KR20200000712A - Water dispersing polyurethane composition for removing chemical warefare agents and method of preparing the same - Google Patents

Abstract

The present invention relates to a water-dispersible polyurethane composition for adsorbing or removing a toxic chemical substance or a chemical agent, comprising: a water-dispersible polyurethane including a carboxyl group as a substituent; and an active material dispersed in the water-dispersible polyurethane and including a metal-organic framework (MOFs). The present invention can improve miscibility with UiO66 by controlling surface energy of polyurethane to have a similar value to UiO66 in order to disperse UiO66, which is an organophosphate-based pesticide and a nerve agent decomposing substance, in water-dispersible polyurethane. In addition, it is possible to prepare coating agents, paints, etc., in which particulate UiO66 having excellent performance in decomposing the organic organophosphate-based pesticides and nerve agent decomposing substance is dispersed, and to prepare films capable of adsorbing and removing enormous toxic industrial chemical substances and chemical agents having structures and properties similar to those of pesticide and nerve agent-like substances by using the coating agents, paints, and the like.

Description

Water dispersible polyurethane composition for chemical agent removal and its manufacturing method {WATER DISPERSING POLYURETHANE COMPOSITION FOR REMOVING CHEMICAL WAREFARE AGENTS AND METHOD OF PREPARING THE SAME}

The present invention relates to a water dispersible polyurethane composition for chemical agent removal, and a method for preparing the same, and more particularly, to a composition comprising a water dispersible polyurethane and active material for adsorbing and removing toxic industrial chemicals and chemical agents, and a method for preparing the same. It is about.

Chemical agent means a compound that is operated to kill, disable or cause serious damage to personnel by its chemical nature. These chemical agents include incapacitating agents, riot suppressing agents, herbicides, etc., and may be classified into persistent agents and non-persistent agents depending on the duration of the agent.

The phenomena and damages caused by the attack by chemical agents can occur very seriously depending on the situation.The chemical weapons, unlike conventional weapons and nuclear weapons, which lose their function and danger at the time of destruction, leave toxic residues. There is a high probability of damaging the surrounding area.

Chemical agents include hydrogen cyanide (AC) and cyan chloride (CK) with low molecular weights, ethyl N, N-dimethylphosphoramidocyanidate (Tabun), isopropyl methylphosphonofluoridate (Sarin), and pita. Various materials such as collyl ylphosphofluoride (Soman) or O-ethyl S- (2-diisopropylaminoethyl) methylphosphonothiolate.

As a method for protecting such chemical agents, a widely used method since World War II to the present is adsorption by activated carbon. High molecular weight chemical agents such as Sarin (GB), Soman (GD) and Mustard (HD) adsorb well on adsorbents with large pore sizes, such as activated carbon or polymer resins, and have low molecular weight chemicals such as hydrogen cyanide ( AC) and cyanide chloride (CK) adsorb well on molecular sieves.

However, the adsorption method is a temporary removal of chemical agents by simple physical adsorption. Existing adsorbents have the disadvantages that the adsorbed materials can be easily desorbed under high temperature and high humidity conditions, and the short lifespan, which is an important requirement for protection, is also short. have.

In addition, as the organophosphate insecticide and nerve agent protective film is known to protect the adsorbent by using a hydrophobic coating to protect the material, the film does not have a degrading function is limited to the protection performance when exposed to high concentrations There was.

On the other hand, UiO66, which is a kind of metal organic framework, is known as organophosphorus insecticide and nerve agent degrading agent, but UiO66 is present in the form of particles and its utilization is limited.

Therefore, there is a need for the development of materials capable of decomposing / removing toxic industrial chemicals and chemical agents using UiO66.

KR 10-1847773 B1

An object of the present invention is to solve the above problems, in order to disperse the organic phosphorus (organophosphate) insecticide and neurodegrading agent UiO66 in the water-dispersible polyurethane, the surface energy of the polyurethane was controlled to have a value similar to UiO66 .

Another object of the present invention is to prepare a coating, paint, etc. dispersed in a particle UiO66 dispersed in the organic phosphorus pesticides and nerve agent chemicals, using this structure similar to the insecticide and nerve agent-like substance And it provides a composition capable of adsorption and removal of a large number of toxic industrial chemicals and chemical agents and properties and a film comprising the same.

According to one aspect of the invention,

Water-dispersible polyurethane containing a carboxyl group as a substituent; And an active material dispersed in the water-dispersible polyurethane and comprising a metal-organic framework (MOFs), wherein the water-dispersible polyurethane composition for adsorption or removal of toxic chemicals or chemical agents To provide.

The water dispersible polyurethane composition further includes polyvinyl alkyral (poly (vinyl alkyral)), wherein the alkyl group contained in the polyvinyl alkral may be C1 to C6.

The water dispersible polyurethane composition may further include a polar solvent.

The water dispersible polyurethane composition is 100 parts by weight of the water dispersible polyurethane; 5 to 30 parts by weight of the active substance: 20 to 50 parts by weight of the poly (vinyl alkyral), and a balance of the polar solvent: may be included.

The water-dispersible polyurethane reacts with a polyol compound, a diol compound having a carboxyl group as a substituent, and a diisocyanate compound to prepare a first prepolymer in which both ends are substituted with an isocyanate group, and the first prepolymer is substituted with a hydroxyl group as a substituent. Reacting with at least one of five alcohol compounds to prepare a second prepolymer in which all or part of 2 to 5 terminals are each substituted with an isocyanate group, and neutralizing the carboxyl group of the second prepolymer by using a neutralizing agent to form a second prepolymer. A salt is prepared and a polyurethane is prepared by reacting an isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender by adding a chain extender to the first prepolymer salt, wherein the polyol compound is linear, and both ends thereof are hydroxyl groups. Substituted polyether A polyol or polyesterpolyol, wherein the diisanate compound is linear, branched, cyclic, or a combination thereof, the alcohol compound is linear, branched, cyclic, or a combination thereof, and the chain extender is a diol compound or diamine It may include a compound.

The polyol compound may be poly (tetramethylene ether) glycol (PTMG), polycaprolactone diol (PCL), polypropylene glycol diol (PPG) and polybutyl 1 or more selected from poly (butylene adipate) diol (PBA), wherein the diol compound is selected from dimethylolpropionic acid, and dimethylolbutanoic acid. Including at least a species, the diisocyanate compound is isophorone diisocyanate (IPDI), 4,4'-methylene-bis-cyclohexyl isocyanate (4,4'-Methylenebis (cyclohexyl isocyanate), H12MDI), hexa Methylene diisocyanate (HDI), ethylene diisocyanate, butane-1,4-diisocyanate, tetra It contains at least one selected from the group consisting of butylbutane-1,4-diisocyanate (Tetramethylbutane-1,4-diisocyanate), the alcohol compound is tris hydroxymethyl propane (1,1,1-Tris (hydroxylmethyl) propane), Glycerin, triethanolamine may include at least one selected from the chain extender may include at least one selected from ethylene glycol, butanediol, hexanediol and propanediol.

The metal-organic framework includes a metal ion and an organic ligand coordinated to the metal ion, and the metal ion includes one of ions selected from zirconium, zinc, manganese, copper, beryllium, magnesium, and cobalt. can do.

The metal-organic framework may include any one selected from UiO-66, UiO-67, and UiO-68.

The weight average molecular weight (Mw) of the polyol compound may be 500 to 3000 g / mol.

The polar solvent is water, methyl ethyl ketone, ethanol, 1-ethyl-2-pyrrolidone (1-Ethyl-2-pyrrolidone), acetone, 1-methyl-2-pyrrolidone (1-methyl-2-pyrrolidinone ) And dimethylformamide (Dimethylformamide).

The toxic chemicals or chemical agents may include one or more selected from organophosphorous insecticides and similar nerve agents.

The neutralizing agent may be an amine compound.

In another aspect of the invention, there is provided a composite film comprising a water dispersible polyurethane composition, for adsorption or removal of toxic chemicals or chemical agents.

In another aspect of the invention, (a) preparing a water-dispersible polyurethane comprising a carboxyl group as a substituent; And (b) mixing an active material including a metal-organic framework (MOFs), the water-dispersible polyurethane, and a polar solvent to prepare a water-dispersible polyurethane composition; It provides a method for producing a water-dispersible polyurethane composition comprising a.

Step (a) is a reaction of the polyol compound (a-1), a diol compound having a carboxyl group as a substituent, and a diisocyanate compound to prepare a first prepolymer, each terminal is substituted with an isocyanate group; (a-2) reacting the first prepolymer with at least one of the alcohol compounds having 2 to 5 hydroxyl groups as a substituent to prepare a second prepolymer in which all or part of the 2 to 5 terminals are each substituted with an isocyanate group And (a-3) neutralizing the carboxy group of the second prepolymer to prepare a second prepolymer salt; And (a-4) adding a chain extender to the second prepolymer salt to react the isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender to prepare a polyurethane, wherein the polyol compound is linear A polyetherpolyol or a polyesterpolyol substituted at both ends with a hydroxy group, wherein the diisoanate compound is linear, branched, cyclic, or a combination thereof, and the alcohol compound is linear, branched, cyclic, or a combination thereof The chain extender may include a diol compound or a diamine compound.

In another aspect of the present invention, a method for producing the water dispersible polyurethane composition; It provides a method for producing a composite film comprising a; and (c) coating the composition on a substrate and dried to produce a composite film.

The present invention can improve the miscibility with UiO66 by controlling the surface energy of the polyurethane to have a value similar to that of UiO66 in order to disperse UiO66, which is an organophosphate insecticide and neuroagent decomposition agent, in a water dispersible polyurethane. have.

In addition, it is possible to prepare coatings and paints in which UiO66 is dispersed in the organic phosphorus-based insecticides and nerve agent chemicals, which have a structure and properties similar to those of insecticides and nerve agent analogs. It is possible to prepare a composition and a film using the same that can absorb and remove toxic industrial chemicals and chemical agents.

1 shows a schematic diagram of a composite film in which UiO66 prepared according to an embodiment of the present invention is dispersed in a water dispersible polyurethane.
2 is a schematic diagram showing the chemical structure and three-dimensional structure of UiO66.
Figure 3 shows a SEM image of the active material UiO66.
Figure 4 is a photograph of a composition of a mixture of polyurethane and UiO66 prepared according to an embodiment of the present invention.
5 shows changes in tensile strength and elongation of the composite film according to the content of UiO66.
6 shows the SEM image of the composite film surface according to the content of UiO66.
7 shows a cross-sectional SEM image of the composite film according to the content of UiO66.
Figure 8 shows the UV-Vis spectral analysis showing the decomposition of methyl paraoxon (methyl paraoxon), a similar chemical agent.
Figure 9 shows the results of absorbance analysis by concentration of Nitrophenolate showing the amount of nitrophenolate produced by the decomposition of methyl paraoxone (methyl paraoxon).
Figure 10 shows the absorbance analysis results for each concentration of Nitrophenolate showing the amount of nitrophenolate produced by the decomposition of methyl parathion (methyl parathion).
FIG. 11 shows changes in tensile strength and elongation of the water-dispersible polyurethane composition including polyvinyl butyral of Example 6. FIG.
12 shows the results of analyzing the decomposition ability of methyl paraoxon (methyl paraoxon) of the water-dispersible polyurethane composition containing polyvinyl butyral of Example 6.
FIG. 13 shows the results of analyzing the decomposition ability of methyl parathion of the water-dispersible polyurethane composition including polyvinyl butyral of Example 6. FIG.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

In addition, when a component is referred to as being "formed" or "laminated" on another component, it may be directly attached to, or laminated to, the front or one side on the surface of the other component, It will be understood that other components may exist in the.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

1 is a schematic view showing a composite film containing a water-dispersible polyurethane and an active material of the present invention.

Hereinafter, the water dispersible polyurethane composition of the present invention will be described.

The present invention is a water-dispersible polyurethane containing a carboxyl group as a substituent; And an active material dispersed in the water-dispersible polyurethane and comprising a metal-organic framework (MOFs), wherein the water-dispersible polyurethane composition for adsorption or removal of toxic chemicals or chemical agents To provide.

The water dispersible polyurethane composition further includes polyvinyl alkyral (poly (vinyl alkyral)), wherein the alkyl group contained in the polyvinyl alkral may be C1 to C6.

The water dispersible polyurethane composition may further include a polar solvent.

The water dispersible polyurethane composition is 100 parts by weight of the water dispersible polyurethane; 5 to 30 parts by weight of the active substance: 20 to 50 parts by weight of the poly (vinyl alkyral), and a balance of the polar solvent: may be included.

The water-dispersible polyurethane reacts with a polyol compound, a diol compound having a carboxyl group as a substituent, and a diisocyanate compound to prepare a first prepolymer in which both terminals are each substituted with an isocyanate group,

Reacting the first prepolymer with at least one of alcohol compounds having 2 to 5 hydroxy groups as a substituent to prepare a second prepolymer in which all or part of 2 to 5 terminals are each substituted with an isocyanate group,

Neutralizing the carboxyl group of the second prepolymer using a neutralizing agent to prepare a second prepolymer salt,

A polyurethane prepared by adding a chain extender to the first prepolymer salt to react an isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender,

The polyol compound is linear and comprises a polyetherpolyol or a polyesterpolyol substituted at both ends with a hydroxy group,

The diisoanate compound may be linear, branched, cyclic, or a combination thereof, the alcohol compound may be linear, branched, cyclic, or a combination thereof, and the chain extender may include a diol compound or a diamine compound.

The polyol compound may be poly (tetramethylene ether) glycol (PTMG), polycaprolactone diol (PCL), polypropylene glycol diol (PPG), polybutyl Ethylene adipate diol (Poly (butylene adipate) diol, PBA) and the like, the diol compound includes dimethylol propionic acid (Dimethylolpropionic acid), dimethylol butanoic acid (Dimethylolbutanoic acid), and the like, Isocyanate compounds include isophorone diisocyanate (IPDI), 4,4'-methylene-bis-cyclohexyl isocyanate (4,4'-Methylenebis (cyclohexyl isocyanate), H12MDI), hexamethylene diisocyanate, HDI), ethylene diisocyanate, butane-1,4-diisocyanate, tetramethylbutane-1,4-diisocyanate (Tetramethylbutane-1,4 -diisocyanate) and the like, the alcohol compound includes tris hydroxymethyl propane (1,1,1-Tris (hydroxylmethyl) propane), glycerin (Glycerin), triethanolamine (Triethanolamine) and the like, the chain extender May include ethylene glycol, butanediol, hexanediol, propanediol, and the like.

The metal-organic framework may include a metal ion and an organic ligand coordinated to the metal ion, and the metal ion may include zirconium, zinc, manganese, copper, beryllium, magnesium, cobalt, and the like. May be an ion in which the metal ion includes zirconium.

The metal-organic framework may include UiO-66, UiO-67, UiO-68, and the like.

In addition, the active substance may include all that include the function of decomposing or removing toxic chemicals or chemical agents.

The water dispersible polyurethane and the active material may have similar surface energy values so that the active material may be uniformly dispersed in the water dispersible polyurethane.

The ratio (E1 / E2, r) of the surface energy (E2) of the metal-organic framework to the surface energy (E1) of the water-dispersible polyurethane may be 0.7≤r≤1.3, preferably 0.9≤r≤1.0 It is not dispersed when the surface energy ratio is out of 0.9 ~ 1.0.

The surface energy of the water-dispersible polyurethane may be 30 to 50 mN / m, preferably 35 to 50 mN / m, more preferably 40 to 50 mN / m.

The weight average molecular weight (Mw) of the polyol compound may be 500 to 3000 g / mol, preferably 600 to 2800 g / mol, more preferably 600 to 2200 g / mol.

The polar solvent is water, methyl ethyl ketone, ethanol, 1-ethyl-2-pyrrolidone (1-Ethyl-2-pyrrolidone), triethanolamine, acetone, 1-methyl-2 pyrrolidone (1- methyl-2-pyrrolidinone), dimethylformamide, and the like.

The toxic chemicals or chemical agents may include organophosphorous insecticides, neuronal agents, and the like.

The toxic industrial chemicals and chemical agents may include an organophosphorous insecticide, a similar nerve agent, and the like, and the organophosphorus insecticide may include methyl parathion. Neurological agents may include methyl paraoxon.

The neutralizing agent may comprise an amine compound.

The present invention comprises a water dispersible polyurethane composition and provides a composite film for adsorption or removal of toxic chemicals or chemical agents.

The water dispersible polyurethane composition of the present invention may be prepared in the following order.

First, a water dispersible polyurethane containing a carboxyl group as a substituent is prepared (step a).

Step (a) may be performed sequentially in the following order.

First, a polyol compound, a diol compound having a carboxyl group as a substituent, and a diisocyanate compound are reacted to prepare a first prepolymer in which both terminals are each substituted with an isocyanate group (step a-1).

The diisoanate compound may comprise linear, branched, cyclic, or a combination thereof.

Next, the first prepolymer is reacted with at least one of alcohol compounds having 2 to 5 hydroxyl groups as a substituent to prepare a second prepolymer in which all or part of 2 to 5 terminals are each substituted with isocyanate groups (a- 2).

The alcohol compound may be linear, branched, cyclic or a combination thereof.

Next, the carboxyl group of the second prepolymer is neutralized to prepare a second prepolymer salt (step a-3).

Finally, a chain extender is added to the second prepolymer salt to prepare a polyurethane by reacting an isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender (step a-4).

The chain extender may include a diol compound or a diamine compound.

Finally, metal-organic Framework (Metal-organic framework, MOFs ), A water-dispersible polyurethane, and a polar solvent are mixed to prepare a water-dispersible polyurethane composition (step b).

The present invention provides a method for producing a composite film comprising the step (c) after the step (b), coating the composition substrate and dried to produce a composite film.

In step (c), the substrate corresponds to a substrate for coating the composition. The substrate may be a glass substrate, stainless steel, aluminum plate, coated steel, etc., but the scope of the present invention is not limited thereto.

EXAMPLE

Preparation Example 1 Preparation of Water Dispersible Polyurethane (Without Ethylene Glycol)

(Prepolymer Preparation Step)

DMPA (2,2-) dissolved in 0.015 mol of poly (tetramethylene ether) glycol, Mw = 2000 g / mol, Sigma Aldrich Co., USA) and NEP (1-Ethyl-2-pyrrolidone) in 500 ml round bottom flask Dimethylolpropionic aicd) 0.015mol was added and stirred at 70 ° C for 30 minutes. DBTDL (Dibutyltin dilaurate) and 0.059mol of IPDI (Isophorone diisocyanate) containing an isocyanate group were added and then reacted at 70 ° C. for 2 hours.

Here, 0.01 mol of TMP (1,1,1-Tris (hydroxylmethyl) propan) dissolved in N-Ethylpyrrolidone (NEP) was added thereto, followed by further reaction for 2 hours, and then cooled to 60 ° C. Acetone was added to prevent the viscosity from increasing during cooling.

(Neutralization and chain extension stage)

When the temperature reached 60 ° C, the solution was neutralized by adding TEA (equivalent to DMPA). At 35 ° C., the chain extension reaction was carried out by adding hydrazine for 1 hour, after which acetone was removed by rotary, to obtain a blue water-dispersible polyurethane dispersion. Solid content of the water dispersible polyurethane solution was adjusted to 30wt%.

The amounts of NEP and acetone did not exceed 4.6wt% and 20wt% of the total solids content, respectively.

Scheme 1

Preparation Example 2 Preparation of Water Dispersible Polyurethane

The same method as in Preparation Example 1, except that PTMG having a weight average molecular weight of Mw = 1000 g / mol was used instead of PTMG (Poly (tetramethylene ether) glycol) having a weight average molecular weight of Preparation Example Mw = 2000 g / mol. A water dispersible polyurethane was prepared.

Preparation Example 3 Preparation of Water Dispersible Polyurethane

The same method as in Preparation Example 1, except that PTMG having a weight average molecular weight of Mw = 650 g / mol was used instead of PTMG (Poly (tetramethylene ether) glycol) having a weight average molecular weight of Preparation Example 1 Mw = 2000 g / mol. A water dispersible polyurethane was prepared.

Preparation Example 4 Preparation of Water Dispersible Polyurethane (Using Ethylene Glycol)

(Prepolymer Manufacturing Step)

DMPA (2,2-) dissolved in 0.015 mol of poly (tetramethylene ether) glycol, Mw = 2000 g / mol, Sigma Aldrich Co., USA) and NEP (1-Ethyl-2-pyrrolidone) in 500 ml round bottom flask Dimethylolpropionic aicd) 0.015mol was added and stirred at 70 ° C for 30 minutes. After the addition of the catalyst DBTDL (Dibutyltin dilaurate) and IPDI (Isophorone diisocyanate) containing an isocyanate group was reacted at 70 ℃ temperature for 2 hours. Thereafter, 0.0117mol of EG (Ethylene glycol) dissolved in acetone was added, followed by reaction at 70 ° C for 1 hour. To this was added 0.0067mol of TMP (1,1,1-Tris (hydroxylmethyl) propan) dissolved in NEP and allowed to react for 2 hours and then cooled to 60 ° C. Acetone was added to prevent the viscosity from increasing during cooling.

(Neutralization and chain extension)

When the temperature reached 60 ° C, the solution was neutralized by adding TEA (equivalent to DMPA), water was added, the rpm was increased to 800, dispersed for 30 minutes, and cooled to 35 ° C. At 35 ° C., hydrazine (NH ₂ -NH ₂ ) was added to the chain extension reaction for 1 hour, after which acetone was removed by rotary, to obtain a blue water-dispersible polyurethane dispersion. Solid content of the water dispersible polyurethane solution was adjusted to 30wt%.

The amounts of NEP and acetone did not exceed 4.6wt% and 20wt% of the total solids content, respectively.

Scheme 2

Preparation Example 5 Preparation of Water Dispersible Polyurethane

0.003 mol of TMP (1,1,1-Tris (hydroxylmethyl) propan) and 0.003 mol and EG (Ethylene) instead of 0.0017 mol of TMP (1,1,1-Tris (hydroxylmethyl) propan) and 0.0117 mol of ethylene (Ethylene glycol) of Preparation Example 4 glyco) A water-dispersible polyurethane was prepared in the same manner as in Preparation Example 4, except that 0.0135 mol was used.

Preparation Example 6 Preparation of Water Dispersible Polyurethane (without TMP)

(Prepolymer)

DMPA (2,2-) dissolved in 0.015 mol of PT (Poly (tetramethylene ether) glycol, Mw = 2000 g / mol, Sigma Aldrich Co., USA) and NEP (1-Ethyl-2-pyrrolidone) in 500 ml round bottom flask Dimethylolpropionic aicd) 0.015mol was added and stirred at 70 ° C for 30 minutes. After the addition of DBTDL (Dibutyltin dilaurate) and IPDI (Isophorone diisocyanate) containing isocyanate groups, the reaction was carried out at 70 ° C for 2 hours, and then 0.15mol of EG (Ethylene glycol) dissolved in acetone was added. After the reaction at ℃ temperature was cooled to 60 ℃. Acetone was added to prevent the viscosity from increasing during cooling.

(Neutralization and chain extension stage)

When the temperature reached 60 ° C, the solution was neutralized by adding TEA (equivalent to DMPA), and water was added to increase the rpm to 800, followed by dispersion for 30 minutes, and then cooled to 35 ° C. At 35 ° C., the chain extension reaction was carried out by adding hydrazine for 1 hour, after which acetone was removed by rotary, to obtain a blue water-dispersible polyurethane dispersion. Solid content of the water dispersible polyurethane solution was adjusted to 30 wt%.

The amounts of NEP and acetone did not exceed 4.6wt% and 20wt% of the total solids content, respectively.

The types, materials and properties of the water-dispersible polyurethane of the polyols of Preparation Examples 1 to 6 are summarized as in Table 1 below, and PTMG2000 in Table 1 means PTMG having a molecular weight of Mw = 2000 g / mol.

division Polyol Type TMP (mol) EG
(mol) DMPA
(mol) Hard segment
(wt%) T _g
(° C) Particle size
(nm) E
(MPa) s (MPa) e
(%) Preparation Example 1 PTMG 2000 0.01 0 0.015 35.55 -72.6 97.2 15.01 7.51 781.49 Preparation Example 2 PTMG 1000 0.01 0 0.015 46.43 -44.9 73.3 91.16 7.73 525.15 Preparation Example 3 PTMG 650 0.01 0 0.015 52.86 -11.5 57.6 121.06 10.76 290.07 Preparation Example 4 PTMG 2000 0.0067 0.0117 0.015 35.38 -73.4 77.6 4.89 5.21 1055.41 Preparation Example 5 PTMG 2000 0.003 0.0135 0.015 35.36 -74.0 76.1 4.19 4.10 1125.24 Preparation Example 6 PTMG 2000 0 0.15 0.015 35.15 -74.5 80.3 3.11 3.30 1301.99

Comparative Production Example  One: PCL2000  Polyurethane containing

Same as Preparation Example 1 except that PCL2000 (polycarprolactone, Mw = 2000 g / mol) was used instead of PTMG (Poly (tetramethylene ether) glycol, Mw = 2000 g / mol, Sigma Aldrich Co., USA) It was prepared by the method.

Comparative Production Example 2: Polyurethane Including PCL530

Same as Preparation Example 1 except that PCL530 (polycarprolactone, Mw = 530 g / mol) was used instead of PTMG (Poly (tetramethylene ether) glycol, Mw = 2000 g / mol, Sigma Aldrich Co., USA) It was prepared by the method.

Example 1 Preparation of a Composite Film and Composition Comprising 7.1wt% UiO66

(Production of Water Dispersible Polyurethane Composition)

The composition was prepared by adding 7.1 wt% of UiO66 dispersed in a methyl ethyl ketone (MEK) solvent to a solution containing the water-dispersible polyurethane prepared according to Preparation Example 1 and then sonicating for 30 minutes.

(Composite film production)

The dispersion of the water-dispersible polyurethane and UiO66 dispersed in a white opaque color, the solution was transferred to a Teflon dish and dried for 12 to 24 hours at 40 ℃ oven to prepare a composite film.

Example 2: Composition and Composite Film Preparation Containing 13.3wt% UiO66

A composite film was prepared in the same manner as in Example 1, except that a composition including 13.3 wt% of UiO66 was used instead of a composition containing 7.1 wt% of UiO66.

Example 3: Composition and Composite Film Preparation Containing 18.7wt% UiO66

A composite film was prepared in the same manner as in Example 1, except that a composition including 18.7 wt% of UiO66 was used instead of a composition containing 7.1 wt% of UiO66.

Example 4 Preparation of a Composite Film and Composition Comprising 23.5 wt% of UiO66

A composite film was prepared in the same manner as in Example 1, except that a composition including 23.5 wt% of UiO66 was used instead of a composition containing 7.1 wt% of UiO66.

Example 5 Preparation of a Composition and Composite Film Comprising 27.7wt% UiO66

A composite film was prepared in the same manner as in Example 1, except that a composition including 27.7 wt% of UiO66 was used instead of a composition containing 7.1 wt% of UiO66.

Example 6: Water Dispersible Polyurethane Composition Comprising Polyvinyl Butyral

(Production of water dispersible polyurethane composition including polyvinyl butyral)

0.6 g of a 6 wt% polyvinyl butyral / ethanol solution and UiO66 dispersed in a solvent of methyl ethyl ketone (MEK) in 0.6 g of a solution containing a water-dispersible polyurethane prepared according to Preparation Example 1 were 18.7 wt% of UiO66. After adding the sonication (sonication) for 30 minutes.

(Composite film production)

The dispersion of the water-dispersible polyurethane and UiO66 dispersed in a white opaque color, the solution was transferred to a Teflon dish and dried for 12 to 24 hours at 40 ℃ oven to prepare a composite film.

Table 2 below shows the types of water-dispersible polyurethane and UiO66 content used in the composite film prepared according to Examples 1 to 5.

division UiO66 Content (Based on Total Solution) UiO66 (Composite Film Weight) Example 1 1 wt% 7.1wt% Example 2 2 wt% 13.3 wt% Example 3 3 wt% 18.7 wt% Example 4 4 wt% 23.5 wt% Example 5 5 wt% 27.7wt%

Comparative example  1: film containing only water-dispersible polyurethane

The film was prepared using the polyurethane prepared according to Preparation Example 1.

Comparative Example 2: Preparation of UiO66 Dispersion Solution

2.5 mg of a solid sample of UiO-66 was added to an n-EM aqueous solution (1 mL, 0.45 M) to disperse UiO-66 while stirring the mixture for 30 minutes to prepare a dispersion.

[Test Example]

Test Example  1: water dispersible polyurethane and UiO66  Of the composition comprising UiO66  Dispersibility Analysis

Table 3 shows the surface energy and UiO66 miscibility of the water dispersible polyurethanes of Preparation Examples 1 to 3 and the polyurethanes of Comparative Preparation Examples 1 and 2, and FIG. 4 shows PCL530 and a composition comprising PTMG2000 and UiO66 It is the photograph which took the composition containing UiO66.

Polyol Type Preparation Example 1 (PTMG2000) Preparation Example 2 (PTMG1000) Preparation Example 3 (PTMG650) Comparative Production Example 1 (PCL2000) Comparative Production Example 2 (PCL530) Surface energy (mN / m) 43.9 46.7 48.5 49.6 50.9 Compatibility with UiO66 height usually lowness lowness lowness

Referring to Table 3 and Figure 4, the polyol PTMG2000 used in the preparation of the water-dispersible polyurethane of the present invention was excellent in the miscibility with UiO66 was found to be well mixed without the layer separation phenomenon.

On the other hand, PCL530 was found to have low layer miscibility with UiO66.

Test Example 2: Tensile Strength and Elongation of Composite Film

Figure 5 shows the tensile strength and elongation of the composite film according to the content of UiO66.

Referring to FIG. 5, in the case of the tensile strength, the tensile strength was lowered as the content of UiO66 included in the composite film was increased.

In the case of the elongation, the elongation was found to increase as the content of UiO66 contained in the composite film increases.

Therefore, it is determined that the elongation and tensile strength of the composite film can be controlled by controlling the content of UiO66.

Test Example 3: Composite film surface and cross-sectional SEM image analysis

6 and 7 are SEM images of the surface and the cross-section of the composite film prepared according to Examples 2 to 4 and the film prepared according to Comparative Example 1.

Referring to FIG. 6, since the composite film prepared according to Examples 2 to 4 contained UiO66, it was confirmed that the UiO66 particles were evenly distributed on the surface. In particular, it was confirmed that the more UiO66 content, the more UiO66 particles are distributed.

In addition, referring to Figure 7, it was found that the UiO66 particles are evenly dispersed throughout the film, it was confirmed that the UiO66 particles are mainly distributed in the lower portion as the UiO66 content increases.

Test Example  4: similar Chemical agent methyl Paraoxone (methyl paraoxon ) Decomposition Characteristic Analysis_UV-Vis Spectrum

8 shows UV-Vis spectra showing degradation of methyl paraoxone, a similar chemical agent.

Referring to FIG. 8, it appears that the nitrophenolate peak (407 nm) generated during methyl paraoxone decomposition increases with time, that is, as methyl paraoxone is degraded.

Therefore, it was analyzed that methyl paraoxone was degraded through nitrophenolate peak analysis.

Test Example 5: Analysis of Degradability

To measure the resolution of UiO-66 particles 2.5 mg of a solid sample of UiO-66 was added to an n-EM aqueous solution (1 mL, 0.45 M) to disperse the UiO-66 while stirring the mixture for 30 minutes. To this mixture was added MPO (6.2 mg, 0.025 mmol). Before the UV-vis measurement, 20 μL was aliquoted periodically and added to the n-EM aqueous solution (10 ml, 0.45 M) and diluted. Progress of the reaction confirmed the absorbance of p-NP at 407 nm.

In addition, to measure the resolution of the WPU / UiO66 composite film, a composite film containing 7.1-27.7 wt% UiO66 dispersed was cut into 1 cm x 1 cm, dropped into an n-EM aqueous solution (1 mL, 0.45 M), and then sonication for 30 minutes. I let you. MPO (6.2 mg, 0.025 mmol) was added to the solution containing the film. Before the UV-vis measurement, 20 μL was aliquoted periodically and added to the n-EM aqueous solution (10 ml, 0.45 M) and diluted. Progress of the reaction confirmed the absorbance of p-NP at 407 nm.

Test Example  5-1: Similar Chemical agent Matyl Paraoxone (methyl paraoxon ) Resolution Analysis

9 shows the results of degrading methyl paraoxone, a similar chemical agent.

Referring to FIG. 9, as a result of observing methyl paraoxone resolution, it was found that the film containing only polyurethane (neat PU) prepared according to Comparative Example 1 had little resolution for methyl paraoxone, and the present invention. In the case of the composite film prepared according to it was confirmed that the decomposition performance similar to the UiO66 slurry (dispersion solution) of Comparative Example 2.

This is because UiO66 showed low stability in the basic solution, and the resolution was relatively low. The composite film was decomposed to the base, and thus, the resolution was similar to that of the composite film.

Test Example  5-2: organophosphorus insecticide methyl  Analysis of methyl parathion degradability

Figure 10 shows the results of the analysis of the decomposition ability of the organophosphorus insecticide methyl parathion.

Referring to FIG. 10, the film including only polyurethane prepared according to Comparative Example 1 (neat PU) showed little resolution for methyl parathion, an organophosphorus insecticide.

On the other hand, the composite film and the UiO66 slurry of the water-dispersible polyurethane and UiO66 of the present invention was found to increase the production rate of nitrophenolate over time, the composite film of the water-dispersible polyurethane and UiO66 of the present invention It was confirmed that the decomposition performance of methyl parathion, an organophosphorus insecticide, similar to that of the UiO66 slurry.

Test Example  6: Polyvinyl butyral  Characterization (degradation performance) analysis of the water-dispersible polyurethane composition containing

11 is a graph showing the tensile strength and elongation of the water-dispersible polyurethane composition comprising a polyvinyl butyral prepared according to Example 6, Table 4 below comprises a polyvinyl butyral prepared according to Example 6 The tensile strength and elongation of the water-dispersible polyurethane film are summarized.

division Tensile strength (MPa) Elongation at break (%) Young's modulus (MPa) Example 6 19.76 ± 3.55 245.10 ± 28.42 46.86 ± 7.06

Referring to FIG. 12, as a result of observing the resolution of methyl paraoxone, the film (PU + PVB) containing only the water-dispersed polyurethane containing polyvinyl butyral prepared according to Comparative Example 1 has a resolution of methyl paraoxone. It was found that almost no, in the case of the composite film of Example 6 it was confirmed that the degradation performance similar to the dispersion solution of UiO66 of Comparative Example 2.

Referring to FIG. 13, it shows a result of analyzing the decomposition ability of metal parathion, an organophosphorus insecticide. On the other hand, the composite film and the UiO66 slurry containing the water-dispersible polyurethane and UiO66 containing the polyvinyl butyral of Example 6 was found to increase the production rate of nitrophenolate over time, the water-dispersible polyurethane of the present invention The composite film containing and UiO66 showed a degrading performance for methyl paraoxone, an organophosphorus insecticide similar to that of the UiO66 slurry.

As mentioned above, although the preferred embodiment of the present invention has been described in detail, the present invention is not limited to the above embodiment, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

Claims (17)

Water-dispersible polyurethane containing a carboxyl group as a substituent; And
And an active material dispersed in the water-dispersible polyurethane and comprising a metal-organic framework (MOFs).
Water dispersible polyurethane composition for adsorption or removal of toxic chemicals or chemical agents. The method of claim 1,
The water dispersible polyurethane composition
Further comprising a polyvinyl alkyral (poly (vinyl alkyral)), wherein the alkyl group contained in the polyvinyl alkral water-dispersible polyurethane composition, characterized in that C1 to C6. The method of claim 1,
The water-dispersible polyurethane composition, wherein the water-dispersible polyurethane composition further comprises a polar solvent. The method of claim 3,
The water dispersible polyurethane composition
100 parts by weight of the water dispersible polyurethane;
5 to 30 parts by weight of the active substance:
20 to 50 parts by weight of the polyvinyl alkyral (poly (vinyl alkyral)): and
A residual amount of the polar solvent: water-dispersible polyurethane composition, characterized in that it comprises a. The method of claim 1,
The water dispersible polyurethane
Reacting a polyol compound, a diol compound having a carboxyl group as a substituent, and a diisocyanate compound to prepare a first prepolymer in which both terminals are each substituted with an isocyanate group,
Reacting the first prepolymer with at least one of alcohol compounds having 2 to 5 hydroxy groups as a substituent to prepare a second prepolymer in which all or part of 2 to 5 terminals are each substituted with an isocyanate group,
Neutralizing the carboxyl group of the second prepolymer using a neutralizing agent to prepare a second prepolymer salt,
A polyurethane prepared by adding a chain extender to the first prepolymer salt to react an isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender,
The polyol compound is linear and comprises a polyetherpolyol or a polyesterpolyol substituted at both ends with a hydroxy group,
The diisoanate compound is linear, branched, cyclic or a combination thereof,
The alcohol compound is linear, branched, cyclic or a combination thereof,
The chain extender is a water-dispersible polyurethane composition, characterized in that it comprises a diol compound or a diamine compound. The method of claim 5,
The polyol compound may be poly (tetramethylene ether) glycol (PTMG), polycaprolactone diol (PCL), polypropylene glycol diol (PPG) and polybutyl Ethylene adipate diol (Poly (butylene adipate) diol, PBA)
The diol compound includes at least one selected from dimethylolpropionic acid (DMPA), and dimethylolbutanoic acid,
The diisocyanate compound is isophorone diisocyanate (IPDI), 4,4'-methylene-bis-cyclohexyl isocyanate (4,4'-Methylenebis (cyclohexyl isocyanate), H12MDI), hexamethylene diisocyanate (Hexamethylene diisocyanate (HDI), ethylene diisocyanate, butane-1,4-diisocyanate, tetramethylbutane-1,4-diisocyanate (Tetramethylbutane-1,4-diisocyanate) Including one or more selected from
The alcohol compound includes at least one selected from 1,1,1-Tris (hydroxylmethyl) propane, glycerin, triethanolamine, and the chain extender includes ethylene glycol, butanediol, hexanediol, and propane. Water-dispersible polyurethane composition, characterized in that it comprises at least one selected from diols. The method of claim 1,
The metal-organic framework includes a metal ion and an organic ligand coordinated to the metal ion, and the metal ion includes one of ions selected from zirconium, zinc, manganese, copper, beryllium, magnesium, and cobalt. Water-dispersible polyurethane composition, characterized in that. The method of claim 1,
The metal-organic framework is water-dispersible polyurethane composition, characterized in that it comprises any one selected from UiO-66, UiO-67, and UiO-68. The method of claim 1,
Water-dispersible polyurethane composition, characterized in that the surface energy of the water-dispersible polyurethane is 35 to 50 mN / m. The method of claim 5,
Water-dispersible polyurethane composition, characterized in that the weight average molecular weight (Mw) of the polyol compound is 500 to 3000g / mol. The method of claim 3,
The polar solvent is water, methyl ethyl ketone, ethanol, 1-ethyl-2-pyrrolidone (1-Ethyl-2-pyrrolidone), acetone, 1-methyl-2-pyrrolidone (1-methyl-2- pyrrolidinone) and dimethylformamide (Dimethylformamide) method for producing a polyurethane composition, characterized in that it comprises one or more selected from. The method of claim 1,
The water-dispersible polyurethane composition, characterized in that the toxic chemicals or chemical agents comprise at least one selected from organophosphorous insecticides and similar nerve agents (Nerve Agent). The method of claim 5,
The water dispersible polyurethane composition, wherein the neutralizing agent is an amine compound. A composite film comprising the water dispersible polyurethane composition of claim 1 for adsorption or removal of toxic chemicals or chemical agents. (a) preparing a water dispersible polyurethane comprising a carboxyl group as a substituent; And
(b) mixing an active material including a metal-organic framework (MOFs), the water-dispersible polyurethane, and a polar solvent to prepare a water-dispersible polyurethane composition; To
Method for producing a water-dispersible polyurethane composition comprising. The method of claim 15,
Step (a)
(a-1) reacting a polyol compound, a diol compound having a carboxyl group as a substituent, and a diisocyanate compound to prepare a first prepolymer having both ends respectively substituted with an isocyanate group;
(a-2) reacting the first prepolymer with at least one of the alcohol compounds having 2 to 5 hydroxy groups as a substituent to prepare a second prepolymer in which all or part of the 2 to 5 terminals are each substituted with an isocyanate group : And
(a-3) neutralizing the carboxy group of the second prepolymer to prepare a second prepolymer salt; And
(a-4) preparing a polyurethane by injecting a chain extender into the second prepolymer salt by reacting an isocyanate group of the second prepolymer salt with a hydroxy group of the chain extender;
The polyol compound is linear and comprises a polyetherpolyol or a polyesterpolyol substituted at both ends with a hydroxy group,
The diisoanate compound is linear, branched, cyclic or a combination thereof,
The alcohol compound is linear, branched, cyclic or a combination thereof,
The chain extender is a method for producing a water dispersible polyurethane composition, characterized in that it comprises a diol compound or a diamine compound. A method for producing a water dispersible polyurethane composition according to claim 15; And
(c) coating the water-dispersible polyurethane composition on a substrate and drying to prepare a composite film;
Method for producing a composite film containing.

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