JPH02235802A - Adsorbent of microorganism - Google Patents

Abstract

PURPOSE:To obtain an adsorbent useful for removing microorganisms in water and air, on the surface of solid, etc., as a microorganism immobilized carrier for biosensor, comprising a crosslinked polymer compound prepared from a vinylpyridine and a polyfunctional vinyl monomer as an active ingredient. CONSTITUTION:An adsorbent of microorganism comprising a crosslinked polymer compound having a repeating unit shown by the formula (R1 to R3 are H, 1-20C straight-chain or branched chain saturated or unsaturated aliphatic hydrocarbon group, aralkyl, hydroxyalkyl or trialkoxysilylalkyl; X<-> and Y<-> are anion; n is 1-20) as an active ingredient. Microorganisms in water, in air, on the surface of solid, etc., can be readily sterilized and removed by bringing the preparation into contact with drinking water, various kinds of service water, air, the surface of solid, etc. The polymer compound is obtained by treating a copolymer of a vinylpyridine and a polyfunctional vinyl monomer with an alkyl dihalide, introducing an alkyl halide to the N-position and reacting the reaction product with a tertiary amine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a microbial adsorbent that exhibits excellent microbial adsorption properties for disinfecting water, air, solid surfaces, etc., and has high disinfecting and sterilizing performance.

[Conventional technology]

Removal of microorganisms floating in, attached to, and propagating in various types of water, wastewater, the surfaces of buildings, and even the air is extremely important in terms of environmental hygiene and increasing the durability of buildings.

Conventionally, for this purpose, a method using a microbicide such as chlorine, a method of killing microorganisms by heating, and a method of phosphorus filtration using a membrane or filter have been mainly used. However, methods that use microbicides generally leave behind harmful substances, so it is
It cannot be applied to transportation equipment or drinking water, and methods using heating, membranes, and filters require bulky equipment and are economically inconvenient. Recently, the following formula has been proposed to easily remove microorganisms in the environment (in the formula, R is a benzol group s C4~Cll-alkyl" group or pentafluorophenylmethyl i X' is a chlorine atom or a bromine atom) There has been provided a biocontrol agent containing as an active ingredient an insoluble polymeric compound having a birizonium group, which is obtained by polymerizing a compound represented by the following formula and a zovinyl compound such as zovinylbenzene at the vinyl group (Japanese Patent Publication No. 41644/1983). issue〕.

[Problem to be solved by the invention]

However, when using the microbial control agent described in Japanese Patent Publication No. 62-41641, even if the microbial control agent is sufficiently contacted with a bacterial suspension of 107 to 108 individuals/d, all bacteria are removed from the liquid. It takes more than 6 hours to be removed, and under the same conditions 10'' to 10' individuals/d
When contacting with a bacterial suspension of

Furthermore, when using the pesticidal agent obtained by the method disclosed in Japanese Patent Publication No. 62-41641, there is a problem in that although microorganisms in the liquid are adsorbed to the pesticide, no bactericidal effect can be expected.

[Means to solve the problem]

Under these circumstances, the inventors of the present invention were able to obtain a microbial adsorbent that solved the above-mentioned drawbacks.As a result of various studies, the present inventors found that by introducing a substituent having a quaternary ammonium group at the N-position of vinylvirison, The present invention was completed by discovering that a microbial adsorbent with high antibacterial and bactericidal effects can be obtained.

That is, the present invention has the following general formula (wherein, Rl
%R, each independently represents a hydrogen atom, C! ~CH represents a linear or branched saturated or unsaturated aliphatic hydrocarbon group, aralkyl group, hydroxyalkyl group, alkoxyalkyl group, monoaryloxyalkyl group, or trialkoxysilylalkyl group, and Xe and Ye are the same or different anions, and n is an integer of 1 to 20.] The present invention provides a microbial adsorbent containing as an active ingredient a crosslinked polymer compound having a repeating unit represented by the following formula.

The polymer compound used in the microbial adsorbent of the present invention is produced by copolymerizing vinylvirisons and a polyfunctional pinyl monomer in the presence or absence of another vinyl monomer that can be copolymerized with them. Next, a halogenated alkyl group is introduced into the N-position of the vinyl bilizo y unit by the action of a zohalogenated alkyl group, and this I
It is produced by reacting a C-tertiary amine.

As the pinyl♂lysines used here, 2-vinylpyrizone, 3-pinylbilizone, and 4-vinylpyrizone are preferably used, but vinylpyridone derivatives having other substituents may also be used.

Examples of polyfunctional vinyl monomers include zopinylbenzene; ethylene glycol zo(meth)acrylate, buta-7zool zo(meth)acrylate, trimethylolzolonotri(meth)acrylate, pentaerythritol zo(meth)acrylate, pentaerythritol tetra( meth]acrylate, polyfunctional (meth)acrylates such as ?lyethylene glycol zo(meth)acrylate; methylenepis(meth)acrylamide, 7″ lopylenepis(meth)acrylamide, N, N'-(1
．． Polyfunctional (meth)acrylamides such as 2-zohydroxyethylene)bis(meth)acrylamide and N,N'-(carximethylene)bis(meth)acrylamide can be used.

Examples of other copolymerizable vinyl monomers (copolymerizable vinyl monomers) include styrene, p-methylstyrene%
Styrenic monomers such as p-chlorosterene; Acrylic ester heptanomers such as ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, somemetelaminoethyl acrylate, zoethylaminoethyl acrylate, 2-hydroxyethyl acrylate; methacryl Methyl ester monomers such as methyl acid, ethyl methacrylate, lauryl methacrylate, zometelamine ethyl methacrylate, zoethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate;
Liethylene glycol mono(meth)acrylate: Alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Vinyl ester monomers such as vinegar pinyl and butyrin pinyl; N-methylacrylamide%N-methylacrylamide, N-methylmethacrylamide, N
- N-alkyl-substituted (meth)acrylamides such as ethylmethacrylamide and N-butylmethacrylamide; nitrile heptanomers such as acrylonitrile and methacrylonitrile, but they are essentially compatible with vinylbilisons. If so, the monomers are not limited to the above monomers. These monomers can be used alone or in combination of two or more.

The blending molar ratio in copolymerization of vinylvirison, polyfunctional vinyl monomer, and copolymerized pinyl monomer is from 50 to
The ratio is preferably about 95:5 to 50:0 to 45.

As the copolymerization method, conventionally known bulk polymerization, solution polymerization, suspension polymerization, etc. can be used.

In the reaction between the obtained copolymer and the alkyl zohalogenide, the alkyl zohalogenide in an amount of 1 to 5 molar equivalents was divided into 1.5 to 4.0 molar equivalents based on the group in the copolymer,
In the presence of a solvent such as methanol or ethanol, normal pressure%50
This is done by mixing at ~70°C.

Further, by reacting the halogenated alkyl substituted product obtained above with a predetermined tertiary amine, the crosslinked polymer compound of the present invention can be obtained.

As the zohalogonated alkyl, zono1logonated alkyl such as zochlor, zoprome or shodine of 01 to cztt is used.

Examples of tertiary amines include saturated or unsaturated aliphatic tertiary amines such as trimethylamine, triethylamine, methylzoetheramine, N-dodenruzomethylamine, N-dodecenylzomethylamine, and N'-octylzomethylamine. Aromatic tertiary amines such as N-pencylzomethylamine and N-7enethylmethylamine; Oxyalkylamines such as tri(hydroxylethyl)amine/, bis(hydroxyethyl)methylamine; N,N -Silylalkylamines such as -somether-3-trimethoxysilylderovylamine, N-methyl-N-ethyl-3-trimethoxysilylzolopylamine, etc. are used. Among these, tertiary amines having a trimethoxysilyl group are used. The polymer compound obtained using the tertiary amine also has the advantage of further improving the bactericidal performance.These tertiary amines can be used alone or in combination of two or more.

Furthermore, the obtained polymer compound is subjected to ion exchange according to a known method, and counter anions are changed to halogen ions, halogenite ions, hypohalonite ions, nitrate ions, nitrite ions, disulfite ions, and thiosulfite ions. , phosphate ion sp-}luenesulfonate ion/% dodecyl sulfonate ion, acetic acid ion, dodecyl phosphate ion, etc.

The microbial adsorbent of the present invention can take the form of powder, granules, fibers, film, etc. depending on the method for producing the polymer compound.

The microbial adsorbent of the present invention can be used, for example, as follows. That is, when removing microorganisms from liquids such as drinking water and various types of water, the microorganism adsorbent of the present invention can be directly added to the water, or a device or fiber filled with the microorganism adsorbent in the form of powder or granules can be used. The water to be treated can be passed through a device equipped with a sheet-like microbial adsorbent. Furthermore, when removing microorganisms floating in a gas such as air, the gas may be passed through a device equipped with the microorganism adsorbent. In the case of removing microorganisms adhering to a solid surface, this can be accomplished, for example, by lightly wiping the surface with a fibrous microorganism adsorbent.

〔Effect of the invention〕

The microorganism adsorbent of the present invention is brought into contact with either a bacterial suspension of 107 to 10' population/d or a bacterial suspension of 103 to 104 population/1 under the conditions described in Japanese Patent Publication No. 62-41641. Even when the microorganisms were removed, all the bacteria in the suspension were adsorbed within 2 to 3 hours.

Furthermore, it was observed that the cell activity of microorganisms adsorbed to the microorganism adsorbent of the present invention was reduced or killed. This is thought to be due to the effective K action of the quaternary ammonium base contained in the side chain of the polymer compound.

Therefore, the microbial adsorbent of the present invention can easily sterilize and remove slag in water, air, and solid surfaces by contacting it with drinking water, cage water, air, and solid surfaces. It is useful for purposes such as environmental hygiene and improving the durability of city structures. Furthermore, the microorganism adsorbent of the present invention can be used as a microorganism immobilization carrier for bioreactors or bioreactors by taking advantage of its large microorganism adsorption ability.

〔Example〕

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of 1-(N-methyl-N-penzoldodecylammonioclovir)-4-vinyl birizonium bromide/sterene/zopinylbenzene copolymer: (1) Stirring device, condenser, thermometer, nitrogen introduction 1j se with tube, 1? Pour 500f of water into a Ruggle flask, add 10t of calcium carbonate powder, and add 150 ml of water.
Stir at a speed of rpm to ensure uniform dispersion. In this state, add 105 f of 4-pynylpyridone, 10 styrene.
? , 13t of zovinylbenzene, 1f of azobisimptilonitrile, and 100f of methyl benzoate, and then stirred at 80° C. with continued stirring at a speed of 150 rpnn. It was heated for f. The nine polymer beads obtained were separated and rinsed with 1% acetic acid to dissolve and remove calcium carbonate, followed by repeated washing with water and 1% sodium chloride, finally washing with ethanol, and then vacuum drying to obtain 4-vinylpyridone. /sterene/zovinylbenzene copolymer spherical particles were obtained. Yield: 110 f, average dry particle size of copolymer particles: 200 μm, nitrogen content: 10%.

These copolymer particles are referred to as vinylbilison polymer (1).

1+) Next is the vinylvirison mentioned above? Rimmer (1):
Mf? fMeI'/-le10 0 fVc@turbidity? , this r1. 3-zogromozoro, 9 soft addition, 60
It was heated at ℃ for 5 hours. The polymer beads were separated by P, washed with ethanol, and then vacuum dried to obtain polymer particles in which the pyrizo/group was replaced with an N-3-promodelopyl birizonium group (counter ion: bromide ion). Ta. Yield 44f. (i) Next, the above birizonium boly-r-particles 21
It was suspended in 100t of ttl-ethanol, and N-medel-N-pesoldodecylamine 130F was added to it to give a suspension of 8%
Heated at 0°C for 6 hours.

? The remer beads were isolated by P separation, washed with ethanol, and then dried under vacuum to remove the C pyrizone groups.
- (N'-Methyl-N'-benzododecyl ammonioderovil) The title polymer particles were obtained in which the birizonium group (counter ion: bromide ion) was replaced. Yield 482.

Synthesis Examples 2 to 9 Woodcutter's copolymerized vinyl heptanomers shown in Table 1 below,
Polyfunctional vinyl monomer, zohalogenated alkyl and 3
The same operation as in Synthesis Example 1 was carried out using grade amine, and spherical particles of vinyl birizonium copolymer (average particle size 10-80
0μ-) 1k obtained.

Example 1 Escherichia coli was suspended in 0.15 molar saline to a concentration of 6.5 x 1 G' population/1, and 20 m of this suspension was preliminarily diluted with saline at 37°C. Swollen 5?
(22 by dry weight) of 1-(N-methyl-N-pensyldodecylammoniozolopyl)-4-vinylpyrizonium gromide/styrene-4zovinylbenzene copolymer (polymer particles obtained in Synthesis Example 1) ) and heat to 35 to 37℃.
．． Stirring was continued at a speed of 100-120 rpm. As a result, after 1.2 and 3 hours, the number of Escherichia coli in the suspension was 3.2 and 3 hours, respectively. IX10'. 1. O x 1
After that, the polymer particles adsorbed with E. coli were cultured on an agar medium, but no bacterial growth was observed, and the coli that had been adsorbed to the polymer particles died. In addition, the time required for 99.9% of the initial population of E. coli to be absorbed by the adsorbent (this is assumed to be the bacterial adsorption capacity) was 24 minutes.

Examples 2 to 9 In the same manner as in Example 1, the bacterial adsorption ability and bactericidal ability of the nine-pinylpyrizonium copolymers obtained in Synthesis Examples 2 to 9 were evaluated. The results are shown in Table 1.

Comparative Example 1 Escherichia coli was suspended in physiological saline at a concentration of 6.5 x 10' population/1, and 37
5F (2F dry weight) swollen with saline at °C
Add the 1-benzol-4-vinylbilizonium gromide/zovinylbenzene copolymer and heat at 35-37°C, 100°C.
Stirring was continued at a speed of ~120 rpm. As a result, after 1, 3.5 and 10 hours, the number of E. coli in the suspension was 8.2 x 10' and 2. OX1
0', 1. I X{O', 1. OX1 decreased to 0”.

Furthermore, the adsorption capacity for bacteria was 2.5 hours, which was significantly lower than that of the adsorbent of the present invention, and the bacteria were adsorbed while still alive.

Margin below

Claims (1)

[Claims] 1. The following general formula ▲mathematical formula, chemical formula, table, etc. are present in the molecule▼ (In the formula, R_1 to R_3 each independently represent a hydrogen atom, C
_1 to C_2_0 represents a linear or branched saturated or unsaturated aliphatic hydrocarbon group, aralkyl group, hydroxyalkyl group, alkoxyalkyl group, aryloxyalkyl group or trialkoxysilylalkyl group,
X^■, Y^■ represent the same or different anions, n
represents an integer from 1 to 20) A microbial adsorbent containing a crosslinked polymer compound having a repeating unit represented by the following as an active ingredient.