KR100752150B1 - Photocurable monomoers having imidazolium salts, antibacterial photocurable compositions comprising the same, and antibacterial polymer materials prepared therefrom - Google Patents

Abstract

Photocurable monomers having imidazolium salts, antibacterial photocurable compositions comprising the same compounds, and antibacterial polymer materials prepared therefrom are provided to improve and semi-permanently maintain antibacterial activity of the antibacterial polymer materials against washing, so that they are applicable to clothes, architecture materials and electronic devices. The photocurable monomers having imidazolium salts represented by the formula(1) are provided, wherein X^- is an anion selected from chlorine ion, bromine ion, BF4^-, PF6^-, SbF6^-, NO3^-, CF3SO3^-, (CF3SO3)2N^-, ArSO3^-, CF3CO2^- and CH3CO2^-; m is an integer from 1 to 12; R^1 is H or CH3; and R^2 and R^3 are each independently (CH2)xY in which x is an integer from 0 to 20, Y is halogen atom selected from fluorine, chlorine and bromine, N, NH2, OH or CO2H. The antibacterial photocurable compositions comprise the photocurable monomers having imidazolium salts represented by the formula(1). The antibacterial polymer materials are prepared by photopolymerization of the antibacterial photocurable compositions.

Description

PHOTOCURABLE MONOMOERS HAVING IMIDAZOLIUM SALTS, ANTIBACTERIAL PHOTOCURABLE COMPOSITIONS COMPRISING THE SAME, AND ANTIBACTERIAL POLYMER MATERIAL THEREFROM}

The present invention relates to an antimicrobial imidazolium salt monomer and a polymer material for antimicrobial photocurable coating using the same.

Recently, as hygienic life is actively demanded in daily life, antibacterial agents are used in various fields. Many products with antimicrobial properties have been developed, and it is necessary to prevent bacterial contamination in various industries such as food, beverages, cosmetics, storage containers, toothbrushes, stationery, home appliances, bedding, etc. It is applied in various fields. If the interior materials such as public telephones, public toilets, subways, buses, etc., which are used by multiple people from all daily household items related to human consciousness, are made of polymer antimicrobial materials that are easy to process, the living environment may be more hygienic and safe. There is a need for an antimicrobial polymer material for coating materials that is excellent in processability.

Many antimicrobial materials have been commercialized, but most of them were mixed type in which an antimicrobial agent was added to a liquid or a high molecular material. Therefore, the antimicrobial activity was gradually removed during use, and thus the antimicrobial activity was not maintained for a long time. In addition, existing antimicrobial agents in which antimicrobial agents are used as additives are convenient to use, but are mainly used in excess, and only a part of the added antimicrobial substances exhibits antimicrobial activity on the surface of the substrate. Antimicrobial activity is drastically reduced.

Accordingly, there is a demand for the development of a polymeric antimicrobial material in which antimicrobial activity is added to the organic polymer chain itself so that the antimicrobial activity is maintained semipermanently and thus the applicability to the substrate is large and convenient to use.

Research has been conducted on antibacterial or biocidal polymers in which a polymer material itself exhibits antimicrobial properties by directly binding a functional group having antimicrobial, bactericidal or mold resistance to the polymer chain [SD Worley, TRIP , 4 , 364 (1996); T. Tashiro, Macromol. Mater. Eng., 286 , 63 (2001).

In general, quaternary ammonium salts, phosphonium salts, pyridine compounds, organic halogen compounds, thiazolin compounds, phenols and the like are known as organic antimicrobial agents exhibiting antimicrobial properties. Compounds which combine these functional groups to show cationicity are effective. Currently, thiazole-imidazolium salts, chlorophenol compounds, pyridinethiol oxide salts, nitro group-containing morpholine compounds, triazine chloride compounds and the like have been put to practical use as antibacterial agents.

Polymers having an antimicrobial function exhibit antimicrobial properties by causing damage to cell membranes and cell walls of microorganisms, degeneration of enzyme proteins or inhibition of respiration. The action of an antimicrobial agent on bacteria is greatly affected by the physical and chemical properties of the antimicrobial agent and the diversity of bacteria and cell structures.

The antimicrobial activity of polycation polymers such as ammonium salts or phosphonium salts is excellent. This antimicrobial activity is known to be because the cell membrane of the bacteria is composed of an anionic phospholipid bilayer membrane like other organisms, so that the electrostatic interaction of negative / positive ions easily occurs, thereby destroying the cell membrane to kill the bacteria. acrylate polymers combined with m-cresol [Kim, et al., Polymer No. 26, No. 3, 293 (2002)], acrylate polymers combined with triclosan commonly used as antimicrobial agents [WJ Cho et al. , J. Appl. Polym. Sci., 54 , 859 (1994)], polystyrenes to which ammonium salts of m-dimethylaminophenol are bound . Korean Chem. Soc. , Vol. 23, 1833 (2002)], polysiloxanes bound with quaternary ammonium salts [G. Sauvet et al., J. Appl. Polym. Sci. , 75, 1005 (2000) and the like have been reported as antimicrobial polymers. In addition, the ammonium salt of 1,4-diazabicyclo [2,2,2] octane (1,4-diazabicyclo [2,2,2] octane, DABCO), which is a bicyclic amine, is bound to the sugar ring structural unit of cellulose. It was reported to exhibit excellent antimicrobial properties in the case [T. Abel, R. Engel et al., Carbohydrate Chem., 337 , 2495 (2002)]. In this case, it was reported that the antimicrobial activity was high when the long alkyl group having 16 carbon atoms was substituted. The antimicrobial activity of polyoxazolines with ammonium bases having 12 or more carbon chains of long alkyl chains has also been reported to be very good [CJ Waschinski, JC Tiller, Biomacromolecules, 6, 235 (2005)].

In addition, related patent documents include Korean Patent No. 405030 (Note / Yurei), Korean Unexamined Patent Publication No. 1999-0078100 (Dainichi Saki Seika High School Kabusaki Kaisha), US Patent No. 6,492,445 (Stepan Company, Northfield, IL) ), And Korean Patent Application Publication No. 2000-0031489 (SKK Co., Ltd.).

Since the antimicrobial polymer material combined with the antimicrobial functional group is retained antimicrobial even after washing, it is very applicable to clothing, bedding, medical textile products. Therefore, since the antimicrobial functional group is directly bonded to the polymer chain, it is required to develop an antimicrobial polymer that exhibits high antibacterial activity even in a fixed state.

However, antimicrobial polymers known to date are not suitable for use as coating materials because they have insufficient antimicrobial activity and are insoluble in organic solvents because they are mostly ammonium salts, and are water-soluble or post-crosslinked to the surface.

In addition, the conventional antimicrobial agents are generally used in the form of additives and are used in excess, and only a part of the added antimicrobial agents exhibits limited antimicrobial activity on the surface of the substrate. The effective antimicrobial component decreases due to the lapse of washing and external exposure period, and thus the antimicrobial activity tends to decrease rapidly.

Therefore, it has excellent antimicrobial activity and is photocurable, so that the development of antimicrobial monomers and polymer materials that can be easily coated on the surface of building interior materials, various electronic devices, household goods, packaging materials, food containers, etc. using photocuring reactions It is required.

An object of the present invention is a novel type of antimicrobial monomer comprising an antimicrobial active imidazolium salt which is water soluble and organic solvent soluble and well mixed with other monomers, a photocurable antimicrobial composition comprising the same and an antimicrobial polymer for surface coating prepared from the composition. To provide the material.

The object of the present invention described above is to introduce photopolymerizable acrylic and methacryl groups into the imidazole, which is a component of histidine amino acid in the human body, and to immobilize various functional groups by varying the number of substituted alkyl group carbons, thereby maximizing antibacterial activity. It is achieved by preparing a salt monomer and photocuring it to provide a polymeric material for antimicrobial coating.

Accordingly, the present invention provides an antimicrobial imidazolium salt monomer which forms a photopolymerizable carbon-carbon double bond in an imidazolium salt which is an important component of histidine, an essential amino acid in the human body, and has excellent antibacterial activity and is commercialized as a water-soluble antimicrobial agent. It relates to a photocurable antimicrobial composition comprising the same and an antimicrobial polymer material for surface coating prepared from the composition.

The photocurable antimicrobial imidazolium salt monomer according to the present invention is represented by the following formula (1).

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion, such _{^{as, - CO 2 -, CH 3}} CO 2

m is an integer from 1 to 12,

R ¹ represents H or CH ₃ ,

R ² and R ³ are alkyl groups represented by (CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH or CO ₂ H Functional groups, such as these, are shown.

The present invention is characterized by preparing an odorless photopolymerizable methacrylic acid and an acrylic ester monomer having an antibacterial function as an imidazolium salt which is well known as an ionic liquid having excellent environmental stability, and using it as a photocurable antibacterial functional coating material.

The imidazolium salt monomer of Formula 1 has low risk to the ecosystem, and can be easily surface coated as an environmentally friendly photocuring agent without using an organic solvent. You can make it appear.

The antimicrobial photocurable imidazolium salt monomer represented by Chemical Formula 1 may be an alkyl acrylate or alkyl methacrylate having 1 to 12 carbon atoms having a halogen atom such as bromine or chlorine at the end as illustrated in Scheme 1 below. It can be prepared by reacting with imidazole substituted with ² and R ³ .

Wherein m, R ¹ , R ² and R ³ are the same as defined in Formula 1,

Z is a halogen atom selected from chlorine and bromine, BF ₄ by subsequent reaction of the reaction shown in above Scheme ^{_{1 -, PF 6 -, SbF}} 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3 ^{_{) 2 N -, ArSO 3 -}} , CF 3 CO 2 - may be substituted with ^- or CH ₃ CO _2.

The term "UV-curable resin composition" or "photocurable composition" refers to a liquid resin composition which is photopolymerized and crosslinked and cured in a short time by a photochemical reaction generated by irradiating short wavelength ultraviolet rays. The photocurable resin composition is a mixture of a photosensitive prepolymer and a difunctional multifunctional (meth) acrylates and a photoinitiator. Exposure to ultraviolet light to this composition generates free radicals from the photoinitiator to initiate chain polymerization of polymerizable (meth) acrylic groups in the prepolymer and diluent, resulting in a crosslinking reaction throughout the coating to form an insoluble coating having excellent physical properties. .

The time required for this photocuring process is usually a few seconds to less than 1 minute, the curing reaction must occur quickly to be used as an efficient photocurable resin. In photocuring resin, photopolymerization reaction is important. This is because the polymerization and crosslinking reaction by the light proceeds at the same time so that the curing and insolubilization of the resin coated on the substrate can be completed to satisfy the desired physical properties and properties as the coating coating material.

A photosensitive prepolymer, a polyfunctional monomer (diluent), and a photoinitiator are three essential components of a photocuring resin, In addition, a photosensitizer, a pigment, a filler, a labelling agent, a polymerization inhibitor, etc. are added according to the use of resin. Typically, the photocurable resin is formulated by mixing 50-60% of a photosensitive prepolymer, 30-40% of a polyfunctional monomer (diluent), and 0.1-10% of a photoinitiator. Since the photosensitive prepolymer cannot be directly used as a paint or coating agent because of its high viscosity, a diluent may be added to decrease the viscosity to improve processability of the composition. The diluent increases the curing rate of the photocuring resin and improves physical properties, such as low viscosity photopolymerizable di- or tri-functional trimethylolpropane tri (meth) acrylic acid ester, diethylene glycol die ( And monomers such as meta) acrylate or monofunctional (meth) acrylic acid ester and en-vinylpyrrolidone.

In general, the photosensitive prepolymer acts as a component to impart properties suitable for physical properties and applications in the final curing state of the photocurable resin. Among many kinds of acrylic ester photosensitive prepolymers, epoxy (meth) acrylates, siloxane (meth) acrylates and urethane (meth) acrylates are commonly supplied commercially.

Most practical photoinitiators are aromatic carbonyl compounds, representative examples of which are dialkyl-hydroxy-acetophenone, dimethoxy-phenyl-acetophenone, benzoinalkyl isomer, or alkylamine to benzophenone or thioxanthone derivatives. Products with the addition of are known.

In addition, the present invention provides an antimicrobial photocurable composition comprising an antimicrobial imidazolium salt monomer represented by the formula (1). The composition comprises an antimicrobial imidazolium salt monomer represented by the formula (1) as an essential component, and optionally contains a photosensitive prepolymer as exemplified above, a diluent and a crosslinker trimethylolpropane triacrylate, a photoinitiator and the like. It may include.

By way of example, the composition may comprise 3-40% of the antimicrobial imidazolium salt monomer represented by Formula 1, 50-60% of a typical photosensitive prepolymer, 30-40 of a conventional multifunctional monomer (diluent) based on the total weight of the composition % And 1-10% of conventional photoinitiators.

The present invention also relates to an antimicrobial polymer material prepared by photopolymerization of an antimicrobial photocurable composition comprising essentially the antimicrobial imidazolium salt monomer represented by Formula 1.

The present invention also relates to a (co) polymer represented by the following Chemical Formula 2, which is prepared by radical polymerization using an antimicrobial imidazolium salt monomer represented by the above Chemical Formula 1.

Wherein X, m, R ¹ , R ² and R ³ are the same as defined in the formula (1),

M is a repeating unit derived from comonomers of various structures known in the present invention, for example, (meth) acrylic acid, (meth) acrylic acid ester system, vinyl acetate, acrylonitrile, (meth) acrylamide system, All commercialized vinyl monomers such as styrene and butadiene are included.

The fraction a of the antimicrobial imidazolium salt monomer component of the formula (1) is 3 to 100%, the fraction b of the comonomer A is 0 to 97%, and a + b = 100.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited thereto.

Example 1: 3-chloropropyl acrylate synthesis

Dissolve 9.45 g (0.10 mol) of 3-chloro-1-propanol in 50 ml of tetrahydrofuran (THF). 15.20 g (0.15 mol) of triethylamine were added thereto, followed by reaction at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 18.10 g (0.2 mol) of acryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.

Yield 10.80 g (73%)

¹ H NMR (CDCl ₃ , 200 MHz) 6.4 (d, 1H), 6.1 (m, 1H), 5.8 (d, 1H), 4.3 (t, 2H), 3.6 (t, 2H), 2.1 (m, 2H) .

Example 2: 3-chloropropyl methacrylate synthesis

47.30 g (0.50 mol) of 3-chloro-1-propanol are dissolved in 150 ml of tetrahydrofuran (THF). 50.60 g (0.50 mol) of triethylamine were added thereto, followed by reaction at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 63.30 g (0.60 mol) of methacryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.

Yield 58.50 g (66%)

¹ H NMR (CDCl ₃ , 200 MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m, 2H), 1.9 (s, 3H)

Example 3: 2-bromoethyl methacrylate synthesis

Dissolve 10.00 g (0.080 mol) of 2-bromoethanol in 100 ml of tetrahydrofuran. 8.00 g (0.080 mol) of triethylamine was added thereto, followed by reaction with stirring at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 10.00 g (0.096 mol) of methacryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.

Yield 13.70 g (89%)

¹ H NMR (CDCl ₃ , 200 MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m, 2H), 1.9 (s, 3H)

Example 4: 1-hexylimidazole synthesis

Dissolve 10.0 g (0.147 mol) of imidazole in 40 ml of dimethylformamide at room temperature. NaH 3.5g (0.147mol) was added slowly at room temperature, followed by stirring for 2 hours. 12.13 g (0.074 mol) of 1-bromohexane was added and reacted at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with 200 ml of methylene chloride and 40 ml of water. Methylene chloride is distilled under reduced pressure and dried to give a colorless liquid product.

Yield 17.60 g (78%)

¹ H NMR (CDCl ₃ , 200 MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25-1.98 (m, 6H), 0.9 (t, 3H).

Example 5: 1-dodecylimidazole synthesis

Dissolve 20.0 g (0.294 mol) of imidazole in 40 ml of dimethylformamide at room temperature. NaH 7.0g (0.294mol) was added slowly, followed by stirring for 2 hours. 36.6 g (0.147 mol) of 1-bromododecane was added thereto and allowed to react at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with 200 ml of methylene chloride and 40 ml of water. Methylene chloride is distilled under reduced pressure and dried to give a colorless liquid compound.

Yield 39.70 g (57%)

¹ H NMR (CDCl ₃ , 200 MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25-1.98 (m, 18H), 0.8 (t, 3H).

Example 6: 3-methyl-1- (3-acryloyloxypropyl) imidazolium chloride synthesis

5.73 g (0.039 mol) of the chloro acrylate compound synthesized in Example 1 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.57 g (0.08 mol) of 1-methylimidazole was added thereto, followed by stirring at 50 ° C. for 6 hours. Let's do it. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a sticky pale brown viscous liquid product.

Yield 7.30 g (81%)

¹ H NMR (CDCl ₃ , 200 MHz) 9.3 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.3 (d, 1H), 6.2 to 6.1 (m, 1H), 6.0 to 5.9 ( d, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m, 2H).

Example 7: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesis

6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.57 g (0.08 mol) of 1-methylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. React. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was precipitated in excess of diethyl ether to give a sticky, slightly yellowish liquid product.

Yield 8.40 g (86%)

¹ H NMR (DMSO, 200 MHz) 9.5 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.0 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m, 2H), 1.8 (s, 3H).

Example 8: 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis

5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethylsulfoside (DMSO), and 2.13 g (0.026 mol) of 1-methylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. And react. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 5.35 g (75%)

Example 9: 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis

5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 3.23 g (0.026 mol) of butylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. React. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 6.75 g (82%)

¹ H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (m, 4H), 2.2 (m, 2H), 1.8 (s, 3H), 1.7 (m, 2H), 1.2 (m, 2H), 0.9 (t, 3H).

Example 10 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesis

6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.09 g (0.04 mol) of 1-hexylimidazole synthesized in Example 4 was added thereto at a temperature of 50 ° C. The reaction is stirred for 6 hours at. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 8.30 g (66%)

¹ H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H).

Example 11: 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis

5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 3.94 (0.026 mol) of 1-hexylimidazole synthesized in Example 4 was added thereto at a temperature of 50 ° C. The reaction is stirred for 6 hours at. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 7.10 g (79%)

¹ H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H).

Example 12 Synthesis of 3-dodecyl-1- (3-methacryloyloxypropyl) imidazolium chloride

6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 9.45 g (0.04 mol) of 1-dodecylimidazole synthesized in Example 5 was added thereto to obtain a temperature of 50 ° C. The reaction is stirred at 6 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 9.90 g (62%)

¹ H NMR (DMSO, 200 MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H).

 Example 13: 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis

5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.12 g (0.026 mol) of 1-dodecylimidazole synthesized in Example 5 was added thereto. The reaction is stirred at 50 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.

Yield 8..70 g (78%)

¹ H NMR (DMSO, 200 MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H)

Example 14 Synthesis of 1- (2-hydroxyethyl) imidazole

Dissolve 10.00 g (0.146 mol) of imidazole in 100 ml of toluene with stirring. 15.52 g (0.176 mol) of ethylene carbonide was added thereto, followed by reaction at 110 ° C. for 5 hours. After completion of the reaction, toluene was discarded and the residue precipitated in diethyl ether to give a brown sticky liquid product.

Yield 14.77 g (89.7%)

Example 15 Synthesis of 1- (2-Methacryloyloxyethyl) imidazole

10.00 g (0.089 mol) of 1- (2-hydroxyethyl) imidazole compound synthesized in Example 14 was dissolved in 100 ml of tetrahydrofuran (THF). Add 8.92 g (0.089 mol) of triethylamine, and react for 1 hour at room temperature. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 13.40 g (0.13 mol) of methacryloyl chloride. After reacting for 5 hours, tetrahydrofuran is distilled under reduced pressure, and the reaction mixture is extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.

Yield 12.34 g (77%)

Example 16: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride polymer synthesis

3.00 g (0.0123 mol) of 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 7 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.02 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to 200 ml of ethyl acetate. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.20 g (73.3%)

Example 17: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride

Copolymerization of Methyl Methacrylate

3.00 g (0.012 mol) of 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 7 was placed in a 20 ml Pyrex glass polymerization tube and 1.23 g (0.012 mol) of methyl methacrylate. ) And initiator AIBN (0.04 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, and then sealed in three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to ethyl acetate in 300 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.60 g (62%)

Example 18 Synthesis of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide polymer

3.00 g (0.011 mol) of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 8 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.018 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to 200 ml of ethyl acetate, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.35 g (78%)

Example 19 Copolymerization of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide with methyl methacrylate

3.00 g (0.011 mol) of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 8 was placed in a 20 ml Pyrex glass polymerization tube and 1.10 g (0.011 mol) of methyl methacrylate. ) And initiator AIBN (0.036 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, and then sealed in three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to ethyl acetate in 200 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.57 g (63%)

Example 20 Polymer Synthesis of 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide

3.00 g (0.0095 mol) of 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 9 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.016 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by sealing with three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to 200 ml of ethyl acetate, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.35 g (78%)

Example 21 Polymer Synthesis of 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride

3.00 g (0.0096 mol) of 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 10 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.0156 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.43 g (81%)

Example 22 Copolymerization of 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide with methylmethacrylate

3.00 g (0.0087 mol) of 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 11 was placed in a 20 ml Pyrex glass polymerization tube and 0.87 g (0.0087 mol) of methyl methacrylate. ) And initiator AIBN (0.029 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, followed by sealing with three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 3.15 g (79%)

Example 23 Polymer Synthesis of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide

3.00 g (0.007 mol) of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 13 was placed in a 20 ml Pyrex glass polymerization tube and the initiator AIBN (0.012 g, monomer 1 mol%), dissolved in 3.0 ml of chloroform, and then subjected to three freeze and thaw cycles under nitrogen gas replacement, followed by sealing. The sealed polymer tube was polymerized at 60 ° C. for 6 hours, diluted with methanol, and added dropwise to ethyl acetate in 200 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.60 g (87%)

Example 24: 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide

 Methyl methacrylate copolymerization

3.00 g (0.007 mol) of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 13 was placed in a 20 ml Pyrex glass polymerization tube and 0.70 g (0.007) of methyl methacrylate. mol) and initiator AIBN (0.023 g, 1 mol% based on monomer) were added, dissolved in 4.0 ml of chloroform, and sealed after 3 cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 3.05 g (82%)

Example 25 Photocuring Experiment of Imidazolium Salt Monomer

Using the antimicrobial imidazolium salt monomer synthesized in the present invention, the following photocuring composition was prepared to evaluate the photocuring reaction.

100 parts by weight of the imidazolium salt monomer prepared in the above embodiment, 100 parts by weight of trimethylolpropane triacrylate as a crosslinking agent and 5 parts by weight of benzoin isobutyl ether as a photoinitiator were mixed well to prepare a photocurable composition. 10 mg of the composition was taken and the photocuring reaction rate was measured using a differential photocolorimeter (DPC). As a photocuring reaction evaluation instrument, a DPC coupled with a Model DSC 2910 manufactured by TA Instruments of 250W mercury lamp was used.

Specific experimental procedures are as described below. A photocurable composition was prepared by mixing 1.00 g of the antimicrobial imidazolium monomer sample of Example 10, 1.00 g of trifunctional trimethylolpropane triacrylate, and 0.05 g of photoinitiator benzoin isobutyl ether.

The photocuring reaction rate of the antimicrobial photocuring composition containing the imidazolium salt monomer described above was evaluated to be fast enough from the result of analyzing the photocuring reaction rate using DPC using 10 mg of the composition. Also, in order to see the actual film forming ability, the viscous photocurable composition sample was made into a 0.2mm thick film on the polyester film, and photocured for 10 seconds using a 250W ultraviolet exposure machine, so that the surface condition was smooth and hardened. It was confirmed that an excellent polymer transparent film was formed.

Photocuring compositions prepared by combining in the same manner as described above using the antimicrobial imidazolium monomer prepared in another embodiment also photocuring reaction occurred within 10 seconds on the substrate to be coated to form an excellent photocurable polymer coating film.

Example 25 Antimicrobial Activity Test on Microorganisms of Imidazolium Salt Monomers and Polymers Obtained from the

In Example 25 benzalkonium chloride (BKC: alkylbenzyldimethylammonium chloride, general formula C ₁₂ H ₂₅ N (CH ₃ ) ₂ C ₇ HCl generally used as an antimicrobial or preservative in the manufacture of disinfectants, household detergents and cosmetics in hospitals ) And water-soluble chitosan (WSC, Mwt. 20,000) used as an antimicrobial polymer by processing chitin and natural products were used as a control group for the antibacterial activity test.

(1) Preparation of Test Microorganisms

Gram-positive bacteria Staphylococcus aureus (ATCC 25923) and Gram-negative bacteria Escherichia coli (ATCC 25922) were used for the antimicrobial activity test. To obtain the Staphylococcus aureus culture, small amounts of colonies formed on nutrient agar plates were inoculated with platinum and inoculated into Brain heart infusion broth (BHIB), followed by aerobic shaking for 3-5 hours at 37 ° C (120 rpm). ) Were cultured. In addition, a small amount of colonies formed on trypticase soy agar plate medium were obtained with platinum to obtain an E. coli exponent culture, and then inoculated into tryticase soy broth (TSB), followed by Staphylococcus aureus. As in ( S. aureus) , shaking culture was aerobic at 37 ℃. The exponential cultures of the bacteria were collected and diluted in Mueller-hinton broth (MHB) to adjust the final concentration of the bacteria solution to 1x10 ⁶ to 1x10 ⁸ CFU / ml.

(2) Test contents and method

A) antimicrobial activity test by disk diffusion method

In order to test the antimicrobial activity of non-suspendable bacteria of the monomer or synthetic polymer sample synthesized in the present invention, Kirby-Bauer modification was performed. In order to produce an antimicrobial test disc, the monomer or polymer sample synthesized in the present invention was dissolved in a solvent such as sterile distilled water, methanol, or dimethyl sulfoxide (DMSO), respectively, to make a final concentration of 100 mg / ml. 20 l of each of these solutions was taken and dropped in the center of a sterile filter paper (6 mm in diameter) containing no antibacterial agent, and dried at room temperature for at least 6 hours. In addition, in order to determine whether the solvent itself affects the antimicrobial test, the disc was manufactured by the same method as above using only a solvent containing no monomer or polymer sample at all. Ultraviolet rays were irradiated at room temperature for 1 hour to sterilize a disk containing a solvent or 2 mg of antimicrobial test substance. S. aureus or E. coli exponential cultures (1 × ^{10 8} CFU / ml) were evenly coated onto the MHA plate medium using a sterile swab, and then different types of antimicrobial test discs were placed thereon at regular intervals. . After incubation of MHA plate medium at 35-37 ° C. for 24 hours, the growth inhibition zone formed around the disc was measured and recorded in mm to evaluate the antimicrobial activity.

B) determination of the sensitivity of the microorganisms to the sample;

In order to test the susceptibility of bacteria to the samples synthesized in the present invention, the minimum inhibitory concentration (MIC) was measured according to the broth dilution method. Sterile distilled water was used to make sample dilutions in the range of 0-1600 μg / ml with a 2-fold concentration gradient, and then each sample dilution was dispensed into the test tube by 3 ml. After adding 3 ml of each of the exponential cultures of each bacterium previously adjusted to 1 × 10 ⁶ CFU / ml, the cells were incubated at 35-37 ° C. for 18 to 20 hours. The final concentration of the antimicrobial agent in vitro where no growth of cultured bacteria was observed visually was determined by the MIC value.

(3) Evaluation result of microorganism's antimicrobial activity on sample

The imidazolium salt monomer synthesized in the present invention and the sample of the polymer is an imidazolium salt polymer of the present invention similar to the water-soluble chitosan (WSC) used as a general antimicrobial polymer as a result of the antimicrobial activity test by the disk diffusion method for two bacteria. All the samples showed excellent antimicrobial activity. Since the disk diffusion method is an antimicrobial evaluation against non-suspendable bacteria, MIC measurement was performed to evaluate the antimicrobial activity against suspended bacteria.

Table 1 shows the bacteria susceptibility of the two imidazolium salt monomers, three homopolymers and three methyl methacrylate copolymers, using BKC and WSC, which are used as antimicrobial agents, as a control group. will be. The susceptibility test of S. aureus showed that the MIC of BKC was 1.563 g / ml, and the long alkyl-substituted imidazolium salt of dodecyl in the imidazolium salt monomer sample (Example 11) Was very good antimicrobial activity like BKC. The antimicrobial activity was tested by dissolving the imidazolium salt polymer in methanol, and all of them showed antimicrobial activity similar to that of the natural polymer WSC. In particular, the copolymer having a long dodecyl alkyl chain (Example 23) had a very good activity similar to that of BKC. appear. In the case of E. coli , the imidazolium salt sample according to the present invention also showed excellent susceptibility as in S. aureus with very good antibacterial activity.

TABLE 1

Antimicrobial Activity Test Results: Minimum Inhibitory Concentration (MIC, μg / ml)

Sample (solvent) Staphylococci [S.aureus] (ATCC 25923) Escherichia coli [E. coli] (ATCC 25922) Example 11 (Methanol) 100 200 Example 13 (Methanol) 1.563 3.125 Example 17 (DMSO) 200 100 Example 18 (Methanol) 25 200 Example 20 (Methanol) 25 50 Example 21 (Methanol) 50 25 Example 22 (Methanol) 50 50 Example 24 (methanol) 3.125 12.5  BKC (distilled water) 1.563 3.125  WSC (distilled water) 25 25

According to the present invention, a photocurable antimicrobial imidazolium salt monomer represented by Formula 1, a photocurable antimicrobial coating composition comprising the same, and an antimicrobial polymer material for surface coating prepared by photocuring are provided.

When the photocurable antimicrobial imidazolium salt-containing monomer according to the present invention is polymerized to prepare a polymer or a photocurable antimicrobial coating composition, it is used in the form of a polymer film having antimicrobial properties by photocuring.

Since the photocurable antimicrobial composition according to the present invention can be used in a photocuring process in an environmentally friendly manner without a solvent, the curing process is simple, convenient and excellent in antimicrobial properties. In other words, antibacterial coating can be easily applied to building materials such as floor coverings and wallpaper, and to interior materials such as public telephones, toilets, subways, buses, etc. It can be used as an environmentally friendly antimicrobial polymer coating material.

Claims (6)

The antimicrobial imidazolium salt monomer represented by the following formula (1): [Formula 1]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ is H or CH ₃ , R ² and R ³ are each an alkyl group represented by (CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH and CO ₂ It is a functional group selected from the group which consists of H. An antimicrobial compound represented by the following formula (1) comprising reacting an alkyl acrylate or alkyl methacrylate having 1 to 12 carbon atoms having a bromine or chlorine atom at the alkyl end with an imidazole substituted with R ² and R ³ Process for preparing imidazolium salt monomer: [Formula 1]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ is H or CH ₃ , R ² and R ³ are each an alkyl group represented by (CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH and CO ₂ It is a functional group selected from the group which consists of H. 3. The method of claim 2, by a chlorine or bromine ion after the reaction step after the reaction _{^{BF 4 -, PF 6 -,}} SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N _{^{-, ArSO 3 -, CF 3}} CO 2 - , or CH ₃ CO ₂ ^- as the manufacturing method of switch. An antimicrobial photocurable composition comprising an antimicrobial imidazolium salt monomer represented by Formula 1 below: [Formula 1]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ is H or CH ₃ , R ² and R ³ are each an alkyl group represented by (CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH and CO ₂ It is a functional group selected from the group which consists of H. An antimicrobial polymer material prepared by photopolymerization of the antimicrobial photocurable composition according to claim 4. A (meth) acrylate-based imidazolium salt-containing antimicrobial polymer represented by the following general formula (2) obtained by radical polymerization of the antimicrobial imidazolium salt monomer according to claim 1: [Formula 2]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ is H or CH ₃ , R ² and R ³ are each an alkyl group represented by (CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH and CO ₂ Is a functional group selected from the group consisting of H, M is a repeating unit derived from a vinyl comonomer selected from (meth) acrylic acid, (meth) acrylic acid ester type, vinyl acetate, acrylonitrile, (meth) acrylamide type, butadiene type and styrene type, a is 3 to 100%, b is 0 to 97%, and a + b = 100.