JPH02237901A - Adsorbent of microorganism - Google Patents

Abstract

PURPOSE:To obtain an adsorbent of microorganism showing excellent adsorbing properties on microorganisms and not exerting bad influence on targets to be sterilized such as water, comprising a crosslinked hydrocarbon compound prepared by copolymerizing a vinylpyridine with a hydrophilic crosslinkable monomer and further quaternizing pyridine group. CONSTITUTION:(A) A vinylpyridine, preferably 2-, 3- or 5-vinylpyridine is copolymerized with (B) a hydrophilic crosslinkable monomer, preferably polyfunctional (meth)acrylate or polyfunctional (meth)acrylamide in the presence or absence of (C) another vinyl monomer copolymerizable with the monomers in the molar ratio of preferably the component A:B:C of about (50-95):(5-50):(0-45) to give a copolymer, and further the pyridine group thereof is quaternized into a crosslinked polymer compound to give an adsorbent of microorganism containing the crosslinked polymer compound as an active ingredient, having the above-mentioned effects, mechanical strength not inferior to existing adsorbents, useful for sterilizing water, air, surface of solid, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a microbial adsorbent that exhibits excellent microbial adsorption properties when disinfecting water, air, solid surfaces, etc., and does not have any adverse effects on the objects to be disinfected. .

[Conventional technology]

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

Conventionally, methods using microbicides such as chlorine, microbicides by heating, and P filtration methods using membranes and filters have been mainly used for this purpose. However, methods using microbicides generally leave harmful substances behind, so they cannot be applied to equipment for manufacturing, storing, and transporting foods and other products, or for drinking water.Methods using heating, membranes, and filters require large-scale equipment and are not economical. It was also inconvenient.

Recently, the following formula (wherein R is a penzol group, a C4-CO-alkyl group, or a pentafluorophenylmethyl group, and X is a chlorine atom or a bromine atom) is used to easily remove microorganisms in the environment. There has been provided a microbial control agent containing as an active ingredient an insoluble polymeric compound having a birizonium group obtained by polymerizing the compound expressed above and a zovinyl compound such as zovinylbenzene at the vinyl group (Japanese Patent Publication No. 62-41641
issue).

[Problem that the invention aims to solve]

However, when using the microbial control agent described in Japanese Patent Publication No. 62-41641, even if this microbial control agent is brought into sufficient contact with a bacterial suspension of 10' to 10' population/d, all the bacteria will be removed. It took more than 6 hours to remove the bacteria from the liquid, and when the bacteria were brought into contact with a suspension of 103 to 104 individuals/d under the same conditions, it took even longer to remove the bacteria from the liquid. There is a drawback that it requires

Further, in Japanese Patent Publication No. 62-41641, zopinylbenzene is used as a crosslinking monomer for producing a microbial control agent. As is well known, zopinylbenzene is excellent in increasing the mechanical strength of the insoluble polymer compound, but its hydrophobicity is high, and it is said that the use of large amounts of zovinylbenzene significantly reduces the ability to adsorb microorganisms. A problem arises.

[Means to solve the problem]

Under these circumstances, the present inventors conducted various studies in order to obtain a microbial adsorbent that eliminates the above-mentioned drawbacks, and as a result, they copolymerized vinylbilisons and a hydrophilic crosslinking monomer and further quaternized it. The cross-linked polymer compound having a pyricinium group obtained by this method has excellent and rapid bacterial adsorption properties, and has no adverse effect on the target of sterilization when sterilizing water, air, and solid surfaces. Furthermore, the present invention was completed based on the discovery that a microbial adsorbent using the polymer compound has mechanical strength comparable to that of conventional adsorbents.

That is, the present invention copolymerizes vinylpyridones and a hydrophilic crosslinkable monomer in the presence or absence of other vinyl heptanomers copolymerizable with them to form a copolymer, and furthermore, the pyridine group The present invention provides a microbial adsorbent containing as an active ingredient a crosslinked polymer compound obtained by quaternizing.

The polymer compound used in the microbial adsorbent of the present invention is a copolymer obtained by copolymerizing pinylpyrizones and a hydrophilic crosslinking monomer in the presence or absence of other pinyl monomers that can be copolymerized with them. It is produced by quaternizing it.

As the vinylpyridines used here, 2-vinylpyridine, 3-vinylpyridone, and 4-vinylpyridine are preferably used, but vinylpyridine derivatives having other substituents may also be used.

Hydrophilic crosslinkable monomers such as ethylene glycolzo(meth)acrylate, butanezoolno(meth)
Acrylate, trimethylolzorononotori (meth)
Acrylate, pentaerythritol (meth)acrylate, hentaerythritol tetra(meth)acrylate, ? Polyfunctional (meth)acrylates such as lyethylene glycol zo(meth)acrylate; methylenebis(meth)acrylamide, propylenebis(meth)acryl7 MiF, NtN'-(1+2-zohydroxyethylene)bis(meth)acrylamide , N, N'-(
Examples include polyfunctional (meth)acrylamides such as calzeximethylene) bis(meth)acrylamide.

Examples of other copolymerizable vinyl monomers include styrene monomers such as styrene, p-methylstyrene, and p-chlorostyrene; ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, zomethylaminoethyl acrylate, and zoethyl. Acrylic acid ester monomers such as aminoethyl acrylate, 2-hydroxyethyl acrylate; methyl methacrylate, ethyl methacrylate, lauryl methacrylate, zomethylaminoethyl meccrylate, zoethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, etc. Methacrylic acid ester monomer;? Liethylene glycol mono(
Meth)acrylates; alkyl pinylethers such as methyl vinyl ether and ethyl vinyl ether; vinyl ester monomers such as vinyl acetate and vinyl butyrate; N-alkyl-substituted (meth)acrylamide; nitrile monomers such as acrylonitrile and methacrylonitrile can be mentioned, but are not limited to the above-mentioned heptanomers as long as they are essentially compatible with vinylpyridones. These monomers can be used alone or in combination of two or more.

The blending molar ratio in the copolymerization of vinylvirisons, hydrophilic crosslinkable monomers, and other vinyl monomers is 50 to 50.
The ratio is preferably about 95:5 to 50:0 to 45.

Copolymerization methods include conventionally known bulk polymerization, solution polymerization,
Suspension polymerization or the like can be used.

For quaternization of the copolymer thus obtained, for example, CI
Alkylating agents such as alkyl halides, aralkyl halides, 7-fluoroalkyl halides such as chloro, prom or iodine of ``-cta'' are used.
A species or two or more species can be used.

The reaction between the copolymer and the alkylating agent is carried out by adding 1 to 5 molar equivalents, particularly 1.5 to 4.0 molar equivalents of the alkylating agent to the hylizone group in the copolymer, and using a solvent such as methanol or ethanol. This is carried out by mixing in the presence of , under normal pressure and at a temperature of 50 to 70°C.

Furthermore, the obtained crosslinkable polymer compound was subjected to ion exchange according to a known method, and the pyrizonium group pair anions were halogen ions, halogenite ions, hypohalite ions, nitrate ions, nitrite ions, disulfite ions, and thiosulfite ions. , can be converted into monovalent anions such as phosphate ions.

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 may be directly added to the water, or a device filled with powdered or granular microorganism adsorbent, or a fibrous or sheet material may be used. The water to be treated can be passed through a device equipped with a type of 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. Further, microorganisms adhering to the solid surface can be removed by, for example, lightly wiping the surface with a fibrous microorganism adsorbent.

The microbial adsorbent of the present invention may further contain optional components such as known antibacterial agents and microbicides, if necessary.

〔Effect of the invention〕

The microbial adsorbent of the present invention was brought into contact with either a bacterial suspension of 107 to 108 individuals/d or a bacterial suspension of 103 to 10' individuals/ml under the conditions described in Japanese Patent Publication No. 62-41641. Even in this case, the microorganism adsorption performance was superior to that of the active ingredient in the microorganism control agent described in the above-mentioned publication, which adsorbed all the bacteria in the suspension in 2 to 3 hours.

Therefore, the microbial adsorbent of the present invention can easily adsorb and remove bacteria in water, air, and solid surfaces by contacting it with drinking water, various types of water, air, and solid surfaces. It is useful for purposes such as improving the durability of objects. Further, the microorganism adsorbent of the present invention can be used as a microorganism immobilization carrier for a bioreactor or a biosensor by taking advantage of its large microorganism adsorption ability.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of 1-benzol-4-vinylpyrizonium bromide/zoethylene glycol zomethacrylate copolymer: (;) Water was placed in a 1T SE, Q Lapple flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube. 500? Put it in,
Add calcium carbonate powder 10F and 150 rpm
The mixture was stirred at a speed of 100 to uniformly disperse the mixture.

In this state, a solution consisting of 4-vinyl bi'l'7105F, 132 zoethylene glycolzomethacrylate, 12 azopisisobutyronitrile, and 100 v of mether benzoate was added, and the mixture was stirred at a speed of 150 rpm. Heated at 80°C for 3 hours. The obtained Rimer beads were taken from house to house, rinsed with 1% acetic acid to dissolve and remove calcium carbonate, and then washed with water and Is heavy soap repeatedly, finally washed with ethanol, and then vacuum dried to form 4-vinylpyrizone/zoethylene. Spherical particles of glycolzomethacrylate copolymer were obtained. Yield 110F
, average dry particle size of copolymer particles 200 μm, nitrogen content 10%.

This copolymer particle is referred to as vinylpyrinone polymer (1).

(M) Next, the vinylvirison mentioned above? Rimmer (1)
219 was suspended in methanol 100F, K bromide be/sol 1202 was added thereto, and the mixture was heated at 60°C for 5 hours.

? After the remer beads were isolated from door to door, they were washed with ethanol and then vacuum dried to remove the virizone groups from N-
Title in place of penzolpyrizonium group (counter ion: bromide ion)? Remer particles were obtained. Yield 48? , bromine content 26%.

Synthesis Examples 2 to 8 The same operations as in Synthesis Example 1 were performed using various vinylpyridines, hydrophilic crosslinking monomers, and alkylating agents shown in Table 1 below to obtain vinyl birizonium/hydrophilic crosslinking. Spherical particles of a monomer copolymer were obtained.

V1 Lower Margin Synthesis Examples 9 to 12 Bromine ions, which are the counter ions of the 1-penzol-2-vinylgirizonium bromide/octaethylene glycol zoacrylate copolymer obtained in Synthesis Example 4, were added to the following second coating by an ion exchange method. were converted to various counterions as indicated.

Table 2 Example 1 Escherichia coli 6. 5 x 10' individuals/1, suspended in 0.15 molar saline, and this suspension was pre-swollen with 20 molar saline at 37°C.
2 (22 by dry weight) of 1-pesol-4-vinyl birizonium bromide/zoetelene glycolzomethacrylate copolymer (obtained in Synthesis Example 1, if reamer particles) was added, and the mixture was heated at 35 to 37°C. ,100~12O rpm
Stirring was continued at a speed of . As a result, after 1.2 and 3 hours, the amount of dog intestine in the suspension was 3.5 hours, respectively. IX1
03, 1. The number of individuals decreased significantly to 0 x 101,0 individuals/d. The time required for 99.9% of the initial population of E. coli to be absorbed by the adsorbent (temporarily assuming this as the body adsorption capacity) was 16 minutes.

Examples 2 to 12 The bacterial cell adsorption ability of the vinyl birizonium/hydrophilic crosslinkable monomer copolymers obtained in Synthesis Examples 2 to 12 was evaluated in the same manner as in Example 1. The results are shown in Table 3. In addition, in Table 3, each of the IJs obtained in Synthesis Examples 2 to 12
The mer particles are represented as adsorbents 2 to 12, respectively.

Add the umpromide/novinylbenzene copolymer from Table 3 in the margin below, and
5-37℃, 100-120 rpm
Stirring was continued at a speed of . As a result, after 1, 3.5 and lo hours, the number of E. coli in the suspension was 8. 2
X 10', 2. OX10, 1. lX10,
1. It decreased to OX10.

Furthermore, the adsorption capacity for bacterial cells was 2.5 hours, which was significantly lower than that of the adsorbent of the present invention.

that's all

Claims (1)

[Claims] 1. A copolymer is obtained by copolymerizing a vinyl pyridine and a hydrophilic crosslinkable monomer in the presence or absence of another vinyl monomer copolymerizable with them, and further A microbial adsorbent containing as an active ingredient a crosslinked polymer compound obtained by quaternizing the pyridine group. 2. The microbial adsorbent according to claim 1, wherein the hydrophilic crosslinkable monomer is a polyfunctional (meth)acrylate or a polyfunctional (meth)acrylamide.