JPS61258806A - Polymeric material with deodorant function - Google Patents

Abstract

PURPOSE:To obtain a polymeric material with semi-permanent deodorant function, capable of simultaneously decomposing both water-soluble and water- insoluble odoriferous matters in a short time, by carrying specific amount of metallic phthalocyanine on a polymer. CONSTITUTION:A metallic phthalocyanine is connected, normally by Friedel- Crafts reaction, to a polymer (e.g., a copolymer from styrene and vinylpyridine) and then coordinate bond formation is accomplished between the central metal M (e.g., Fe, Co) of said metallic phthalocyanine and the lone pair of electrons in the atoms (e.g., N) present in either the main chain on side chain of said polymer to crosslink the polymer, thus obtaining the objective polymeric material with 0.5-20wt% of said metallic phthalocyanine carried thereon. EFFECT:For example, since the central metal M of the metallic phthalocyanine represents a 5-coordinated, divalent or trivalent spin state, an electron state will be provided in which odoriferous matters are easy to coordinate with said metallic atom M.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymeric substance having a deodorizing function that changes a substance emitting an unpleasant odor into an odorless substance.

[Conventional technology]

Conventional deodorization treatment methods for bad odors include activated carbon adsorption, catalytic combustion, ozone or chemical liquefaction,
Neutralization methods, bacterial decomposition methods, and enzyme decomposition methods are known, but all of them have shortcomings such as short-lasting deodorizing ability, low deodorizing efficiency, and secondary contamination. .

Malodorous substances in daily life include ammonia,
These include amines, hydrogen sulfide, mercaptans, indoles, and carbonyl compounds. These substances are described in Japanese Unexamined Patent Publication No. 5
As described in Japanese Patent No. 5-32519, biological enzymes act as oxidation catalysts and are decomposed. Among biological enzymes, metalloporphyrins and metalvolfrazins are excellent, and they are advantageous in that they can be synthesized artificially and are relatively easily available, as disclosed in JP-A-50-54590, for example. It is.

The invention of using metal porphyrins and metal porphyrins as a deodorant is based on the invention of the present inventors,
This is already known from the above-mentioned Japanese Unexamined Patent Publication No. 55-32519. The disclosed deodorant is superior compared to other deodorants.

[Problem that the invention seeks to solve]

The inventor of the present invention made this result as a result of further research, and was able to decompose water-soluble and water-insoluble foul-smelling substances at the same time and in a short time by using the deodorant disclosed in the above-mentioned publication. The object of the present invention is to provide a deodorizing polymeric substance that is a type of deodorant that is improved in this respect.

[Means for solving and resolving problems]

Through research on the use of metal porphyrins and metal porphyrins as deodorants, the present inventor found that the most excellent deodorant is the metal phthalocyanine shown in the structural formula in Figure 1. . At the same time, we obtained the following knowledge.

In order for a deodorant to act as an oxidation catalyst on all kinds of odor substances and decompose them in a short time, it is necessary to have the following functions.

■Function as oxidase Oxidation reaction by molecular oxygen (autooxidation effect by oxygen in the air).

2(Sub)H+ 02 2 5ub-Sub+
Sub in the formula in 8202 is 5ubstrate
Abbreviation for (substrate).

NPC: Metal phthalocyanine (Sub) H: Off-odor substances such as H2S, R-SH (
Mercaptan derivative), R-CHO (aldehyde derivative), R-N)12 (amine derivative), R-OH (alcohol derivative) Sub-9ub: Oxidation product ■Function as peroxidase Hydrogen peroxide generated in above ■ (Honguchi) oxidation reaction (
(This occurs in a chain reaction to ■).

2(Sub)H+ 8202" -!-!-E-)
5ub-Sub +2820 ■ Function as oxygenase For example, reaction to oxidize and cleave malodorous substances consisting of heterocyclic compounds such as indole nucleus and pyridine nucleus. In the case of indole nuclei, the following reaction occurs.

The products resulting from oxidative cleavage may be further decomposed by the reactions (1) and (2) above. In addition, malodorous substances (Sub) H are easily released, including heterocyclic compounds such as indole nuclei.
It is characterized by having an H group.

The reaction mechanisms (1) to (4) above, centering on metal phthalocyanine, will be explained with reference to (a) to (f) in FIG.

Note that Fe-Pc shown in FIG. 2 is shown with the three-dimensional structure omitted when the central metal M of the metal phthalocyanine shown in FIG. 1 is Fe.

(a) A malodorous substance (S) is present in the catalytic reaction zone of metal phthalocyanine.
ub) H approaches.

(b) The malodorous substance (Sub) H coordinates with the metal phthalocyanine metal atom Fe(I[I) to form a complex.

(C) 02 (H202 in the case of reaction (■)) is adsorbed.

(d) Electron e moves and Fe(III) becomes Fe(II)
So Sub゛ and H2O2 (or H2O for the reaction of ■)
) leaves. Sub' immediately reacts with the other (7) Sub' to produce Te5ub-Sub. In other words, the above ■
(or ■) reaction occurs.

(e) Electron e moves from Fe(II) to nearby 02.

(f) Fe(II) returns to the original Fe(m) and generates superoxide radical oxygen 02-.

The generated 02- decomposes the malodorous substance (Sub)H according to the following formula (see reaction ① above).

2(Sub)H+ 02 5ub-Sub +
The H2O2 reactions (1) to (2) above occur through the circulation mechanisms (a) to (f), and it is difficult for the metal phthalocyanine itself to sufficiently exhibit its catalytic function. That is, the first
If -X in the structural formula shown in the figure is a group with a small steric structure, the metal phthalocyanine dimer shown in Figure 5 (A) or the metal phthalocyanine oxodimer shown in Figure 5 (CB) will result. Catalytic activity will be weakened.

To this end, the present invention prevents the formation of such dimers by binding metal phthalocyanine to a polymer and causing steric hindrance between the metal phthalocyanines by the polymer chain. However, even if the metal phthalocyanine is bound to a polymeric substance, if the amount of the metal phthalocyanine bound is too large, the probability of close contact between the metal phthalocyanines increases and dimers are generated, which may actually worsen the deodorizing efficiency. On the other hand, if the amount of metal phthalocyanine is too small, the deodorizing effect cannot be maintained.According to the results of various experiments, the appropriate amount of metal phthalocyanine is 0.5 to 20% by weight based on the total amount. More preferably, it is 1.0 to 10% by weight.

The bond between the polymer and metal phthalocyanine is as follows. For example, a copolymer of styrene and vinylpyridine as a polymer in which -X (see Figure 1) of metal phthalocyanine is substituted with at least one carbonyl chloride group, preferably 2 to 8 carbonyl chloride groups, is subjected to a free delta shift reaction. Combine (see formula below).

Pc Furthermore, the central metal M of metal phthalocyanine (MPc) and the N of the pyridine nucleus form a coordination bond. As a result, a polymer material crosslinked with metal phthalocyanine is produced, as shown in FIG. The central metal M of the metal phthalocyanine at this time is five-coordinated.

The central metal M of metal phthalocyanine is Fe, Go, Mn
, Ti, V, Ni, Cu, Zn, Mo, W, and Os. Fe and Go are particularly preferred since they can easily create a divalent or trivalent high spin state or a divalent and trivalent mixed valence state.

Also preferred is a mixture of Fe and Co.

The polymer to which the metal phthalocyanine is bonded is, in addition to the above-mentioned copolymer of styrene and vinylpyridine, for example, a copolymer of styrene and vinylimidazole, vinylarylamine, acrylic acid, methacrylic acid, and the like. Furthermore, other vinyl groups such as vinyl chloride may be copolymerized.

At least one group, preferably 2 to 8 groups, are substituted on -X of the metal phthalocyanine, in addition to the carbonyl chloride group mentioned above, examples include a hydroxyl group, a carboxyl group, an amide group, a chloromethyl group, and a sulfone group. .Also, except where the above groups of -X are substituted, hydrogen groups,
It can be any alkyl group, alkyl silicon group, etc.

[Effect]

As mentioned above, since the metal phthalocyanine is bound to the polymer substance, the metal phthalocyanine is hindered by the polymer chain and dimers (see Figure 5) are not easily formed. Since the amount is 20% by weight, the amount of catalyst is appropriate, and the probability of proximity between metal phthalocyanines is also small, so that very few dimers are produced. Therefore, the function of the oxidation catalyst can be fully exhibited.

Furthermore, since the central metal M of the metal phthalocyanine is in a penta-coordinated divalent or trivalent high spin state, as mentioned above (b
) (see Figure 2), the malodorous substance (Sub) H is in an electronic state that facilitates coordination with the metal atom M□ in the metal phthalocyanine. For example, in the iron phthalocyanine shown in Figure 3, Fe(m) 1 to 5 are in a state of coordination bonding, so the malodorous substance (Sub) H is likely to coordinate to the 6 position, and the The reactions of the circulation mechanism described in (a) to (f) in Figure 2 are likely to occur, therefore, the above-mentioned ■ to ■
reaction is more likely to occur quickly.

Since there are parent wood groups and hydrophobic groups in a polymeric substance, the vicinity of the former becomes the parent tree region, and the vicinity of the latter becomes the hydrophobic region. Therefore, water-soluble off-flavor substances enter the former region, water-insoluble off-odor substances enter the latter region, and the metal phthalocyanine decomposes both of these off-odor substances.

(Effects of the Invention) The polymeric substance of the present invention can decompose almost all of the malodorous substances present in the daily life of humans, regardless of whether they are water-soluble or water-insoluble, due to the reactions described in (1) to (2) above.

Furthermore, the substance itself does not absorb or store off-flavor substances, nor is it consumed in the deodorizing reaction system. Therefore, the deodorizing effect can be maintained semi-permanently.

Since it is a polymeric substance, it can be in the form of fibers, films, chips, rubber, powders, or objects by itself, copolymerized with other polymeric substances, or blended with other polymeric substances. Can be formed into structures. It can also be mixed into paper. It can also be mixed into paints and the like. Therefore, depending on the respective shape, for example clothing, bedding, carpets.

It can be used in all kinds of polymer materials currently used, such as building materials, filters for air purifiers and sewage treatment equipment, packaging materials, and containers, and can be given a deodorizing function.

〔Example〕

Example 1 40g of copolymer of styrene and vinylpyridine and Fe(m
)-phthalocyanine tetracarbonyl chlorite 20
10 g of aluminum chloride is added to 10 g of nitrobenzene solution, and the mixture is stirred at room temperature for about 5 hours to react (Friedel-Crafts reaction). The reaction product is extracted with n-hexane, and further extracted with benzene using a Tuxhlet extractor until nitrobenzene is no longer detected. The product was filtered and washed with an aqueous alkaline solution to remove unreacted Fe(m)-phthalocyanine tetracarbonyl chloride, and the reaction product (see Figure 3) was dissolved in methanol and then precipitated in ether. It is purified by

Example 2゜Fe(m)-phthalocyanine tetracarbonyl chloride is bonded to the copolymer of styrene and vinylimidazole using a copolymer of vinylimidazole instead of the copolymer of vinylpyridine in Example 1, but under the same conditions as above. A polymer material with

The polymer substances obtained in Examples 1 and 2 above were packed in a glass tube, and the vapors of malodorous substances such as ammonia, amines, hydrogen sulfide, and mercaptans were passed through the tubes, and the gas chromatograph examination revealed that these substances were well decomposed. showed that it had been done. Performance did not deteriorate at all even after one year of continuous testing. Furthermore, it has received very good reviews for natural foul-smelling substances such as manure, fish pulp, and sewage sludge. For evaluation, 1 of the above gas chromatographs was used.
In addition, we have also conducted sensitivity tests using monitors, and in these tests we have obtained better evaluations than conventional deodorants.

[Brief explanation of the drawing]

Figure 1 shows the structural formula of metal phthalocyanine, Figure 2 explains the reaction mechanism of metal phthalocyanine, Figure 3 shows an example of a structure in which metal phthalocyanine is bonded to a polymer, and Figure 4 The figure is a schematic diagram explaining the three-dimensional structure of metal phthalocyanine, and FIG. 5 is a diagram showing the structure of a dimer of metal phthalocyanine.

Claims (1)

[Claims] The central metal of the metal phthalocyanine bonded to the polymer coordinates to the lone pair of an atom in the main chain or side chain of the polymer, and the polymer is crosslinked, and the polymer has 0.
A polymer substance having a deodorizing function, characterized in that 5 to 20% by weight of the metal phthalocyanine is supported.