A quaternary ammonium carbamate salt, its preparation method and application

Abstract

This invention belongs to the field of antibacterial materials technology, specifically relating to a urethane quaternary ammonium salt, its preparation method, and its application. The preparation method includes the following steps: reacting a compound containing a -NH-COO- group with a haloalkane under the action of a catalyst to undergo a quaternization reaction, thereby obtaining the urethane quaternary ammonium salt. The preparation method of this invention is simple, low in cost, and the obtained quaternary ammonium salt antibacterial agent exhibits good antibacterial properties.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial materials technology, specifically relating to a quaternary ammonium carbamate salt, its preparation method, and its application. Background Technology

[0002] Microorganisms have been virtually ubiquitous throughout history. Beneficial microorganisms contribute to human development, while the spread of harmful microorganisms seriously threatens human health, forcing people to control and / or eliminate the growth and reproduction of harmful bacteria and fungi. Antibacterial agents are a class of microbial killers widely used in daily life, such as clothing, furniture, and cleaning products. Antibacterial agents can resist or inhibit the growth and reproduction of microorganisms, and can inhibit bacterial growth and reproduction for a certain period of time, leading to their death.

[0003] As living standards improve, people's awareness of their own health and environmental protection is gradually increasing, and the requirements for antibacterial agents are also getting higher and higher. At present, antibacterial agents are gradually developing towards environmentally friendly, non-toxic and harmless, and low-cost.

[0004] Currently, widely used antibacterial agents include organic, inorganic, and composite antibacterial agents. Among organic antibacterial agents, quaternary ammonium salt antibacterial agents are widely used and researched due to their advantages such as low price and rapid bactericidal speed. The current preparation of quaternary ammonium salt antibacterial agents mainly involves repeatedly grafting amino groups onto the corresponding materials to obtain the quaternary ammonium salt. This method is costly and difficult to prepare, and the resulting quaternary ammonium salt contains a large number of impurities, resulting in poor antibacterial properties. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a quaternary ammonium salt antibacterial agent and its preparation method. The preparation method involves directly quaternizing a compound containing a -NH-COO- group. This method is simple, low-cost, and yields a product with good antibacterial properties. Specifically, this invention provides the following solution:

[0006] A method for preparing a quaternary ammonium carbamate salt, the method comprising the following steps:

[0007] Compounds containing -NH-COO- groups are quaternized with haloalkanes under the action of a catalyst to obtain urethane quaternary ammonium salts.

[0008] According to an embodiment of the present invention, the temperature of the quaternization reaction is 40–120°C.

[0009] According to an embodiment of the present invention, the quaternization reaction time is 8h to 120h.

[0010] According to an embodiment of the present invention, the molar ratio of the compound containing the -NH-COO- group to the haloalkanes is at least 1:2.

[0011] According to an embodiment of the present invention, the compound containing the -NH-COO- group has the structure of Formula 1 below.

[0012]

[0013] The quaternization reaction of this compound is shown in the following reaction formula 1:

[0014]

[0015] Wherein, R1 and R2 may be the same or different, and are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl. The substituent may be selected from one of the following groups: C(R4)(R5)=C(R6)-COO- group, C(R4)(R5)=C(R6)-COO-(CH2). n -OCO-NH- group, polyester group, polyether group, halogen, alkoxy or hydroxyl; R4, R5, R6 are the same or different, and are independently selected from H, alkyl, cycloalkyl, aryl or alkenyl; n is an integer from 1 to 20;

[0016] R3 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl, and the substituents are defined as in R1 and R2;

[0017] X is selected from halogens.

[0018] According to an embodiment of the present invention, the compound containing the -NH-COO- group is selected from polyurethane resin, and the polyurethane resin is reacted with the halohydrocarbon R3-X (R3 and X are defined as above) under the action of a catalyst to obtain urethane quaternary ammonium salt, i.e., quaternary ammonium salt of polyurethane.

[0019] According to an embodiment of the present invention, the catalyst is one or a mixture of more than one of sodium hydride, lithium hydride, and potassium hydride.

[0020] According to an embodiment of the present invention, the molar ratio of the compound containing the -NH-COO- group to the catalyst is 1:(1-2).

[0021] According to an embodiment of the present invention, the solvent is an anhydrous aprotic solvent selected from one or a mixture of several of the following: acetonitrile, tetrahydrofuran, dioxane, chloromethane, dichloromethane, trichloromethane, chloroform, acetone, methyl ethyl ketone, nitromethane, nitrobenzene, pyridine, quinoline, dimethyl sulfoxide, formamide, diformamide, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoramide, chlorobenzene, benzene, toluene, xylene, n-hexane, heptane, and petroleum ether.

[0022] The present invention also provides a urethane quaternary ammonium salt, wherein the urethane quaternary ammonium salt is a quaternary ammonium salt of a polyurethane resin or at least one of a compound having the structure shown in Formula 2.

[0023]

[0024] In Equation 2, R1, R2, R3 and X are defined as before.

[0025] According to embodiments of the present invention, R1 and R2 may be the same or different, and are independently selected from H, substituted or unsubstituted C1-C8 alkyl groups, and substituted or unsubstituted C3-C4 alkyl groups. 10 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C2-C 10 The definitions of alkenyl and substituent are the same as above.

[0026] According to an embodiment of the present invention, at least one of R1 and R2 is selected from C(R4)(R5)=C(R6)-COO- or C(R4)(R5)=C(R6)-COO-(CH2). n Alkyl groups substituted with -OCO-NH- groups, C(R4)(R5)=C(R6)-COO- groups or C(R4)(R5)=C(R6)-COO-(CH2) n The -OCO-NH- group can have one, two or more substitutions, and the definitions of R4, R5, R6 and n are the same as before.

[0027] According to an embodiment of the present invention, the urethane quaternary ammonium salt is a quaternary ammonium salt of polyurethane resin or a quaternary ammonium salt of urethane dimethacrylate.

[0028] The present invention also provides the application of the above-mentioned carbamate quaternary ammonium salt in antibacterial applications.

[0029] The present invention also provides an antibacterial material comprising a cured product of the above-mentioned urethane quaternary ammonium salt and a compound containing a -NH-COO- group.

[0030] Beneficial effects

[0031] 1. This invention discloses a method for preparing quaternary ammonium carbamate salts. This method provides a new approach and concept for the preparation of quaternary ammonium salt antibacterial agents, and also offers a simple and low-cost solution for the antibacterial properties of materials containing carbamate groups, such as polyurethane. The method of this invention eliminates the need for re-grafting amino groups onto the raw materials when preparing quaternary ammonium salt antibacterial agents; instead, it directly quaternizes compounds containing -NH-COO- groups. The preparation method is simple, low-cost, and yields quaternary ammonium salt antibacterial agents with good antibacterial properties. The minimum inhibitory concentration (MIC) against *Escherichia coli* can reach 800 μg / mL, and the MIC against *Staphylococcus aureus* can reach 200 μg / mL.

[0032] 2. The present invention also provides a quaternary ammonium salt antibacterial agent containing at least two ammonium ions, which has beneficial antibacterial properties, for example, the minimum inhibitory concentration (MIC) against Escherichia coli can reach 800 μg / mL; and the minimum inhibitory concentration (MIC) against Staphylococcus aureus can reach 200 μg / mL.

[0033] 3. The present invention also provides an antibacterial material, which is obtained by mixing and curing a quaternary ammonium carbamate salt with a compound containing a -NH-COO- group. The preparation method is simple and low in cost, and the obtained antibacterial material has good antibacterial properties. Attached Figure Description

[0034] Figure 1 This is an X-ray photoelectron spectroscopy (XPS) analysis diagram of the urethane quaternary ammonium salt prepared in Example 1 of the present invention.

[0035] Terminology definitions and explanations:

[0036] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. It should be understood that the foregoing summary and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of this application. In this application, unless otherwise stated, “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0037] The term "alkyl" refers to a straight-chain or branched alkyl group having 1 to 12, preferably 1 to 10, carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, and neopentyl.

[0038] The term "cycloalkyl" refers to a monocyclic or bicyclic hydrocarbon group having 3 to 10 cyclic carbon atoms, preferably a monocyclic hydrocarbon group having 3 to 8 cyclic carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, or bicyclo[2.2.2]octyl.

[0039] The term "aryl" should be understood to preferably refer to a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 5 to 20 carbon atoms with monovalent aromaticity or partial aromaticity, preferably "C6-14 aryl". The term "C6-14 aryl" should be understood to preferably refer to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C6-14 aryl") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms, particularly a ring having 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C9 aryl"), such as indenyl or indenyl, or a ring having 10 carbon atoms ("C10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or a ring having 13 carbon atoms ("C13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C14 aryl"), such as anthracene.

[0040] The term "alkenyl" should be understood to preferably refer to a straight-chain or branched hydrocarbon group containing one or more double bonds and having 2 to 12 carbon atoms, preferably "C2-10 alkenyl". "C2-10 alkenyl" should be understood to preferably refer to a straight-chain or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, particularly 2 or 3 carbon atoms ("C2-3 alkenyl"). It should be understood that when the alkenyl group contains more than one double bond, the double bonds may be separable or conjugated. The alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, hex-5 -alkenyl, (E)-hex-4-alkenyl, (Z)-hex-4-alkenyl, (E)-hex-3-alkenyl, (Z)-hex-3-alkenyl, (E)-hex-2-alkenyl, (Z)-hex-2-alkenyl, (E)-hex-1-alkenyl, (Z)-hex-1-alkenyl, isopropenyl, 2-methylprop-2-alkenyl, 1-methylprop-2-alkenyl, 2-methylprop-1-alkenyl, (E)-1-methylprop-1-alkenyl, (Z)-1-methylprop-1-alkenyl. Detailed Implementation

[0041] [Preparation of carbamate quaternary ammonium salts]

[0042] As mentioned above, the present invention provides a method for preparing a quaternary ammonium carbamate salt, the method comprising the following steps:

[0043] Compounds containing -NH-COO- groups are quaternized with haloalkanes under the action of a catalyst to obtain urethane quaternary ammonium salts.

[0044] According to an embodiment of the present invention, the temperature of the quaternization reaction is 40–120°C, exemplarily the temperature of the quaternization reaction is 50–100°C, further, the temperature of the quaternization reaction is 60–80°C, for example the temperature of the quaternization reaction is any point value or the middle value of any range formed by any two points from 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C.

[0045] According to an embodiment of the present invention, the quaternization reaction time is 8h to 120h, exemplaryly the quaternization reaction time is 15h to 100h, further, the quaternization reaction time is 30h to 60h, for example the quaternization reaction time is any point value or the middle value of any range formed by any two points from 8h, 10h, 15h, 20h, 25h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h, 120h.

[0046] According to embodiments of the present invention, the molar ratio of the compound containing the -NH-COO- group to the haloalkane is at least 1:2; exemplaryly, the molar number of the haloalkane is greater than 2 mol; specifically, it is greater than or equal to twice the molar number of the -NH- groups in the compound containing the -NH-COO- group. Exemplarily, for a compound containing two NH groups, the molar ratio of the compound containing the -NH-COO- group to the haloalkane can be 1:(2-4), exemplaryly, it can be 1:(2.2-3.2), further, it can be 1:(2.6-3), for example, 1:2.0, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3.0, 1:3.2, 1:3.6, 1:3.8, or 1:4.0. This can be extrapolated to compounds containing other numbers of NH groups. If the compound containing the -NH-COO- group is a polymer, such as polyurethane, the molar ratio of the compound containing the -NH-COO- group to the halohydrocarbon is at least 1:2, and the molar number of halohydrocarbons can be appropriately increased according to the required degree of quaternization.

[0047] According to an embodiment of the present invention, the quaternization reaction is carried out under stirring conditions.

[0048] According to an embodiment of the present invention, the compound containing the -NH-COO- group has the structure of Formula 1 below.

[0049]

[0050] The quaternization reaction based on this compound is shown in the following reaction formula 1:

[0051]

[0052] Wherein, R1 and R2 may be the same or different, and are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl, and the substituent may be selected from one of the following groups:

[0053] C(R4)(R5)=C(R6)-COO- group, C(R4)(R5)=C(R6)-COO-(CH2) n -OCO-NH- group, polyester group, polyether group, halogen, alkoxy, hydroxyl, etc., R4, R5, R6 are selected from H, alkyl, cycloalkyl, aryl or alkenyl, n is an integer from 1 to 20, n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20;

[0054] R3 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl, and the substituents are defined as in R1 and R2;

[0055] X is selected from halogens (e.g., F, Cl, Br, or I).

[0056] According to an embodiment of the present invention, the polyester in the polyester group is a polymer obtained by polycondensation of polyols and polyacids; exemplaryly, the polyol is a diol (such as ethylene glycol, propylene glycol, diallyl alcohol, butanediol, etc.), a triol (such as glycerol, etc.) or a polypolyol (polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.); exemplaryly, the polyacid is an aromatic polyacid or an aliphatic polyacid or a mixture of the two, specifically, the aromatic polyacid can be terephthalic acid, phthalic acid, isophthalic acid, etc., and the aliphatic polyacid can be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanoic acid, etc.

[0057] According to an embodiment of the present invention, the polyether group is, for example, a polyethylene glycol group or a polypropylene glycol group.

[0058] According to embodiments of the present invention, when the compound shown in Formula 1 includes two or more -NH- groups, at least one of its -NH- groups will react to form a quaternary ammonium group. Exemplarily, when the compound shown in Formula 1 includes two -NH- groups, only one of its -NH- groups reacts to form a quaternary ammonium salt containing one quaternary ammonium group, or both -NH- groups react to form a quaternary ammonium salt containing two quaternary ammonium groups; when the compound shown in Formula 1 includes three -NH- groups, only one of its -NH- groups reacts to form a quaternary ammonium salt containing one quaternary ammonium group, or only two -NH- groups react to form a quaternary ammonium salt containing two quaternary ammonium groups, or all three -NH- groups react to form a quaternary ammonium salt containing three quaternary ammonium groups; and so on.

[0059] According to an embodiment of the present invention, in Formula 1, R1 and R2 may be the same or different, and are independently selected from H, substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C4 alkyl groups. 10 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C2-C 10 The definitions of alkenyl and substituent are the same as above.

[0060] According to an embodiment of the present invention, the compound having the structure shown in Formula 1 is selected from carbamate dimethacrylate.

[0061] According to an embodiment of the present invention, the compound containing the -NH-COO- group is selected from polyurethane resin, and the polyurethane resin is reacted with the halohydrocarbon R3-X (R3 and X are defined as above) under the action of a catalyst to obtain urethane quaternary ammonium salt, i.e., quaternary ammonium salt of polyurethane.

[0062] According to embodiments of the present invention, the polyurethane resin (PU) refers to a polymer containing -NH-COO- groups in its molecular structure. Polyurethane is generally obtained by reacting polyisocyanates and polyols. Exemplarily, the polyisocyanate is selected from aliphatic or aromatic polyisocyanates, specifically from diisocyanates. More specifically, the diisocyanate includes, but is not limited to, at least one of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI). Exemplarily, the polyol is selected from at least one of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, and polypropylene glycol.

[0063] According to an embodiment of the present invention, the number-average molecular weight of the polyurethane resin is not particularly limited, for example, it can be 5000 to 20000. Exemplarily, the number-average molecular weight of the polyurethane resin is 8000 to 15000. Further, the number-average molecular weight of the polyurethane resin is 10000 to 12000. For example, the number-average molecular weight of the polyurethane resin can be any point value or the middle value of any two points within a range of 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, and 15000.

[0064] According to an embodiment of the present invention, the structural formula of the halohydrocarbon is R3-X.

[0065] Wherein, R3 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl, and the definition of substituent is the same as above; X is selected from halogen elements, such as F, Cl and / or Br.

[0066] According to an embodiment of the present invention, the halogenated hydrocarbon is selected from halogenated hydrocarbons that are liquid at room temperature and pressure.

[0067] According to an embodiment of the present invention, R3 is selected from C4-C. 10 Alkyl, C3-C 10 cycloalkyl, C6-C 14 Aryl, C3-C 10 Alkenyl group.

[0068] Preferably, the haloalkane is selected from one or a mixture of several of bromobutane (BB), bromohexane (BH), bromooctane (BD), and benzyl bromide (BLB).

[0069] Preferably, the structures of bromobutane, bromohexane, bromooctane, and benzyl bromide are as follows:

[0070]

[0071]

[0072] According to an embodiment of the present invention, the catalyst is one or a mixture of more than one of sodium hydride, lithium hydride, and potassium hydride.

[0073] According to an embodiment of the present invention, the molar ratio of the compound containing the -NH-COO- group to the catalyst is 1:(1 to 2); exemplaryly, it can be 1:(1.1 to 1.7), further, it can be 1:(1.2 to 1.5), for example, 1:1, 1:1.1, 1:1.2, 1.25, 1.3, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.

[0074] According to the present invention, the solvent is an anhydrous aprotic solvent selected from one or a mixture of several of the following: acetonitrile, tetrahydrofuran, dioxane, chloromethane, dichloromethane, trichloromethane, chloroform, acetone, methyl ethyl ketone, nitromethane, nitrobenzene, pyridine, quinoline, dimethyl sulfoxide, formamide, diformamide, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoramide, chlorobenzene, benzene, toluene, xylene, n-hexane, heptane, and petroleum ether.

[0075] [Carbamate Quaternary Ammonium Salts]

[0076] The present invention also provides a urethane quaternary ammonium salt, which is a quaternary ammonium salt of a polyurethane resin or a compound having the structure shown in Formula 2.

[0077]

[0078] In Equation 2, R1, R2, R3 and X are defined as before.

[0079] According to an embodiment of the present invention, the polyurethane resin is defined as before.

[0080] According to embodiments of the present invention, R1 and R2 may be the same or different, and are independently selected from H, substituted or unsubstituted C1-C8 alkyl groups, and substituted or unsubstituted C3-C4 alkyl groups. 10 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C2-C 10 The definitions of alkenyl and substituent are the same as above.

[0081] According to an embodiment of the present invention, at least one of R1 and R2 is selected from C(R4)(R5)=C(R6)-COO- or C(R4)(R5)=C(R6)-COO-(CH2). n Alkyl groups substituted with -OCO-NH- groups. Exemplarily, C(R4)(R5)=C(R6)-COO- groups or C(R4)(R5)=C(R6)-COO-(CH2) groups. n The -OCO-NH- group can have one, two, or more substitutions.

[0082] According to an embodiment of the present invention, R3 is selected from C4-C. 10 Alkyl, C3-C 10 cycloalkyl, C6-C 14 Aryl, C3-C 10 Alkenyl groups, R4, R5, R6, and n, have the definitions described above.

[0083] According to an embodiment of the present invention, R3 is selected from butyl, hexyl, octyl or benzyl.

[0084] According to an embodiment of the present invention, the urethane quaternary ammonium salt is selected from the quaternary ammonium salt of polyurethane resin or the quaternary ammonium salt of urethane dimethacrylate.

[0085] According to an embodiment of the present invention, the urethane quaternary ammonium salt is prepared by the above-described method for preparing urethane quaternary ammonium salts.

[0086] Applications of carbamate quaternary ammonium salts

[0087] The present invention also provides the application of the above-mentioned carbamate quaternary ammonium salt in antibacterial applications.

[0088] The present invention also provides an antibacterial material comprising a cured product of the above-mentioned urethane quaternary ammonium salt and a compound containing a -NH-COO- group.

[0089] According to embodiments of the present invention, the compound containing the -NH-COO- group is the same as or different from the compound containing the -NH-COO- group used to prepare the quaternary ammonium carbamate salt, for example, the same.

[0090] According to embodiments of the present invention, the compound containing the -NH-COO- group has the definition described above.

[0091] According to an embodiment of the present invention, the mass ratio of the urethane quaternary ammonium salt to the compound containing the -NH-COO- group is 1:(1000 to 100000); exemplaryly, it can be 1:(3000 to 90000), further, it can be 1:(10000 to 60000), for example, the mass ratio of the urethane quaternary ammonium salt to the compound containing the -NH-COO- group is 1:1000, 1:2000, or 1:30. Any value from any of the following: 00, 1:4000, 1:5000, 1:8000, 1:10000, 1:15000, 1:20000, 1:25000, 1:30000, 1:35000, 1:40000, 1:45000, 1:50000, 1:60000, 1:70000, 1:80000, 1:90000, 1:100000, or any value within a range of any two points.

[0092] This invention also provides a method for preparing the above-mentioned antibacterial material, the method comprising the following steps:

[0093] The above-mentioned urethane quaternary ammonium salt is mixed with a compound containing -NH-COO- groups and then cured to obtain an antibacterial material.

[0094] According to embodiments of the present invention, the compound containing the -NH-COO- group is the same as or different from the compound containing the -NH-COO- group used to prepare the quaternary ammonium carbamate salt, for example, the same.

[0095] According to embodiments of the present invention, the compound containing the -NH-COO- group has the definition described above.

[0096] According to an embodiment of the present invention, the curing includes photocuring and / or heat curing.

[0097] According to an embodiment of the present invention, when the curing is photocuring, the preparation method further includes the step of adding a photoinitiator.

[0098] According to an embodiment of the present invention, the mass ratio of the urethane quaternary ammonium salt to the compound containing the -NH-COO- group has the definition described above.

[0099] According to an embodiment of the present invention, the amount of photoinitiator added is 1 to 5 wt% of the total amount of the mixture, preferably 2 to 4 wt% of the total amount of the mixture, for example, 2 wt%.

[0100] According to an embodiment of the present invention, the photocuring time is 1 min to 10 min, preferably 3 min to 5 min, for example 2 min.

[0101] According to an embodiment of the present invention, the temperature for heat curing is 80-150°C, preferably 90-120°C, for example 100°C.

[0102] According to an embodiment of the present invention, the heating and curing time is 30 min to 200 min, preferably 60 min to 130 min, for example 120 min.

[0103] As an example, the method includes mixing the urethane quaternary ammonium salt, urethane dimethacrylate, and photoinitiator, and then curing them in an ultraviolet curing oven for 2 minutes.

[0104] As an example, the method includes mixing the urethane quaternary ammonium salt with a polyurethane resin and drying it at a temperature of 100°C.

[0105] The following detailed description, in conjunction with specific embodiments, illustrates the general formula compounds of the present invention, their preparation methods, and applications in further detail. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0106] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0107] The urethane dimethacrylate used in the following examples is a mixture of isomers of diurea dimethacrylate, CAS Registry No. 72869-86-4, comprising compounds with structures shown in Formulas a-1 and a-2 below, with the compound with structure shown in Formula a-2 being the main component:

[0108]

[0109] Example 1

[0110] 4.1 g (10 mmol, containing 20 mmol of urethane), 48 mmol of bromobutane (BB), and 100 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH (0.3 g) was then added as a catalyst. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. After washing the product with petroleum ether, it was centrifuged (3000 r / min) to separate the product. The precipitate was then washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PUA-BB.

[0111] See Figure 1 The figure shows the X-ray photoelectron spectroscopy (XPS) analysis of the PUA-BB prepared in this embodiment. It can be seen from the figure that the peak of bromine still exists in the PUA-BB after multiple washings, indicating that the quaternary ammonium salt was successfully prepared.

[0112] Example 2

[0113] 4.1 g (10 mmol, containing 20 mmol of urethane), 48 mmol of hexane (BH), and 100 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH (0.3 g) was then added as a catalyst. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. After washing the product with petroleum ether, it was first centrifuged (3000 r / min) to separate the product, then washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PUA-BH.

[0114] Example 3

[0115] 4.1 g (10 mmol, containing 20 mmol of carbamate), 96 mmol of bromooctane (BD), and 100 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH (0.3 g) was then added as a catalyst. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min), and the precipitate was washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the quaternary ammonium carbamate salt, named PUA-BD.

[0116] Example 4

[0117] 4.1 g (10 mmol, containing 20 mmol of carbamate), 48 mmol of benzyl bromide (BLB), and 100 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH (0.3 g) was then added as a catalyst. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min), and the precipitate was washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the quaternary ammonium carbamate salt, named PUA-BLB.

[0118] Example 5

[0119] 20 g (1 mmol, containing 8-10 mmol of urethane) of polyurethane resin (molecular weight approximately 20,000), 20 mmol of bromobutane (BB), and 200 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH was then added as a reaction catalyst (0.3 g) and mixed. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min) to separate the product, and then washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PU-BB.

[0120] Example 6

[0121] 20 g (1 mmol, containing 8-10 mmol of urethane) of polyurethane resin (molecular weight approximately 20,000), 24 mmol of hexane (BH), and 200 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH (0.3 g) was then added as a reaction catalyst. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min), and the precipitate was washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PU-BH.

[0122] Example 7

[0123] 20 g (1 mmol, containing 8-10 mmol of urethane) of polyurethane resin (molecular weight approximately 20,000), 30 mmol of bromooctane (BD), and 250 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH was then added as a reaction catalyst (0.3 g) and mixed. The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min) to separate the product, and then washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PU-BD.

[0124] Example 8

[0125] 20 g (1 mmol, containing 8-10 mmol of urethane) of polyurethane resin (molecular weight approximately 20,000), 48 mmol of benzyl bromide (BLB), and 300 mL of acetonitrile were added to separate three-necked flasks equipped with a mechanical stirrer and thermometer. NaH was then added as a reaction catalyst (0.3 g). The mixture was heated to 80 °C and stirred for 72 h to obtain the reaction product. The product was then washed with petroleum ether, centrifuged (3000 r / min), and the precipitate was washed three times with acetonitrile to remove polar byproducts and excess catalyst. The solvent was removed by rotary evaporation to obtain the urethane quaternary ammonium salt, named PU-BLB.

[0126] Example 9: Preparation of antibacterial materials:

[0127] Prepare quaternary ammonium carbamate salts PUA-BB, PUA-BH, PUA-BD, and PUA-BLB at concentrations of 200 μg / mL, 400 μg / mL, 800 μg / mL, 1000 μg / mL, 2000 μg / mL, 4000 μg / mL, 6000 μg / mL, 8000 μg / mL, and 10000 μg / mL, respectively. Add each salt to 1 g of carbamate dimethacrylate, then add photoinitiator 184 (added at 2 wt%), stir evenly, and wait for the photoinitiator to completely dissolve before curing in a UV curing oven for 2 minutes.

[0128] Different amounts of the antibacterial agents PU-BB, PU-BH, PU-BD and PU-BLB were added to polyurethane resin (molecular weight approximately 20,000), stirred evenly, and dried in an oven at 100°C for 2 hours.

[0129] Test Example 1

[0130] Antibacterial properties of carbamate quaternary ammonium salts:

[0131] To determine the antibacterial properties of carbamate quaternary ammonium salts, the most common Gram-negative bacterium *Escherichia coli* and Gram-positive bacterium *Staphylococcus aureus* were cultured in LB broth (LB Broth, a bacterial culture medium). Before each experiment, bacteria were inoculated into 5 mL of LB broth and incubated overnight at 37°C to obtain a stationary phase. Then, 100 μL of bacteria was incubated in 5 mL of fresh LB broth at 37°C for 1 h to obtain a logarithmic mid-phase culture. 200 μL of bacteria (density 1 × 10⁻⁶) was then cultured... 6 Add CFU / mL to a 48-well plate and incubate overnight at 37°C. Add 20 μL of sodium resazurin (1 mg / mL) to each well and incubate for another hour.

[0132] Different solid LB plates (blister packs) were treated with carbamate quaternary ammonium salts PUA-BB, PUA-BH, PUA-BD, and PUA-BLB at concentrations of 200 μg / mL, 400 μg / mL, 800 μg / mL, 1000 μg / mL, 2000 μg / mL, 4000 μg / mL, 6000 μg / mL, 8000 μg / mL, and 10000 μg / mL, respectively. 100 μL of bacteria (density 1 × 10⁻⁶) were inoculated onto each plate. 5 The minimum inhibitory concentration (MIC) was obtained by incubating at 37°C overnight (CFU / mL). The antibacterial properties (MIC values) of different carbamate quaternary ammonium salts are shown in Table 1.

[0133] Table 1. Minimum inhibitory concentrations of different carbamate quaternary ammonium salts

[0134]

[0135] The carbamate quaternary ammonium salts prepared in this invention have a minimum inhibitory concentration (MIC) of less than 8000 μg / mL against Escherichia coli, for example, less than 6000 μg / mL, 4000 μg / mL, 2000 μg / mL, and 800 μg / mL; and a minimum inhibitory concentration (MIC) of less than 6000 μg / mL against Staphylococcus aureus, for example, less than 4000 μg / mL, 2000 μg / mL, 800 μg / mL, and 200 μg / mL.

[0136] The specific embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a quaternary ammonium carbamate salt, characterized in that, The preparation method includes the following steps: Compounds containing -NH-COO- groups are quaternized with haloalkanes under the action of a catalyst to obtain quaternary ammonium carbamate salts; The compound containing the -NH-COO- group is selected from a mixture of isomers of diurea dimethacrylate; The halohydrocarbon is selected from one or a mixture of several of bromobutane, bromohexane, bromooctane, and benzyl bromide; The catalyst is selected from one or a mixture of more than one of sodium hydride, lithium hydride, and potassium hydride.

2. The preparation method according to claim 1, characterized in that, The quaternization reaction is carried out at a temperature of 40~120℃; And / or, the quaternization reaction takes 8 h to 120 h; And / or, the molar ratio of the compound containing the -NH-COO- group to the haloalkanes is at least 1:

1.

3. The preparation method according to any one of claims 1-2, characterized in that, The molar ratio of the compound containing the -NH-COO- group to the catalyst is 1:(1~2); And / or, the solvent is an anhydrous aprotic solvent selected from one or more of acetonitrile, tetrahydrofuran, dioxane, chloromethane, dichloromethane, trichloromethane, chloroform, acetone, methyl ethyl ketone, nitromethane, nitrobenzene, pyridine, quinoline, dimethyl sulfoxide, formamide, diformamide, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoramide, chlorobenzene, benzene, toluene, xylene, n-hexane, heptane, and petroleum ether.

4. A quaternary ammonium carbamate salt, characterized in that, The urethane quaternary ammonium salt is obtained by quaternization reaction of a mixture of isomers of diurea dimethacrylate with a haloalkanes under the action of a catalyst. The halohydrocarbon is selected from one or a mixture of several of bromobutane, bromohexane, bromooctane, and benzyl bromide; The catalyst is selected from one or a mixture of more than one of sodium hydride, lithium hydride, and potassium hydride.

5. The use of the urethane quaternary ammonium salt according to claim 4, or the urethane quaternary ammonium salt prepared by any one of claims 1-3, in the preparation of antibacterial agents.

6. An antibacterial material, which is obtained by mixing and curing a urethane quaternary ammonium salt prepared according to claim 4 or the preparation method according to any one of claims 1-3 with a compound containing a -NH-COO- group.

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