JP2556362B2 - Method for producing microbial adsorbent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a microorganism adsorbent, and more specifically, a microorganism that can be suitably used for controlling microorganisms from the environment and adsorbing useful microorganisms. The present invention relates to a method for producing an adsorbent.

[Conventional technology]

The phenomenon that microorganisms adhere to polymer surfaces has been known for a long time, and a strongly basic anion exchange resin has been used for collecting microorganisms in water. It is also well known that a microorganism is adsorbed on an ion-exchangeable derivative of a polysaccharide or an ion-exchange resin to be used as a bioreactor.

More recently, as a substituent on N, a benzyl group, C ₄ -C ₁₆
It has been reported that an insoluble polymer compound having a pyridinium group in the form of vinyl polymerization of 4-vinylpyridinium halide having an alkyl group and a pentafluorophenylmethyl group and a divinyl compound is useful as a microbial control agent ( Japanese Patent Publication No. 62-41641).

[Problems to be Solved by the Invention]

The resin disclosed in Japanese Patent Publication No. 62-41641 is certainly an excellent microbial adsorbent, but since a cross-linking resin is synthesized by vinyl polymerization, spherical or amorphous lump-shaped or powdered resin can be easily obtained. Although obtained, it was difficult to obtain a fibrous or film-like resin. Further, in the case of spherical, lumpy or powdery resin, the portion used for adsorption of microorganisms is only the surface thereof, and the inside is not used at all, which is economically disadvantageous. Furthermore, when a vinylpyridine-based crosslinked polymer is quaternized to obtain the resin, the quaternization inside the resin is not sufficient, and the unreacted vinylpyridine moiety is an acid salt formed from a quaternizing agent such as hydrogen halide. In such a case, when the resin is used in an aqueous system, there is a problem that the pH of the aqueous solution changes with time.

Therefore, there has been a demand for providing a microbial adsorbent that overcomes the drawbacks of these conventional techniques.

[Means for solving the problem]

The present inventors have conducted earnest research to develop a microbial adsorbent that adsorbs microorganisms efficiently and can be in a form such as powder, fiber or film that is easy to use, and is relatively inexpensive. As a result, they have found that the above object can be achieved by supporting a specific polypyridinium polymer on a polymer molded product, and completed the present invention.

That is, the present invention provides a water-insoluble polymer molded product having a halomethyl group represented by the following formula XCH ₂ — (wherein X represents a chlorine atom, a bromine atom or an iodine atom) in the molecule (hereinafter, “halomethyl A vinyl pyridine homopolymer or a copolymer of vinyl pyridine and another monomer (hereinafter referred to as “vinyl pyridine polymer”).
The halomethyl group and the pyridine moiety are subjected to a quaternization reaction, and then the unreacted pyridine moiety of the resulting product is converted into a benzyl group, a phenethyl group, a carbon number of 1 to 1 by its alkyl group. The present invention provides a method for producing a microbial adsorbent characterized by quaternizing with an alkylating agent selected from 12 alkyl groups and pentafluorophenylmethyl group.

The halomethyl polymer molded article can be synthesized, for example, by the method described below, and can be appropriately selected according to the form of the intended final product, use conditions, and the like. The halomethyl group referred to herein includes an alkyl group substituted with a halomethyl group such as an ω-monohalogenated alkyl group, an aryl group, and the like.

(A) Chlormethylstyrene, 2-chloroethyl vinyl ether, 2-chloroethyl (meth) acrylate, 2
-Homopolymerization of a monomer having a haloalkyl group such as bromoethyl (meth) acrylate and vinyl chloroacetate,
Alternatively, a method of copolymerizing them with a copolymerizable monomer.

(B) By homopolymerization of a monomer having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminostyrene, or by copolymerization with a monomer copolymerizable therewith. 1,3-dibromopropane in the obtained polymer,
A method of reacting a dihalide such as 1,4-dibromobutane or bischloromethylbenzene.

(C) Homopolymers of aromatic monomers such as styrene, methylstyrene and vinylnaphthalene, copolymers of monomers copolymerizable therewith, or aromatic aromatic ring-like polyesters, polyamides or polyurethanes, and aromatics such as phenolic resins. A method of chlormethylating a polymer having a ring by a known method.

(D) A method of introducing a tertiary amino group into a polymer having an aromatic ring as in the above (c) by utilizing a known Mannich reaction, and then reacting with a dihalide as described in the above (b).

(E) Polyvinyl alcohol, modified polyvinyl alcohol, cellulose, chitin and hydroxyethyl (meth) acrylate or hydroxypropyl (meth)
A polymer compound having a hydroxyl group such as a homopolymer of acrylate and a copolymer with a monomer copolymerizable therewith, chloroacetic acid chloride, bromoacetic acid chloride,
A method for haloacetylation using a known acylating agent such as chloroacetic anhydride, bromoacetic anhydride, monochloroacetic acid, monobromoacetic acid, monochloroacetic acid ester, monobromoacetic acid ester.

(F) A method of reacting a polymer compound having a hydroxyl group as in (e) above with epichlorohydrin or epibromohydrin.

(G) A method of forming an acetal bond between a polymer compound such as polyvinyl alcohol, modified polyvinyl alcohol and vinylon and chloracetaldehyde.

Examples of the vinylpyridine-based polymer used in the present invention include 4-vinylpyridine, 3-vinylpyridine, homopolymers of 2-vinylpyridine and copolymers thereof, and styrene and derivatives thereof copolymerizable with monomers thereof. Copolymers with monomers such as (meth) acrylic acid esters, (meth) acrylamide and its derivatives, and (meth) acrylonitrile can be used, but 60 mol% or more of vinyl pyridine is used to develop high microbial adsorption capacity. What is contained is desirable.

The vinylpyridine polymer used in the present invention preferably has a molecular weight of about 1,000 to 1,000,000.

These vinylpyridine-based polymers can be produced by conventionally known methods such as solution polymerization and suspension polymerization.

The quaternization reaction of the halomethyl polymer molded product and the vinylpyridine-based polymer is carried out by using alcohols such as methanol, ethanol, propanol, chloroform, dichloromethane, N, N-dimethylformamide, N, N-dimethylacetamide or dimethyl sulfoxide. It can be carried out by bringing a halomethyl polymer molded product into contact with a solution obtained by dissolving a vinylpyridine polymer in a solvent. Contact between the two should be done by suspending the halomethyl polymer molding in the vinylpyridine polymer solution or by passing the vinylpyridine polymer solution through a container filled with the halomethyl polymer molding. You can

The reaction between the halomethyl polymer molded product and the vinyl pyridine-based polymer may be carried out at a temperature at which quaternization of pyridine with an alkyl halide is usually performed, for example, at a temperature of 40 to 100 ° C.

The quaternization of the unreacted pyridine moiety of the vinyl pyridine-based polymer supported on the surface of the polymer molded product by the above method is carried out by benzyl halide such as benzyl chloride, benzyl bromide and benzyl iodide and its aromatic ring substitution. , Phenethyl chloride, phenethyl bromide, phenethyl iodide, halogenated phenylethyl and its aromatic ring-substituted products, pentafluorophenylmethyl chloride, pentafluorophenylmethyl bromide, pentafluorophenylmethyl iodide Such as halogenated pentafluorophenylmethyl halides, alkyl halides having 1 to 12 carbon atoms, disulfate esters of alcohols having 1 to 12 carbon atoms, p-toluenesulfonic acid ester, trifluoromethanesulfonic acid ester, etc. Alkylating agent The reaction may be carried out under the conditions where grading is usually performed.

Unlike the quaternization reaction of cross-linked vinylpyridine polymer, the quaternization reaction of the vinylpyridine polymer supported on the surface of the polymer molding is not affected by the diffusion of the quaternizing agent into the polymer. Therefore, it progresses easily.

Before reacting the vinyl pyridine-based polymer with the polymer molded product having the halomethyl group, a part of the vinyl pyridine unit may be quaternized with the alkylating agent in advance. It should be limited to a range that does not hinder the reaction with the polymer molding having a halomethyl group.

Among the microorganism adsorbents thus obtained, particularly preferable ones are those in which the substituents on the nitrogen atom of the pyridinium group are benzyl, phenylethyl, ethyl and methyl, which adsorb microorganisms particularly strongly.

The microbial adsorbent of the present invention can take various forms such as a granular form, a powder form, a lump form, a fibrous form, a cloth form, a film form, and a sponge form depending on the form of the polymer molded product as a carrier. In addition, by selecting the type of carrier, it is possible to have various properties from flexible to hard, hydrophilic to hydrophobic, and select the most suitable one according to the application. can do.

The thus-obtained microbial adsorbent of the present invention has excellent adsorbability for microorganisms such as bacteria, fungi, algae, viruses, and protozoa, and thus removes microorganisms existing in the environment such as the atmosphere and water. Can be used for Specific methods include contacting water containing microorganisms and various aqueous solutions or dispersions, air and various gases, and various organic or inorganic solid surfaces with the above-mentioned microorganism adsorbent, More microorganisms can be removed. At this time, the above-mentioned microorganism adsorbent may be used alone or in combination with a known bactericide / antibacterial agent.

Therefore, the microbial adsorbent of the present invention, drinking water, food, pharmaceuticals, manufacturing water such as cosmetics, pool water, pulp mill,
It can be effectively used for removal of microorganisms contained in water for chemical industries such as fermentation factories, various cooling waters, various wastewaters and treated waters thereof. By passing air through a column or the like filled with the controlling agent, it is possible to prevent the contamination of air with microorganisms in hospital rooms, operating rooms, breeding and cultivation fields for microorganisms, precision machine factories and the like. Furthermore, hygiene products, buildings,
It can also be used to prevent the growth of microorganisms on solid surfaces in public transportation.

Furthermore, the microbial adsorbent of the present invention can be used as a carrier for producing useful substances and for preparing immobilized microbial cells for microbial sensors by utilizing its ability to strongly adsorb microorganisms.

〔The invention's effect〕

The microorganism adsorbent of the present invention is a polyvinylpyridinium-based polymer having a microorganism adsorbing ability supported on the surface of a polymer that has already been molded, and thus can be formed into various shapes suitable for use. It also has good microbial adsorption efficiency.

〔Example〕

Next, the present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited to these examples and the like.

Synthesis Example 1 Synthesis of crosslinked chloromethylstyrene / styrene copolymer polymer beads: 20 g of p-chloromethylstyrene, 70 g of styrene, 10 g of divinylbenzene and 1 g of separable flask equipped with a stirrer, condenser, thermometer and nitrogen introducing tube. A solution consisting of 1 g of lauroyl peroxide and a solution consisting of 380 g of water and 2.3 g of polyvinyl alcohol (Gothenol GH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added. Then 200 rpm
The mixture was heated at 80 ° C. for 8 hours while stirring at the rate of After separating the obtained polymer beads, washing with water, washing with acetone and vacuum drying were carried out to obtain crosslinked chloromethylstyrene / styrene copolymer polymer beads. yield
95g, average particle size of polymer beads 300μm, chlorine content 4.
6%. Let this polymer bead be a haloalkylated polymer (1).

Synthesis Example 2 Synthesis of 1,3-dibromopropane reaction product of polymer beads having tertiary amino group: In the same manner as in Synthesis Example 1, 20 g of dimethylaminoethyl methacrylate, 70 g of styrene, 10 g of divinylbenzene and azobisisobutyronitrile. A solution consisting of 1 g, water 380 g and polyvinyl alcohol 2.3 g (Gohsenol GH-17)
The resulting solution was mixed, stirred and heated at 65 ° C. for 8 hours. The obtained polymer beads were subjected to the same post-treatment as in Synthesis Example 1 and then isolated. Yield 90 g, average particle size of polymer beads 300 μm, nitrogen content 1.6%.

Next, 50 g of the polymer beads described above was suspended in 200 g of isopropyl alcohol, 30 g of 1,3-dibromopropane was added thereto, and the mixture was heated at 80 ° C. for 8 hours. The polymer beads were separated from the reaction mixture, washed with acetone, and then vacuum dried to obtain polymer beads having a 3-bromopropyldimethylammonio group. Yield 51g,
Bromine ion content 5.2%, covalent bromine content 5.2%.
This polymer bead is referred to as a haloalkylated polymer (2).

Synthesis Example 3 Synthesis of chloracetalized polyvinyl alcohol fiber: 50 g of polyvinyl alcohol fiber was added to 200 ml of a mixed solution of 200 g / sodium sulfate, 200 g / sulfuric acid and 400 g / chloracetaldehyde and heated at 50 ° C for 30 minutes. After the reaction, the fiber was taken out, washed with water, and dried in vacuum to obtain a fiber acetalized with chloracetaldehyde. Yield 53g, chlorine content 5.0%. This acetalized fiber is referred to as a haloalkylated polymer (3).

Synthesis Example 4 Synthesis of bromoacetylated cotton cloth: 50 g of cotton cloth was suspended in a solution consisting of 350 g of acetic anhydride, 100 g of bromoacetic acid and a catalytic amount of sodium acetate, and heating was continued at 35 ° C. for 5 hours. After completion of the reaction, the cotton cloth was taken out, washed with acetone and then vacuum dried to obtain a bromoacetylated cotton cloth. Yield 50.5g, covalent bromine content 3.3%. This bromoacetylated cotton cloth is used as a haloalkylated polymer (4).

Example 1 10 g of the haloalkylated polymer (1) obtained in Synthesis Example 1 was converted into poly (4-vinylpyridine) (number average molecular weight 50,000) 10
suspended in a solution consisting of g and 100 g of methyl alcohol,
Heating was continued under reflux for 5 hours. The reaction mixture was separated and the obtained polymer beads were washed by Soxhlet extraction using methanol as a solvent. The washed polymer beads were vacuum dried to obtain polyvinylpyridine-supported polymer beads. Yield 9.8g, nitrogen content 1.2
%. Then, 8.0 g of the obtained polyvinylpyridine-supported polymer beads was suspended in a solution consisting of 8.0 g of benzyl bromide and 50 g of methyl alcohol, and heating was continued under reflux for 5 hours.
The reaction mixture was separated, the obtained polymer beads were washed with acetone, and then vacuum dried to obtain poly (N-benzylvinylpyridinium) bromide-supported polymer beads. Yield 9.25g, bromine ion content 6.5%. From this, it is understood that 290 mg of poly (N-benzylvinylpyridinium) bromide-supported polymer beads were obtained per 1 g of haloalkylated polymer (1). This polymer bead is used as a microorganism adsorbing polymer (1).

Example 2 The same operation as in Example 1 was performed using poly (4-vinylpyridine) (number average molecular weight 1,000) instead of poly (4-vinylpyridine) (number average molecular weight 50,000). Polymer beads with a nitrogen content of 0.40% were obtained. 8.0 g of the obtained polymer beads were suspended in a solution of 8.0 g of ethyl bromide and 50 g of methyl alcohol, and heating was continued under reflux for 5 hours. The reaction mixture was separated, the obtained polymer beads were washed with acetone, and then vacuum dried to obtain poly (N-ethylvinylpyridinium) bromide-supported polymer beads. Yield 8.2g, bromine ion content 2.2%. From this, haloalkylated polymer (1) 1
63 mg of poly (N-ethylvinylpyridinium) per g
It can be seen that polymer beads carrying bromide were obtained. The polymer beads are used as a microorganism adsorption polymer (2)
And

Example 3 In Example 1, the same operation was performed using poly (4-vinylpyridine) (number average molecular weight 200,000) instead of poly (4-vinylpyridine) (number average molecular weight 50,000). Polymer beads with a nitrogen content of 0.80% were obtained. 8.0 g of the obtained polymer beads were mixed with phenethyl bromide 10.0.
suspended in a solution consisting of 50 g of methyl alcohol and 50 g of methyl alcohol,
Heating was continued under reflux for 5 hours. The reaction mixture was separated, the obtained polymer beads were washed with acetone, and then vacuum dried to obtain poly (N-phenethylvinylpyridinium) bromide-supported polymer beads. Yield 8.7g, bromine ion content 4.1%. From this, it can be seen that polymer beads carrying 177 mg of poly (N-phenethylvinylpyridinium) bromide per 1 g of haloalkylated polymer (1) were obtained. This polymer bead is used as a microorganism adsorbing polymer (3).

Example 4 Using 10 g of the haloalkylated polymer (2) obtained in Synthesis Example 2, the same operation as in Example 1 was carried out to obtain polyvinylpyridine-supporting polymer beads. Yield 9.5g, nitrogen content
1.8%.

Then, 8.0 g of the obtained polyvinylpyridine-supported polymer beads was suspended in a solution consisting of 8.0 g of benzyl chloride and 50 g of methyl alcohol, and heating was continued for 5 hours under reflux.
The reaction mixture was separated, the obtained polymer beads were washed with acetone, and then vacuum dried to obtain poly (N-benzylvinylpyridinium) chloride-supporting polymer beads. Yield 8.3g, chloride ion content 0.49%. From this, 41 mg of poly (N-) per gram of haloalkylated polymer (2)
It can be seen that polymer beads carrying benzylvinylpyridinium) chloride were obtained. This polymer bead is used as a microorganism adsorption polymer (4).

Example 5 Using 10 g of the haloalkylated polymer (3) obtained in Synthesis Example 3, the same operation as in Example 1 was performed to obtain a polyvinylpyridine-supported polymer. Yield 10.5g, nitrogen content 0.62
%.

8.0 g of the obtained polyvinyl pyridine-supporting polymer
Was suspended in a solution of 8.0 g of decyl bromide and 50 g of methyl alcohol, and heating was continued under reflux for 5 hours. The reaction mixture was separated, the obtained polymer was washed with acetone, and then vacuum dried to obtain a poly (N-decylvinylpyridinium) bromide-supported polymer. Yield 8.5g, bromine ion content 3.2%. From this, it is understood that a polymer carrying 116 mg of poly (N-decylvinylpyridinium) bromide was obtained per 1 g of the haloalkylated polymer (3). This polymer bead is used as a microorganism adsorbing polymer (5).

Example 6 Haloalkylated polymer (4) obtained in Synthesis Example 4 (cloth)
30 g of poly (4-vinylpyridine) (number average molecular weight 50,00
0) added to a solution consisting of 10 g and 200 g of methyl alcohol,
Heating was continued under reflux for 5 hours. The cloth was taken out from the reaction mixture and washed by Soxhlet extraction using methanol as a solvent. The washed cloth was vacuum-dried to obtain a polyvinylpyridine-supported cloth. Yield 31.1g, nitrogen content 0.32%.

Next, 10 g of the obtained polyvinyl pyridine-supported cloth was suspended in a solution of 8.0 g of benzyl bromide and methyl alcohol, and heating was continued for 5 hours under reflux. The cloth was taken out from the reaction mixture cloth, washed with acetone, and then vacuum-dried to obtain a poly (N-benzylvinylpyridinium) bromide-supported cloth. Yield 10g, bromine ion content 1.7%. From this, 80 mg of poly (N) per gram of haloalkylated polymer (4)
It can be seen that a cloth bearing -benzylvinylpyridinium) bromide was obtained. This polymer bead is used as a microorganism adsorbing polymer (6).

Example 7 10 g of the polyvinylpyridine-supported cloth obtained in Example 6 and 50 g of methyl chloride were charged into an autoclave, and heating was continued at 60 ° C. for 8 hours. After the reaction, the product was dried as it was under reduced pressure to obtain a cloth supporting poly (N-methylvinylpyridinium) chloride. Yield 10g, chloride ion content 0.80%. From this, it can be seen that a cloth carrying 50 mg of poly (N-methylvinylpyridinium) bromide per 1 g of the haloalkylated polymer (4) was obtained. This cloth is used as a microorganism adsorbing polymer (7).

Example 8 Escherichia coli was suspended in 0.85% saline to a concentration of 5.0 × 10 ⁶ / ml, and 20 g of this suspension was added with 2.0 g of the microorganism-adsorbing polymer (1) obtained in Example 1 and the mixture was incubated at 37 ° C. While keeping on 15
Stirring was continued at a speed of 0 rpm. As a result, after 1, 2, 3 and 5 hours, the bacterial numbers were 4.7 × 10 ⁵ / ml, 3.0 × 10 ⁴ / ml,
It was reduced to 2.5 × 10 ³ / ml and 1.3 × 10 ² / ml.

Example 9 Salmonella typhimurium 6.5 in 0.85% saline
The suspension was suspended in a concentration of × 10 ⁶ / ml, and 20 ml of this suspension was used in Example 2.
2.0 g of the microorganism-adsorbing polymer (2) obtained in 1. was added, and stirring was continued at a speed of 150 rpm while maintaining the temperature at 37 ° C. As a result, 1,3
And after 5 hours, the number of bacteria was 5.8 × 10 ^{4 /} ml, 4.2 ×
It was reduced to 10 ³ / ml and 1.2 × 10 ² / ml.

Example 10 Staphylococcus aureus in 0.85% saline 3.
The suspension was suspended at a concentration of 0 × 10 ⁶ / ml, and 2.0 g of the microorganism-adsorbing polymer (3) obtained in Example 3 was added to 20 ml of this suspension, and stirring was continued at a speed of 150 rpm while maintaining the temperature at 37 ° C. As a result, the bacterial counts were 2.5 × 10 ^{5 /} ml and 2.0 × 10 after 1, 3 and 5 hours, respectively.
It decreased to ³ / ml and 1.8 × 10 ² / ml.

Example 11 Streptococcus fuecalis in 0.85% saline 5.
The suspension was suspended at a concentration of 0 × 10 ⁶ / ml, 2.0 g of the microbial adsorption polymer (4) obtained in Example 4 was added to 20 ml of this suspension, and stirring was continued at a speed of 150 rpm while maintaining the temperature at 37 ° C. As a result, 1,
After 3 and 5 hours, the bacterial counts were 3.8 × 10 ^{5 /} ml and 2.5, respectively.
It decreased to × 10 ³ / ml and 1.8 × 10 ² / ml.

Example 12 Escherichia coli was suspended in 0.85% saline at a concentration of 7.8 × 10 ⁶ / ml, and 20 g of this suspension was added with 2.0 g of the microorganism-adsorbing polymer (5) obtained in Example 5, and the mixture was incubated at 37 ° C. While keeping on 15
Stirring was continued at a speed of 0 rpm. As a result, after 1, 2, 3 and 5 hours, the number of bacteria was 6.2 × 10 ⁵ / ml, 4.8 × 10 ⁴ / ml,
It decreased to 3.5 × 10 ³ / ml and 2.3 × 10 ² / ml.

Example 13 Escherichia coli was suspended in 0.85% saline at a concentration of 6.0 × 10 ⁶ / ml, and 20 g of this suspension was added with 2.0 g of the microorganism-adsorbing polymer (6) obtained in Example 6, and the mixture was incubated at 37 ° C. While keeping on 15
Stirring was continued at a speed of 0 rpm. As a result, after 1, 3 and 5 hours, the bacterial count was 4.5 × 10 ⁴ / ml, 3.2 × 10 ³ / ml and
It decreased to 2.1 × 10 ² / ml.

Example 14 Streptococcus fuecalis in 0.85% saline 3.
The suspension was suspended at a concentration of 0 × 10 ⁶ / ml, 20 g of this suspension was added with 2.0 g of the microorganism-adsorbing polymer (7) obtained in Example 7, and stirring was continued at a speed of 150 rpm while maintaining the temperature at 37 ° C. As a result, 1,3
And after 5 hours, the number of bacteria was 2.1 × 10 ^{5 /} ml and 1.8 ×, respectively.
It was reduced to 10 ³ / ml and 1.2 × 10 ² / ml.

Example 15 Bacteriophage T ₄ in 0.85% saline solution at 5.4 × 10 ⁶ / ml
To 20 ml of this suspension, 2.0 g of the microorganism-adsorbing polymer (1) obtained in Example 1 was added, and the temperature was maintained at 37 ° C.
Stirring was continued at a speed of 150 rpm. As a result, the number of bacteria was reduced to 3.8 × 10 ⁵ / ml, 2.3 × 10 ³ / ml and 1.5 × 10 ² / ml after 1, 3 and 5 hours, respectively.

Example 16 The microbial adsorption polymer (6) obtained in Example 6 was mounted on a membrane filter holder having a diameter of 35 mm, and Escherichia coli was suspended in 0.85% saline at a concentration of 4.0 × 10 ⁴ / ml. (Liquid flow rate 100 ml / min). The concentration of bacteria in the water that has permeated the microbial adsorption polymer (6) (cloth-like) is 2.
It had dropped to 0 × 10 ² / ml.

Example 17 A column having an inner diameter of 20 mm and a length of 1000 mm was packed with the microorganism-adsorbing polymer (1) obtained in Example 1 to give a staphylococcus
When a solution of aureus suspended in 0.85% saline at a concentration of 2.0 × 10 ⁶ / ml was passed at a rate of 10 ml / min, the above-mentioned microorganism was not detected at all in the effluent.

Claims (1)

(57) [Claims] 1. A water-insoluble polymer molding having a halomethyl group represented by the following formula XCH ₂ — (wherein X represents a chlorine atom, a bromine atom or an iodine atom) in the molecule, and a vinylpyridine homopolymer Alternatively, a copolymer of vinyl pyridine and another monomer is brought into contact to carry out a quaternization reaction of the halomethyl group and the pyridine moiety, and then the unreacted pyridine moiety of the resulting product is converted to its alkyl group. A method for producing a microbial adsorbent, wherein the group is quaternized with an alkylating agent selected from a benzyl group, a phenethyl group, an alkyl group having 1 to 12 carbon atoms and a pentafluorophenylmethyl group.