulfide gas was added to a deodorizing reaction section in which 5 g of the above-mentioned deodorizing fine particles were filled inside a glass tube.
air containing 0 ppm at a rate of 10 ioo at per minute
The gas that had passed through the reaction section was stored in a bag, and 10 adult monitors were allowed to smell the gas stored in the bag to perform a sensory test on odor. The results showed that some monitors could only slightly detect the odor of hydrogen sulfide. Furthermore, when a color reaction test using lead acetate was conducted, almost no reaction was observed. These experiments were conducted continuously over several days, but no decrease in the deodorizing effect was observed, and it was confirmed that the deodorizing ability lasted for a long time.

Similar tests were conducted on the odors of methyl mercaptan, methyl sulfide, ammonia formaldehyde, valeric acid, skatole, and the like. The results of the sensory tests are summarized in Table 1, and the deodorizing effect of the deodorizing porous fine particles was sufficiently recognized.

Example 2 The same procedure as Example 1 was carried out except that 50 parts by weight of stearyl methacrylate was used instead of methyl methacrylate.
Synthesize stearyl methacrylate-based porous particles,
This is immersed in an aqueous solution of cobalt phthalocyanine polycarboxylic acid (aqueous solution concentration 3 g/β, pH 12) and then dehydrated and dried to form porous fine particles containing 3.5% by weight of cobalt phthalocyanine polycarboxylic acid and having a deodorizing function. I got it.

When the porous fine particles were washed again with water and dried, and the amount of cobalt phthalocyanine/polycarboxylic acid released was examined, almost no loss of cobalt phthalocyanine/polycarboxylic acid was observed.

A human sensory test was conducted using the same apparatus as in Example 1 to examine the deodorizing activity of the deodorizing porous fine particles containing cobalt phthalocyanine against various malodors. The results are summarized in Table 1.

Example 3 Instead of 50 parts by weight of methyl methacrylate in Example 1,
Monomethacrylate of 25 parts by weight of methyl methacrylate and 200 parts of polyethylene glycol (commercial product, Bremmer P
E-200) The same procedure as in Example 1 was carried out except that 25 parts by weight was used to obtain hydrophilized methyl methacrylate-based porous 'Jim particles containing polyethylene glycol chains. The fine particles were immersed in an aqueous solution of iron phthalocyanine polycarboxylic acid (aqueous solution concentration 3 g/l, pH 12) and dehydrated and dried. The thus obtained deodorizing fine particles contain approximately 0.06 iron phthalocyanine polycarboxylic acid per 3 g of fine particles.
g tB was held. As in Example 1, the deodorizing performance of the deodorizing porous 'i fine particles was investigated through a human sensory test. The results are summarized in Table 1.

Example 4 Instead of 50 parts by weight of methyl methacrylate in Example 1,
Hydroxyethyl methacrylate-based porous fine particles were synthesized in the same manner as in Example 2, except that 25 parts by weight of 2-hydroxyethyl methacrylate and 25 parts by weight of methyl methacrylate were used, and cobalt phthalocyanine polycarboxylic acid was supported in the same manner as in Example 2. As a result, approximately 0.04 g of cobalt phthalocyanine polycarboxylic acid was supported on 3 g of fine particles. As in Example 1, the deodorizing performance of the deodorizing porous fine particles was investigated through human sensory tests. The results of the deodorization test are summarized in Table 1.

Example 5 Instead of 50 parts by weight of methyl methacrylate in Example 1,
The same procedure was repeated except that 50 parts by weight of styrene and 50 parts by weight of polyethylene glycol dimethacrylate were used to synthesize styrene-based hydrophilic porous fine particles, and cobalt phthalocyanine/polycarboxylic acid was supported in the same manner as in Example 2. However, for 3g of fine particles, cobalt phthalocyanine
Approximately 0.05 g of polycarboxylic acid was supported. As in Example 1, the deodorizing performance of the deodorizing porous fine particles was investigated through human sensory tests. The results of the deodorization test are summarized in Table 1.

The numerical values shown in Table 1 are the results of sensory tests conducted by 10 monitors for each example. In other words, the sensory test was carried out using a 100 liter monitor, containing Table 1 in deodorizing porous fine particles.
Air containing 500 ppm of odor components shown in Figure 1 was passed through the bag, and the participants were asked to smell the gas contained in the bag.The participants were asked to evaluate the odor using the following criteria, and the average value was recorded.

I feel it very strongly 4 I feel it strongly 3 I feel it a little 2 I feel it a little 1 I don't feel it at all 0 In the reference example, 10 monitors similarly smelled each gas before deodorizing it using the porous fine particles of each example. These are the sensory test results I received.

Claims (1)

[Scope of Claims] 1) A porous material having a deodorizing function, characterized in that 0.01% by weight or more of a metal complex having redox ability is supported on porous fine particles having countless continuous pores. Fine particles. 2) The deodorizing function according to claim 1, wherein the metal complex contains at least one selected from metal porphyrin, metal porphyrazine, derivatives thereof, and polymer metal complexes thereof. porous fine particles.