JP3118604B2 - Microbial adsorption resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an excellent adsorbent for microorganisms used in water treatment as an adsorbent for microorganisms in water, a carrier for holding microorganisms and cells in bioreactors and biosensors, and the like. And a microorganism-absorbing resin having the ability to adsorb microorganisms.

[0002]

2. Description of the Related Art Insoluble polymer compounds comprising a crosslinked polyvinylpyridinium halide have been proposed as a material for satisfying requirements for a microorganism removing material for water treatment and a carrier for a bioreactor.

This compound is capable of capturing microorganisms in a highly efficient and alive state and, furthermore, is insoluble in water and, therefore, has a very good ability to adsorb microorganisms without polluting the environment. It is.

However, the above-mentioned crosslinked polyvinylpyridinium halide is insoluble not only in water but also in a common organic solvent, and can be handled only as a solid. For this reason, processing is difficult, and since it is generally used in the form of beads that are relatively easy to process, there is a problem that the surface area per unit weight is small and the efficiency of adsorbing microorganisms is poor. In order to solve this problem, for example, the diameter of the beads may be reduced. However, in this case, there is a possibility that the beads may be clogged and cannot be used.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and is capable of adsorbing microorganisms with high efficiency without lowering its activity, It is an object of the present invention to provide a microorganism-adsorbing resin which is insoluble or hardly soluble in organic solvent but is soluble in an organic solvent and can be used as a solution.

[0006]

In order to achieve the above object, the present invention provides a vinyl copolymer represented by the following general formula, which is insoluble or hardly soluble in water and soluble in an organic solvent. The gist of the present invention is a microorganism adsorption resin characterized by the following.

[0007]

Embedded image In the formula, R ₁ is a benzyl group, a C ₄ -C ₁₆ alkyl group or a pentafluorophenylmethyl group, R ₂ is a hydrogen atom or a C ₁ -C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, alkyl group of ₁ -C _3, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group or an aryl group.

[0008] The vinyl copolymer constituting the microorganism-adsorbing resin of the present invention is obtained by copolymerizing 4-vinylpidine and a monovinyl monomer and then reacting the copolymer with a halide. Monovinyl monomers used in the production of this vinyl copolymer include ethylene, propylene, monoolefins such as butene, styrene, vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, aliphatic vinyl ester, Acrylonitrile and derivatives thereof can be used alone or in combination. However, it is not desirable to use a monovinyl monomer having a highly hydrophilic functional group because the monomer becomes water-soluble depending on the degree of polymerization of the obtained copolymer.

The ratio of 4-vinylpyridine to the monovinyl monomer, that is, the ratio of n: m in the above general formula, varies depending on the type of the vinyl monomer used and the degree of polymerization, but is generally about 10:90 to 10:90. It is desirable to be in the range of 80:20. If the proportion of 4-vinylpyridine is smaller than this range, sufficient microorganism adsorption cannot be obtained, and if it is larger than this range, the obtained copolymer becomes highly water-soluble.

The degree of polymerization of the above-mentioned vinyl copolymer is desirably at least 300 or more. If the degree of polymerization is lower than this, the resulting polymer has high water solubility.

A copolymer of 4-vinylpyridine and a monovinyl monomer is quaternized by reacting with a halide such as an alkyl halide, a benzyl halide or a pentafluorophenylmethyl halide to obtain a quaternary pyridine. Form the functional group represented. Formula: X ^- R ₁ -N ⁺

It is considered that this functional group mainly acts to adsorb the microorganism while maintaining the active state of the microorganism. Although the mechanism is not clear, this functional group is positively charged, and the cell surface of microorganisms is generally negatively charged, so it is presumed that electrostatic interaction is one important factor. You.

The microorganism-adsorbing resin comprising the vinyl copolymer thus obtained has the same excellent microorganism-adsorbing ability as the conventional crosslinked polyvinylpyridinium halide. Further, this microorganism-adsorbing resin is insoluble or hardly soluble in water, but is soluble in an organic solvent. Utilizing this property, the vinyl copolymer can be dissolved in an organic solvent such as alcohols, esters, and ethers to form a solution.

For this reason, according to this microorganism-adsorbing resin,
Processing such as impregnation or coating of other base materials, which was not possible with conventional cross-linked polyvinyl pyridinium halide, becomes possible.For example, a solution in which this microorganism-adsorbing resin is dissolved is impregnated, sprayed, and coated by means such as coating. By applying it to the surface of the substrate and drying it, a microorganism adsorbent having an excellent ability to adsorb microorganisms can be obtained.

By using the microorganism-adsorbing material provided with the microorganism-adsorbing resin as a water treatment material, microorganisms contained in the water to be treated can be efficiently adsorbed and removed, thereby purifying the water. In addition, according to the microorganism adsorbent to which the polymer is added, the microorganism adsorption ability does not easily decrease even after a lapse of time, and troubles such as clogging hardly occur. In addition, if the microorganism adsorbing material provided with the microorganism adsorbing resin of the present invention is used as a biosensor or a bioreactor, the microorganisms can be adsorbed and immobilized with high activity in a living state with high efficiency. Therefore, a reaction product can be obtained or a substance can be selected by utilizing an enzyme contained in these cells, and an excellent biocatalytic function can be sufficiently utilized.

The microorganism-absorbing resin of the present invention provides
The microorganisms to be adsorbed include bacteria, fungi, algae, viruses, and the like.

[0017]

EXAMPLES Hereinafter, the microorganism-adsorbing resin of the present invention will be described in more detail with reference to Examples. Example 1 After copolymerizing 4-vinylpyridine and styrene at a ratio of 40:60 mol%, the resulting mixture was quaternized with an equimolar amount of benzyl bromide to obtain a microorganism-adsorbing resin composed of a vinyl copolymer. .

On the other hand, rayon fiber (denier 1.5 denier)
Is subjected to hydroentanglement treatment, and the basis weight is 90 g / m ² ,
A nonwoven fabric having a thickness of 0.5 mm was obtained.

The hydroentangled nonwoven fabric is impregnated with an ethanol solution in which the above-mentioned vinyl copolymer is dissolved, and then dried at 75 ° C., so that the adhesion of the vinyl copolymer to the nonwoven fabric is 1.
5% by weight of the microorganism adsorbent was obtained.

This microbial adsorbent was punched into 3 cmφ, and 30 layers were packed and packed in a column having an inner diameter of 3 cm. Then, a liquid obtained by suspending Escherichia coli at a concentration of 4.6 × 10 ⁸ cells / ml in 0.85% saline was prepared. The solution was passed through the column at a rate of 45 ml / hr.

The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals using an agar plate pour method, and the eradication rate was determined.
It is shown in the table.

Comparative Example 1 Without using the vinyl copolymer of the present invention, only the hydroentangled nonwoven fabric used in Example 1 was packed in a column, and Escherichia core was added to a 0.85% saline solution in 5.5 × 10 5 ^The liquid suspended at a concentration of ⁸ cells / ml was passed through the column at a rate of 35 ml / hr.
The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals, and the eradication rate was determined. The results are shown in Table 1.

Example 2 A vinyl copolymer obtained by copolymerizing 4-vinylpyridine and styrene at a ratio of 40:60 mol% and then quaternizing with benzyl chloride at an equal mol% was used. Except for the above, a microorganism adsorbent was obtained in the same manner as in Example 1.

After packing the microorganism-adsorbing material in a column in the same manner as in Example 1, a solution obtained by suspending Escherichia core at a concentration of 5.6 × 10 ⁸ cells / ml in 0.85% saline was added at 40 ml / hr. The solution was passed through the column at a speed of, and the number of viable bacteria in the filtrate was measured at regular intervals, and the results are shown in Table 1.

As apparent from Table 1, Examples 1 and 2
The microbial adsorbent using the water-entangled nonwoven fabric to which the microbe-adsorbing resin of the present invention was adhered was excellent in bacteria-adsorbing power and showed a high eradication rate, but Comparative Example 1 in which the microbial-adsorbing resin of the present invention was not applied. The product had a weak adsorbing power of the bacteria and decreased remarkably with the passage of time, showing only about 10% of the eradication rate.

[0026]

Example 3 The microbial adsorbent of Example 1 was punched into 3 cmφ, and 30 layers were packed and packed in a column having an inner diameter of 3 cm, and Staphylococcus aureus was added to 0.85% saline at a concentration of 2.8 × 10 ⁸ cells / ml. Was passed through the column at a rate of 60 ml / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals, and the eradication rate was determined. The results are shown in Table 2.

Example 4 The microbial adsorbent of Example 1 was punched out to a size of 3 cmφ, and 30 layers were packed and packed in a column having an inner diameter of 3 cm. Pseudomonas aeruginosa was suspended in 0.85% saline at a concentration of 6.2 × 10 ⁸ cells / ml. The turbid liquid was passed through the column at a rate of 30 ml / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals, and the eradication rate was determined. The results are shown in Table 2.

As is evident from Table 2, regardless of the type of bacteria, the microorganism adsorbent using the microorganism-adsorbing resin of the present invention exhibited good bacteria-adsorbing power.

[0030]

Example 5 The microbial adsorbent of Example 1 was punched into 1.6 cmφ and had an inner diameter of 1.6 cm.
After laminating and packing 20 sheets in a column of 20 cm, a solution of T-4 bacteriophage suspended in 0.85% saline at a concentration of 1.3 × 10 ⁶ cells / ml was passed through the column at a rate of 20 ml / hr. . The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals, and the eradication rate was determined. The results are shown in Table 3.

Comparative Example 2 The hydroentangled nonwoven fabric of Example 1 was punched out into a 1.6 cmφ size in the same manner as in Example 5, and 20 pieces of this were stacked and filled in a column having an inner diameter of 1.6 cm. Bacteriophage
A liquid suspended in 0.85% saline at a concentration of 1.3 × 10 ⁶ cells / ml was passed through the column at a rate of 20 ml / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured at regular intervals, and the eradication rate was determined,
The results are shown in Table 3.

From Table 3, it was found that the microorganism adsorbent using the vinyl copolymer of the present invention works more effectively against microscopic viruses than bacterial cells.

[0034]

Example 6 A vinyl copolymer obtained by copolymerizing 4-vinylpyridine and styrene at a ratio of 25:75 and then quaternizing with benzyl bromide in an equimolar amount was used. Example 1
A microorganism adsorbent was obtained in the same manner as described above.

After the microorganism adsorbent was packed in a column in the same manner as in Example 1, a solution obtained by suspending Escherichia coli at a concentration of 2.3 × 10 ⁸ cells / ml in 0.85% saline was added at 70 ml / hr.
The solution was passed through the column at a rate of, and the number of viable bacteria in the filtrate was measured at regular intervals to determine the eradication rate.

Example 7 4-vinylpyridine and methyl methacrylate were copolymerized at a ratio of 40:60, and then copolymerized with an equimolar amount of benzyl bromide.
A microbial adsorbent was obtained in the same manner as in Example 1 except that a vinyl copolymer subjected to a grading treatment was used.

After the microorganism adsorbent was packed in a column in the same manner as in Example 1, Escherichia coli was suspended in 0.85% saline at a concentration of 3.8 × 10 ⁸ cells / ml.
The solution was passed through the column at a rate of, and the number of viable bacteria in the filtrate was measured at regular intervals to determine the eradication rate.

Table 4 shows that the ratio of 4-vinylpyridine, which is the raw material of the vinyl copolymer of the present invention, to the vinyl monomer causes a difference in the ability of the microorganism adsorbent to adsorb microorganisms. From Table 4, it was also found that even if the vinyl monomer component was changed, a microorganism adsorbing power having a good adsorbing power could be obtained.

[0040]

[0041]

As described above, the microorganism-adsorbing resin of the present invention has excellent microorganism-adsorbing ability and is soluble in an organic solvent, so that it can be used as a solution for impregnating other substrates or coating. It can be processed and does not suffer from the limitation that it can be handled only as a solid unlike the conventional crosslinked polyvinylpyridinium halide. Therefore, the surface area per unit weight of the microorganism-adsorbing resin, which determines the magnitude of the microorganism-adsorbing ability of the microorganism-adsorbing material, can be freely set by selectively using the substrate to which the microorganism-adsorbing resin is applied. Thus, a microorganism adsorbing material having a desired microorganism adsorbing ability can be obtained. Further, since the microorganism-absorbing resin is insoluble or hardly soluble in water, it does not dissolve and pollute the environment.

Since the microorganism-adsorbing resin is soluble in an organic solvent, it can be applied to a desired substrate surface by a simple operation such as impregnation, spraying, coating, etc., and has excellent microorganism-adsorbing ability. The microorganism adsorbent can be obtained by a simple manufacturing process.

Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI C12N 11/08 C12N 11/08 A (56) References JP-A-2-237903 (JP, A) JP-A-2-237902 (JP, A JP-A-2-237901 (JP, A) JP-A-2-235802 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/44

Claims (1)

(57) [Claims] 1. A microorganism-adsorbing resin represented by the following general formula, comprising a vinyl copolymer insoluble or hardly soluble in water and soluble in an organic solvent. Embedded image In the formula, R ₁ is a benzyl group, a C ₄ -C ₁₆ alkyl group or a pentafluorophenylmethyl group, R ₂ is a hydrogen atom or a C ₁ -C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, alkyl group of ₁ -C _3, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group or an aryl group.