JP5353114B2 - Allylamine cross-linked polymer and deodorant - Google Patents

Description

  The present invention relates to an allylamine crosslinked polymer and a deodorant comprising the polymer.

  As deodorants capable of removing hydrogen sulfide, those using inorganic substances such as activated carbon, silica, zeolite and the like are known.

  Moreover, as a deodorizer which can remove both hydrogen sulfide and an aldehyde type compound, the deodorizer containing a polyvinylamine compound and an inorganic compound is disclosed, for example (patent document 1).

Japanese Patent Laid-Open No. 9-201405

  However, although the deodorizer using an inorganic substance has an effect of removing hydrogen sulfide, the effect of removing an aldehyde compound which is a neutral substance is not sufficient. Further, the deodorant described in Patent Document 1 is obtained by adsorbing polyvinylamine having aldehyde adsorbing ability on a water-insoluble clay such as zeolite, sepiolite, bennite, etc., depending on the pH of the solution at the time of adsorption. The absorptivity of the water changes and is unstable. Furthermore, it takes a lot of time and effort to remove and purify water, residual polyvinylamine and the like from viscous insolubles during production.

  Therefore, the present invention exhibits an excellent adsorptivity to aldehyde compounds and sulfur compounds, is excellent in water resistance and moisture resistance, and can be used as a solid deodorant without being supported on a solid carrier. The object is to provide a polymer.

  The present invention provides an allylamine crosslinked polymer obtained by reacting a resin containing an allylamine unit represented by the following general formula (1) as a repeating unit with a crosslinking agent in the presence of a metal salt.

In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  Since the allylamine cross-linked polymer of the present invention is cross-linked in the presence of a metal salt, it exhibits excellent adsorptivity for both aldehyde compounds and sulfur compounds. The cross-linked polymer produced by the reaction of the resin and the cross-linking agent and then added with a metal salt is significantly reduced in deodorizing ability due to moisture or the like, whereas the allylamine cross-linked polymer of the present invention, That is, a polymer obtained by reacting the above resin with a cross-linking agent in the presence of a metal salt has excellent water resistance and moisture resistance without deodorizing ability being lowered by washing with water or the like. Furthermore, since the allylamine crosslinked polymer can be an insoluble solid, it can be easily used as a solid deodorant without being supported on a solid carrier or the like.

  The resin is preferably a water-soluble resin. By making the resin a water-soluble resin, the above reaction can be performed in a polar solvent containing water. By performing the above reaction in a polar solvent containing water, the deodorizing ability, water resistance and moisture resistance of the allylamine crosslinked polymer are further improved.

  In the resin containing the allylamine unit represented by the general formula (1) as a repeating unit and the crosslinking agent, the amount of the crosslinking agent is 0.5 to 45 mol% with respect to the total molar amount of amino groups in the resin. It is preferable to make it react so that.

  If the amount of the cross-linking agent is less than 0.5 mol%, gelation by the cross-linking reaction may not sufficiently proceed. If it exceeds 45 mol%, most of the amino groups in the resin are subjected to the reaction with the cross-linking agent. As compared with the case where the amount of the crosslinking agent is within the above range, the deodorizing performance of the crosslinked polymer may be lowered.

  Examples of the crosslinking agent include epichlorohydrin, 1,4-butanediol diglycidyl ether, 1,2-ethanediol diglycidyl ether, 1,3-dichloropropane, 1,2-dichloroethane, and 1,3-dibromo. A crosslinking agent containing at least one selected from the group consisting of propane, 1,2-dibromoethane, succinyl dichloride, dimethyl succinate, toluene diisocyanate, acryloyl chloride, and pyromellitic dianhydride can be used.

  These cross-linking agents are not only excellent in crosslinkability with a resin containing an allylamine unit represented by the general formula (1) as a repeating unit, and adsorbability to both aldehyde compounds and sulfur compounds is improved. Water resistance and moisture resistance are significantly improved.

  The allylamine crosslinked polymer described above can be used as a deodorant.

  The deodorant comprising the allylamine cross-linked polymer exhibits excellent adsorptivity to both aldehyde compounds and sulfur compounds and has excellent water resistance and moisture resistance.

  According to the present invention, an allylamine cross-linking compound that exhibits excellent adsorptivity to aldehyde compounds and sulfur compounds, has excellent water resistance and moisture resistance, and can be used as a solid deodorant without being supported on a solid carrier. Coalescence can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The allylamine crosslinked polymer of the present invention comprises a resin containing an allylamine unit represented by the following general formula (1) as a repeating unit (hereinafter sometimes referred to as “allylamine polymer”) and a crosslinking agent in the presence of a metal salt. It is obtained by reacting below. In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  The allylamine crosslinked polymer preferably has a structure in which the main chain in which the allylamine unit represented by the general formula (1) in the allylamine polymer is repeated is chemically or physically crosslinked with a crosslinking agent. The metal salt used during the reaction is contained in the allylamine polymer crosslinked in the form of metal ions or the like.

  In the allylamine polymer, the content of the allylamine unit represented by the general formula (1) is preferably 10% by mass or more, more preferably 30% by mass or more based on the total amount of the allylamine polymer. preferable. Furthermore, the allylamine polymer is preferably an allylamine homopolymer from the viewpoint of water solubility. Examples of the allylamine homopolymer include polyallylamine, poly (N-methylallylamine), poly (N-ethylallylamine), poly (N, N-dimethylallylamine) and the like.

  As the allylamine polymer, a copolymer of an allylamine constituting the allylamine unit represented by the general formula (1) and a monomer copolymerizable with the allylamine may be used. Examples of the allylamines include monoallylamine, N-methylallylamine, N-ethylallylamine, N, N-dimethylallylamine and the like. The monomers copolymerizable with the allylamines include N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N- (2-hydroxyethyl) diallylamine, N- (2-hydroxypropyl) diallylamine. N- (3-hydroxypropyl) diallylamine, N, N-dimethyldiallylammonium chloride, N, N-diethyldiallylammonium chloride, N, N-dipropyldiallylammonium chloride, N, N-dibutyldiallylammonium chloride, vinylpyrrolidone , Dimethylaminoethyl methacrylate, β-methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylonitrile, hydroxyethyl acrylate, vinyl acetate, styrene, acrylic , Vinyl chloride, vinyl isocyanate, methacrylonitrile, methacrylic acid, methyl vinyl ketone, methyl vinyl ether, vinyl pyridine, acrolein, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc. Is mentioned.

  A part of the amino group in the allylamine polymer may form a salt with an acidic compound. Examples of the acidic compound include hydrochloric acid, acetic acid, sulfuric acid and the like.

  As the crosslinking agent, a compound containing at least two functional groups capable of forming a covalent bond with an amino group in the allylamine polymer is preferable. Examples of such functional groups include halogen groups, aldehyde groups, epoxy groups, carboxyl groups, acid anhydride groups, acid halide groups, N-chloroformyl groups, chloroformate groups, imide ether groups, amidinyl groups, and isocyanates. Group, vinyl group and the like. Moreover, since formaldehyde can react with two amino groups to form aminal, it can be suitably used as a crosslinking agent.

  Cross-linking agents include ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, methylene bisacrylamide, and methylene. Bismethacrylamide, ethylenebisacrylamide, epichlorohydrin, toluene diisocyanate, ethylenebismethacrylamide, ethylidenebisacrylamide, divinylbenzene, bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol diglycidyl ether, 1, 2-Ethanediol diglycid Ether, 1,3-dichloropropane, 1,2-dichloroethane, 1,3-dibromopropane, 1,2-dibromoethane, succinyl dichloride, dimethyl succinate, acryloyl chloride, and the like pyromellitic dianhydride is. Among these, epichlorohydrin, 1,4-butanediol diglycidyl ether, 1,2-ethanediol diglycidyl ether (ethylene glycol diglycidyl ether), 1,3-dichloropropane, 1,2-dichloroethane, 1 , 3-dibromopropane, 1,2-dibromoethane, succinyl dichloride, dimethyl succinate, toluene diisocyanate, acryloyl chloride and pyromellitic dianhydride are preferred.

There is no restriction | limiting in particular as said metal salt, For example, the metal salt represented by following formula (2) can be used.
(M ^{a +} ) _n (X ^b− ) _{(an / b)} (2)

  In the formula, M represents a metal, a represents the valence of M, X represents an anion, b represents the valence of X, and an represents the product of the value of a and the value of n.

  In the above formula (2), the metal represented by M is preferably at least one metal selected from the group consisting of Group 8 to Group 12 metals and calcium. Moreover, as said group 8-12 metal, silver, zinc, copper, and iron are preferable from a viewpoint which is further excellent in deodorizing property.

  As the anion represented by X in the above formula (2), for example, a halogenated anion, a sulfate anion, a nitrate anion, a carboxylate anion and the like can be used. Among these, when using a solvent at the time of a crosslinking reaction, a halogenated anion is preferable from the viewpoint of good solubility in the solvent.

  The allylamine crosslinked polymer is obtained by reacting an allylamine polymer and a crosslinking agent in the presence of the metal salt (hereinafter, this reaction may be referred to as “crosslinking reaction”).

  The crosslinking reaction may be performed by adding a metal salt before the crosslinking is completed. The allylamine polymer and the crosslinking agent are dissolved or dispersed in a solvent (polar solvent, nonpolar solvent, or a combination thereof), and crosslinking is performed. The reaction can be carried out at an optimum pH above the reaction temperature of the agent. The crosslinking reaction can also be performed by mixing an allylamine polymer and a crosslinking agent in a non-solvent.

  The amount of the metal salt used in the crosslinking reaction is preferably 0.1 to 10 parts by weight with respect to the total amount of the allylamine polymer. When the amount of the metal salt used is larger than this, when a solvent is used during the crosslinking reaction, the metal salt becomes difficult to dissolve in the solvent. Moreover, when the usage-amount of metal salt becomes less than this, deodorizing property may fall.

  The crosslinking reaction is preferably performed in the presence of a solvent. Examples of the solvent include water, a polar solvent, or a mixed solvent of water and a polar solvent. Examples of the polar solvent include methanol, ethanol, DMF, acetonitrile, tetrahydrofuran, and the like. Among these solvents, water or a mixed solvent of water and a polar solvent is preferable, and water is more preferable, from the viewpoint of facilitating post-treatment after the reaction and improving the solubility of the metal salt.

  The amount of the solvent used in the crosslinking reaction is preferably 0.5 to 15 parts by weight with respect to the total amount of allylamine polymer. When the amount of the solvent used is larger than this, the time required for the post-treatment tends to increase. When the amount of the solvent used is smaller than this, the allylamine polymer tends to be difficult to disperse in the solvent.

  In the crosslinking reaction, it is preferable that at least a part of the allylamine polymer is dissolved in the solvent. If the allylamine polymer is dissolved in the above solvent, the deodorizing property, water resistance, and moisture resistance of the allylamine crosslinked polymer tend to be further improved.

  The conditions for the crosslinking reaction can be appropriately selected depending on the allylamine polymer and the crosslinking agent used. For example, the reaction temperature when polyallylamine and ethylene glycol diglycidyl ether are reacted in water in the presence of a metal salt is preferably 5 to 60 ° C, more preferably 10 to 30 ° C.

  The allylamine crosslinked polymer obtained by the above crosslinking reaction is usually a water-insoluble solid and can be suitably used as it is as a solid deodorant. Further, for example, it can be used as a deodorant after being pulverized in a mortar or the like, air-dried, and powdered.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
To 56.81 g of a 20.1% polyallylamine aqueous solution (average molecular weight of polyallylamine: 3000, polyallylamine content: 0.2 mol), 0.57 g of zinc chloride was added and stirred at room temperature to obtain a uniform solution. To this solution, 10.45 g (0.06 mol) of ethylene glycol diglycidyl ether was added and stirred at room temperature to obtain a gel-like crosslinked polymer. The obtained gel-like cross-linked polymer was pulverized in a mortar, air-dried for 1 week, passed through a sieve having a diameter of 590 μm and a diameter of 300 μm, and a cross-linked zinc-containing polyallylamine having a particle size of 300 to 590 μm (zinc-containing allylamine cross-linked polymer). Combined) was obtained.

(Example 2)
In the same manner as in Example 1, 1.5 g of a crosslinked zinc-containing polyallylamine was synthesized, 200 mL of distilled water was added, and the mixture was stirred at room temperature for 1 hour. After the cross-linked product was filtered off with a filter cloth and transferred to a beaker, 200 mL of distilled water was added again and stirred at room temperature for 1 hour. The same washing operation was repeated 10 times, followed by filtration and air drying for 1 week to obtain a washed zinc-containing polyallylamine crosslinked product.

(Comparative Example 1)
10.56 g (0.06 mol) of ethylene glycol diglycidyl ether was added to 56.81 g of a 20.1% polyallylamine aqueous solution (average molecular weight of polyallylamine: 3000, polyallylamine content: 0.2 mol) at room temperature. To obtain a gel-like crosslinked polymer. The obtained gel was pulverized in a mortar and air-dried for 1 week, and then passed through a sieve having a diameter of 590 μm and a diameter of 300 μm to obtain a crosslinked polyallylamine having a particle diameter of 300 to 590 μm. 1.0 g of 5% zinc chloride aqueous solution was added to 1.0 g of this polyallylamine crosslinked polymer, mixed and air-dried for 1 week to obtain a polyallylamine crosslinked polyallylamine added after zinc.

(Comparative Example 2)
A cross-linked polyallylamine having a particle size of 300 to 590 μm was produced in the same manner as in Comparative Example 1, 1.5 g of 5% zinc chloride aqueous solution was added and mixed, 200 mL of distilled water was added, and the mixture was stirred at room temperature for 1 hour. The crosslinked polymer was filtered off with a filter cloth, transferred to a beaker, 200 mL of distilled water was added again, and the mixture was stirred at room temperature for 1 hour. The same washing operation was repeated 10 times, followed by filtration and air drying for 1 week to obtain a post-zinc added polyallylamine crosslinked product after washing.

(Comparative Example 3)
In the same manner as in Comparative Example 1, a crosslinked polyallylamine having a particle size of 300 to 590 μm was produced as a crosslinked polyallylamine without addition of metal.

(Evaluation test)
About the crosslinked body obtained in Examples 1-2 and Comparative Examples 1-3, the deodorizing performance with respect to hydrogen sulfide, methyl mercaptan, and acetaldehyde was evaluated by the following method.

  The crosslinked body and ion-exchanged water having the same weight as the crosslinked body were mixed in a petri dish. The petri dish was placed in a 300 mL conical beaker together with a stirrer, the mouth of the conical beaker was sealed with parafilm, and a certain amount of malodorous gas (hydrogen sulfide, methyl mercaptan or acetaldehyde) was injected. The hole of the syringe needle at the time of bad odor gas injection was closed with vinyl tape, and the inside of the conical beaker was stirred with a magnetic stirrer. After 1 hour, the concentration of residual malodorous gas in the conical beaker was measured using a detector tube manufactured by GASTEC (hydrogen sulfide detector tube No. 4L, methyl mercaptan detector tube No. 71, acetaldehyde detector tube No. 92M). It was measured.

  Moreover, the measurement of the residual malodorous gas concentration of the blank was performed as follows. A stirrer was placed in a 300 mL conical beaker, the mouth of the conical beaker was sealed with parafilm, and a certain amount of malodorous gas (hydrogen sulfide, methyl mercaptan or acetaldehyde) was injected. The hole of the syringe needle at the time of bad odor gas injection was closed with vinyl tape, and the inside of the conical beaker was stirred with a magnetic stirrer. After one hour, the concentration of residual malodorous gas in the blank in the conical beaker was measured using the detector tube manufactured by Gastec.

Based on the residual gas concentration, the deodorization rate was calculated from the following formula (3).
Deodorization rate (%) = {(B−S) / B} × 100 (3)

  In the formula, S represents the residual malodorous gas concentration (ppm) in the presence of the crosslinked product, and B represents the residual malodorous gas concentration (ppm) in the blank.

  In the above evaluation test, the amount of the crosslinked product used was 0.02 g when hydrogen sulfide was used as the malodorous gas, and 0.1 g when methyl mercaptan or acetaldehyde was used as the malodorous gas.

  The results of the evaluation test are shown in Table 1.

  The crosslinked product of Example 1 showed a high deodorization rate with respect to hydrogen sulfide, methylcaptan and acetaldehyde. The crosslinked product of Example 2, which was washed with water, showed almost no decrease in deodorization rate and showed a high deodorization rate.

  Although the crosslinked product of Comparative Example 1 showed a high deodorization rate with respect to hydrogen sulfide, methylcaptan and acetaldehyde, the deodorized rate of the crosslinked product of Comparative Example 2 which was washed with water was greatly reduced.

From the above results, it was confirmed that the crosslinked product of Example 1 was superior in water resistance and moisture resistance as compared to the crosslinked product added with metal after the crosslinking reaction (Comparative Example 1).

Claims (5)

An allylamine crosslinked polymer obtained by reacting a resin containing an allylamine unit represented by the following general formula (1) as a repeating unit with a crosslinking agent in the presence of a metal salt represented by the following formula (2) .

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
(M ^{a +} ) _n (X ^b− ) _{(an / b)} (2)
[Wherein, M is at least one metal selected from the group consisting of Group 8 to Group 12 metals, a represents the valence of M, X represents the anion, and b represents the valence of X. An represents the product of the value of a and the value of n. ]   The allylamine crosslinked polymer according to claim 1, wherein the resin is a water-soluble resin.   The allylamine crosslinked polymer of Claim 1 or 2 made to react so that the quantity of the said crosslinking agent may be 0.5-45 mol% with respect to the total molar amount of the amino group of the said resin.   The crosslinking agent is epichlorohydrin, 1,4-butanediol diglycidyl ether, 1,2-ethanediol diglycidyl ether, 1,3-dichloropropane, 1,2-dichloroethane, 1,3-dibromopropane, 4. The method according to claim 1, comprising at least one selected from the group consisting of 1,2-dibromoethane, succinyl dichloride, dimethyl succinate, toluene diisocyanate, acryloyl chloride and pyromellitic dianhydride. Allylamine cross-linked polymer.   The deodorizer which consists of an allylamine crosslinked polymer of any one of Claims 1-4.