KR100325121B1 - Delayed release water treatment agent and preparation method thereof - Google Patents

Abstract

PURPOSE: A delayed release water treatment agent for inhibiting the growth of microbe in water circulation system and pipe corrosion, and a preparation method thereof are provided. CONSTITUTION: The delayed release water treatment agent comprises quaternary ammonium phosphate represented by formula I; and biodegradable or aqueous soluble polymer wherein R1 is C1-C27 straight or branched alkyl radical or aryl radical including ether bonding, R2 and R3 is respectively C1-C10 alkyl radical or heterocyclic compounds including oxygen and nitrogen, and Bn is benzyl.

Description

Controlled release water treatment agent and its manufacturing method

[Industrial use]

The present invention relates to a controlled release water treatment agent, and more particularly, to a controlled release water treatment agent that can be applied to cooling towers, flooring materials, wallpaper, sinks and the like to inhibit the microorganisms in the water and to prevent corrosion.

[Prior art]

Most water treatment systems consist of a variety of metals, including carbon steel and copper, and are always exposed to corrosiveness because water is circulated inside. In addition, to improve heat exchange efficiency, open circulation is adopted rather than closed, so the circulating water in the system is continuously evaporated, discharged and replenished to the outside. Therefore, the chemicals injected into the water treatment system should be maintained in a certain amount at an appropriate concentration, there should be no problem of corrosion and scale on the metal material, and should be able to suppress the growth of microorganisms.

Various types of water treatment fungicides are known, and are classified into oxidizing, non-oxidizing, chlorine, non-chlorine, and the like. Representative water treatment fungicides include calcium hypochlorite, sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, trichloroisocyanuric acid, hydantoin, glutaaldehyde, and isothiazolone. have. In particular, calcium hypochlorite and trichloroisocyanuric acid have been used as sterilizing and disinfecting agents made of circular, elliptical or necessary tableting agents using tableting techniques using mechanical pressure.

However, the tableting agent as a chlorine disinfectant is a simple manufacturing process, but a lot of working dust is generated, the obtained formulation should be added from time to time it is necessary to use. Tableting agents composed of chlorine fungicides have two major disadvantages. The first is that the concentration is high only at the beginning, and the concentration decreases or disappears thereafter, so that the optimum concentration for the retained water cannot be maintained. Second, the chlorine disinfectant dissociates chlorine ions from the water, causing severe material corrosion, especially in carbon and stainless steels. Will cause. Therefore, its basic function of sterilization is good, but it cannot be used in the field requiring corrosion protection.

In addition, since the non-chlorine fungicide is mainly an organic material and a reactive material, there is no material stability in the solid phase, and thus it is not suitable to be used as a tableting agent.

The present invention is to solve the problems of the prior art as described above, the object of the present invention is to maintain and control the appropriate concentration without generating the working dust from time to time, and can exhibit the effect of sterilization and corrosion protection at the same time To provide a controlled release water treatment agent.

1 is a sustained release graph showing the amount of fungicide discharged as a function of time of the water treatment composition prepared according to one embodiment of the present invention.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a controlled release water treatment composition comprising a disinfectant of quaternary ammonium phosphate represented by the formula (1) and a polymer material compounded with the disinfectant.

[Formula 1]

In Formula 1, R ₁ may include an ether bond as a linear or pulverized alkyl radical or aryl radical having 1 to 27 carbon atoms, and R ₂ and R ₃ may each represent an alkyl radical having 1 to 10 carbon atoms or oxygen and nitrogen. Heterocyclic compound containing, Bn represents a benzyl group.

In another aspect, the present invention provides a method for producing a water treatment composition comprising the step of compounding the disinfectant and the polymer material of the quaternary ammonium phosphate represented by the formula (1).

Compounding is the modification of plastic materials using chemical changes or additives to change the state of the plastic properties and apply it to a particular end use.

The quaternary ammonium phosphate fungicide of Formula 1 used in the present invention has an inhibitory function against aquatic microorganisms such as mold, bacteria, yeast, and anticorrosive function against metals such as carbon steel, copper, and the like, powder, granules, and flakes. Solid forms such as the like.

As the polymer material, any polymer capable of working at low temperatures having a low melting point can be used, and water-soluble materials such as polyethylene oxide (PEO, molecular weight 5,000 to 100,000), polyacrylic series (molecular weight 1,000 to 100,000) and polyvinylacetate (PVA, molecular weight 1,000) To 1,000,000), and water-insoluble materials such as biodegradable polyesters. Biodegradable polyesters are aliphatic polyesters with a melting temperature of 180 ° C. or less, aliphatic / aromatic random copolymers with a melting temperature of 180 ° C. or less, blends of block copolymers and aliphatic polyesters thereof, and number average molecular weights of 80,000 or less, and melt flow Index (190 degreeC, 2160g) contains 0.1 or more.

Biodegradable aliphatic polyesters with a melting temperature of 180 ° C or less are polybutylene succinate (Tm 113 ° C), polybutylene succinate adipate (Tm 60-112 ° C), polycaprolactone (Tm 60 ° C), PLA (polylactic acid or polylactide, Tm 165 ° C.), and polybutylene succinate is preferred and does not limit the particular polymer.

Aliphatic polyesters of the polybutylene succinate type include two types of SKYGREEN and Bionolle of Showa Hipolymer, which are developed by polymerizing acid monomers and alcohol monomers, and having a number average molecular weight of 10,000 to 60,000. It is a thermoplastic aliphatic polyester represented by the formula (2) having a melting point of 60 to 120 ° C.

[Formula 2]

In Formula 2, R ₄ is hydrogen or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, R ₅ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and n is an integer of 150 to 300.

The acid component monomers constituting the aliphatic polyester include dicarboxylic acids represented by the formula (3), such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and sumeric acid, having 1 to 3 carbon atoms. It is preferable to use at least one selected from the group consisting of dicarboxylic acid alkyl esters and anhydrides of the dicarboxylic acids, and those selected from the group consisting of succinic acid, adipic acid, methyl esters thereof and anhydrides thereof. It is more preferable to use species or more.

[Formula 3]

R ₄ in Formula 3 is hydrogen or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.

As the alcohol component monomer constituting the aliphatic polyester, it is preferable to use one or more diols of the formula (4) such as substituted or unsubstituted ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, and octanediol. More preferably, ethylene glycol, 1,4-butanediol or mixtures thereof. In the case of substituted diols, lower alkyl groups and / or hydroxy groups are preferred as substituents.

[Formula 4]

R ₅ in Chemical Formula 4 is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.

In addition, the biodegradable aliphatic polyester of the present invention is polymerized by introducing polyethyleneglycol, isocyanate, oxazoline, epoxide, polyfunctional alcohol and / or polyfunctional carboxylic acid having a molecular weight of 100 to 9,000 as a third component in addition to the monomers described above. You may use what was manufactured.

Aliphatic / aromatic copolymers are random and block copolymers prepared by esterifying or exchanging an aliphatic acid with an aromatic acid, an ester and an anhydride, and a substituted or unsubstituted diol having 2 or more carbon atoms, and having a melting temperature of 180 ° C. or less. It is a polymer. It also includes blends of aliphatic polyesters with aromatic polyesters such as polyethylene terephthalate (PET) or polybutyleneterephthalate (PBT) and aliphatic polyesters.

According to the present invention, a quaternary ammonium phosphate fungicide and a biodegradable polyester polymer are compounded to form a plate or granule, thereby describing a method of preparing a controlled release water treatment agent capable of controlling the amount of release required.

Polyester resins and disinfectants in consideration of degradability, physical properties, etc. are compounded and pelletized by using an extruder equipped with a single or twin screw. When compounding, the temperature range of the cylinder is determined by the melting point of the resin and the sterilizing agent, and preferably 100 ° C to 150 ° C. When the temperature is less than 100 ° C., the dispersity of the quaternary ammonium phosphate in the resin decreases, and when the temperature exceeds 150 ° C., the internal temperature of the extruder is higher than the actual temperature due to frictional heat and retention time, and thermal decomposition of the sterilizer may occur. The preferred mixing ratio of the polyester resin and the sterilizing agent is 10:90 to 99.9: 0.1 by weight, more preferably 20:80 to 80:20. When the mixing ratio of the polyester resin is less than 10% by weight, compounding is difficult and workability is poor, when the mixing ratio of the disinfectant is less than 0.1% by weight, the release effect as a disinfectant is inferior. The pellets are extruded again with an extruder to obtain a plate of the desired thickness and area. The thickness or diameter of the plate or granule of the final product is 0.1 to 50 mm, which varies depending on the resin content of the sterilizing agent, and preferably 0.3 to 7.0 mm. When it is less than 0.3 mm, the sustained release effect is hardly expected, and when it exceeds 7.0 mm, effective controlled elution is not obtained. The release duration of the product is 24 hours or more, which is the minimum time to dissolve and disperse when a water-soluble polymer is used in the binding polymer, and in a water treatment system, the half-life of the chemicals staying is operated to 24 hours or more.

The water treatment composition prepared according to the present invention can be used in the field of antibacterial treatment for light-dissipating sheets, polymer containers requiring microbial inhibition by contacting a large amount of water or moisture, sterilization-corrosive agents for cooling towers, sinks and toilets.

EXAMPLE

The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

65% by weight of aliphatic polyester polybutylene succinate and 35% by weight of benzethonium phosphate having a melting point of 113 ° C. and a number average molecular weight of 35,000 were twin screw extruded at a cylinder temperature of 120 to 140 ° C. Compounds were used to make pellets.

Example 2

It was prepared in the same manner as in Example 1 except that 55% by weight of polybutylene succinate and 45% by weight of benzesonium phosphate were used.

Example 3

It was prepared in the same manner as in Example 1 except that 45% by weight of polybutylene succinate and 55% by weight of benzesonium phosphate were used.

Example 4

It was prepared in the same manner as in Example 1 except that 65% by weight of aliphatic polyester polybutylene succinate adipate having a melting point of 80 ° C and a number average molecular weight of 31,000 and 35% by weight of benzesonium phosphate were used.

Example 5

It was prepared in the same manner as in Example 1 except that 65% by weight of aliphatic polyester polycaprolactone and 35% by weight of benzesonium phosphate having a melting point of 60 ° C. and a number average molecular weight of 40,000 were used.

Example 6

It was prepared in the same manner as in Example 1 except that 65% by weight of aromatic / aliphatic copolymer polybutylene succinate terephthalate having a melting point of 90 ° C. and a number average molecular weight of 28,000 was used and 35% by weight of benzesonium phosphate.

Example 7

Except for using 50% by weight of polybutylene succinate and 50% by weight of benzalkonium phosphate (benzalkonium phosphate) was prepared in the same manner as in Example 1.

Comparative Example 1

It was prepared in the same manner as in Example 1 except that 5 wt% of polybutylene succinate having a melting point of 113 ° C. and a number average molecular weight of 35,000 and 95 wt% of benzesonium phosphate were used.

Comparative Example 2

Tween with 65% by weight of aromatic / aliphatic copolymer polybutylene succinate terephthalate and 35% by weight of benzesonium phosphate having a melting point of 180 ° C and a number average molecular weight of 28,000 Except for using a screw extruder was prepared in the same manner as in Example 1.

Table 1 shows the insertion values, analytical values and workability of each of the compositions prepared according to the methods of Examples and Comparative Examples. Inserted value is the weight value measured for compounding, and analytical value is an experimental value of the content of the disinfectant contained in the obtained injection product. The appropriate amount of the injection product is dissolved in boiling chloroform to elute the disinfectant, and water is added to convert the polymer into insoluble. After filtration, the filtrate is a value quantified by spectroscopy with a wavelength of 700 nm. The workability was judged based on the volatility of harmful substances due to pyrolysis and chip cutting as a criterion.

Content analysis and workability results for fungicides division Insertion Analysis Workability Example 1 35 34 Good Example 2 45 43 Good Example 3 55 51 Good Example 4 35 33 Good Example 5 35 32 Good Example 6 35 33 Good Example 7 50 40 Good Comparative Example 1 95 ^-a Bad Comparative Example 2 35 1 ^b Bad

a: Not measurable (compounded, chipped and shattered)

b: 1 or less (all disinfectants are pyrolyzed)

[Effect Example 1]

The pellet of Example 4 was extruded again, and the plate shape of thickness 1.35mm was manufactured. The prepared plate was cut into 5 cm in diameter, filled with water in a 1 L beaker, and the concentration of the disinfectant released while stirring at 40 rpm at 100 rpm was quantitatively analyzed. A sustained release graph showing the amount of fungicide released as a function of time is shown in FIG. 1.

[Effect Example 2]

The experiment was carried out in the same manner as in Example 1 except that the thickness was adjusted to 4.2 mm.

[Effect Example 3]

Except that the pellet of Example 7 was extruded again and the plate shape of thickness 1.4mm was manufactured, it experimented by the method similar to the effect example 1.

[Effect Example 4]

Except that the pellet of Example 7 was extruded again and the plate shape of thickness 4.0mm was manufactured, it experimented by the method similar to the effect example 1.

[Example 5]

Except that the pellet of Example 7 was extruded again and the plate shape of 5.3 mm thickness was manufactured, it experimented by the method similar to the effect example 1.

A sustained release graph showing the amount of fungicide released in Effect Examples 1 to 5 as a function of time is shown in FIG. 1, and the sustained effect period measured therefrom is shown in Table 2. In the sustained effect period, a section of 150 hours to 470 hours is assumed to be a primary function section in FIG. 1, and an X value when Y = 100 is defined as a sustained effect period.

Western effect period division Effect example 1 Effect example 2 Effect example 3 Effect example 4 Effect example 5 Western effect period (days) 88.7 82 8.6 174 379

The present invention can be prepared by controlling the disinfectant and the naturally decomposed polymer material to maintain and control the proper concentration of the disinfectant without the need for frequent input, and to produce a controlled release water treatment agent that simultaneously exhibits sterilization and corrosion protection.

Claims (6)

a) fungicide of quaternary ammonium phosphate represented by the following formula (1); And b) biodegradable or water soluble polymer materials compounded with the fungicides Sustained release solid water treatment composition comprising: [Formula 1]

In Chemical Formula 1, R ₁ includes an ether bond as a linear or pulverized alkyl radical or aryl radical having 1 to 27 carbon atoms, R ₂ and R ₃ are each an alkyl radical having 1 to 10 carbon atoms or a heterocyclic compound containing oxygen and nitrogen, Bn is a benzyl group. The method of claim 1, The biodegradable polymer material is polyethylene oxide, wherein the water-soluble polymer material is selected from the group consisting of polyacrylic, polyvinylacetate, biodegradable polyester, sustained-release solid water treatment composition. The method of claim 2, The sustained release solid water treatment composition of the biodegradable polyester is selected from the group consisting of aliphatic polyesters, aliphatic / aromatic random copolymers, block copolymers, and blends thereof with aliphatic polyesters. The method of claim 3, The aliphatic polyester is a sustained-release solid water treatment composition is selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, polycaprolactone, and PLA. The method of claim 3, The aliphatic polyester is represented by the following general formula (1), and is a sustained-release solid water treatment composition is prepared by polymerization of an acid component monomer and an alcohol component monomer: [Formula 2]

In Chemical Formula 2, R ₄ is hydrogen or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, R ₅ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, n is an integer of 150 to 300. A fungicide of quaternary ammonium phosphate represented by the following formula (1). And compounding the biodegradable or water soluble polymer material. Method for producing a sustained-release solid-state water treatment composition comprising: [Formula 1]

In Chemical Formula 1, R ₁ includes an ether bond as a linear or pulverized alkyl radical or aryl radical having 1 to 27 carbon atoms, R ₂ and R ₃ are each an alkyl radical having 1 to 10 carbon atoms or a heterocyclic compound containing oxygen and nitrogen, Bn is a benzyl group.

Images