A preparation method and application of amino-terminated quaternary ammonium salt polymer material

Abstract

The invention belongs to the technical field of polymer materials, and discloses a preparation method and application of a terminal amino quaternary ammonium salt polymer material. The present invention reacts polyol and isocyanate monomers, then reacts with Boc aminobenzene quaternary ammonium salt compounds, and finally removes the Boc protecting group through trifluoroacetic acid to obtain a polyurethane-based polymer material containing amino and quaternary ammonium salt groups at the terminal position. The terminal amino quaternary ammonium salt polymer material is used as a toughening agent and added to an epoxy resin. The terminal amino quaternary ammonium salt polymer material contains amino groups and can undergo a thermosetting reaction with the epoxy resin, thereby grafting polyurethane flexible molecular chains into the epoxy resin to form a flexible curing cross-linking network, which has a good toughening effect and improves the elongation at break and the impact strength of the epoxy resin. The terminal amino quaternary ammonium salt polymer material contains a unique quaternary ammonium salt group, so that the epoxy resin material shows good antibacterial properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a preparation method and application of an amino-terminated quaternary ammonium salt polymer material. Background Art

[0002] Currently, the amino-terminated materials on the market are primarily polyetheramines, a class of polymers with a polyether backbone and amine-terminated reactive functional groups. Polyetheramines are obtained by ammoniation of polyethylene glycol, polypropylene glycol, or ethylene glycol / propylene glycol copolymers under high temperature and pressure. They are widely used in a variety of applications, including polyurea spray coatings, large-scale composite materials, epoxy resin curing agents, and automotive gasoline detergents. However, polyetheramines typically require high temperature and high pressure reaction conditions, making the reaction conditions relatively complex.

[0003] Epoxy resin has high strength, excellent insulation properties, and good curing properties. It is widely used in adhesives, coatings, etc. However, traditional epoxy resin does not have antibacterial properties, which limits its practical application in antibacterial products, medical supplies, etc. Epoxy resin also has the problem of brittleness and poor toughness. Polyurethane is a type of polymer material with high elasticity and good toughness, and has broad application prospects in the toughening and modification of epoxy resins. The master's thesis "Research on Amine-Terminated Polyurethane Toughened Epoxy Resin Adhesives" discloses that the reaction of polyethylene glycol, toluene diisocyanate, and meta-xylenediamine to obtain an amino-terminated polyurethane can improve the toughness, strength and other properties of epoxy resins. However, the paper did not give the epoxy resin antibacterial properties. Summary of the Invention

[0004] The invention provides a preparation method and application of an amino-terminated quaternary ammonium salt polymer material, which solves the problems that epoxy resin has poor toughness and no antibacterial performance.

[0005] The technical solution is: a preparation method of an amino-terminated quaternary ammonium salt polymer material, comprising the following steps: adding a polyol into a flask, vacuum drying and dehydration, introducing nitrogen, adding an isocyanate monomer, heating to 80-90°C, stirring and reacting for 2-5 hours, then adding a viscosity reducer, lowering the temperature to 35-60°C, adding a Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate, reacting for 2-3 hours, rotary evaporation, then adding dichloromethane, stirring and dispersing, then adding trifluoroacetic acid, stirring and reacting at room temperature for 18-24 hours, rotary evaporation, washing with a sodium bicarbonate solution and ethanol in sequence, and drying to obtain the amino-terminated quaternary ammonium salt polymer material.

[0006] The general chemical formula of the amino quaternary ammonium salt compound is shown in formula (I):

[0007] Where n=8-16.

[0008] Preferably, the molar ratio of the polyol, isocyanate monomer, and Boc aminophenyl quaternary ammonium salt compound is 1:(2-3):(2-2.6). The polyol is a polyether polyol, polyester polyol, or vegetable oil polyol; the molecular weight of the polyol is 1000-3000. The isocyanate monomer is toluene-2,4-diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, or isophorone diisocyanate.

[0009] Preferably, the amount of the viscosity reducer added is 10-20% of the total mass of the polyol and isocyanate monomer. The viscosity reducer is one or a combination of acetone, ethyl acetate, dichloromethane, 1,2-dichloroethane, benzene, toluene, and xylene.

[0010] Preferably, the preparation method of Boc aminophenyl quaternary ammonium salt compound is:

[0011] Step (1) is added to a flask, tert-butyl (4-hydroxyphenyl) carbamate, water, polyethylene glycol 400, and epichlorohydrin is added dropwise after stirring. After stirring, potassium hydroxide aqueous solution is added dropwise, wherein the molar ratio of (4-hydroxyphenyl) carbamate, water, polyethylene glycol 400, epichlorohydrin, and potassium hydroxide is 1: (0.045-0.05): (2.5-3.2): (2.5-3.2), heated to 80-95 ° C, reacted for 4-10 hours, cooled, added hydrochloric acid solution to neutralize, then added dichloromethane to extract, the organic phase was collected, dried over anhydrous sodium sulfate, rotary evaporated, and washed with petroleum ether to obtain Boc aminophenyl glycidyl ether. The reaction formula is:

[0012]

[0013] Step (2), add isopropyl alcohol, water, Boc aminophenyl glycidyl ether to a flask, add HCl aqueous solution dropwise, stir and add N, N-dimethylalkylamine, wherein the molar ratio of Boc aminophenyl glycidyl ether, HCl, N, N-dimethylalkylamine is 1:1:(0.9-1.1), and the structural formula of N, N-dimethylalkylamine is wherein n=8-16; heating to 55-70°C, reacting for 1-2 hours, removing isopropyl alcohol by rotary evaporation, separating out the precipitate, filtering, washing with petroleum ether, and recrystallizing the product from ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound. The reaction formula is:

[0014]

[0015] Preferably, the amino-terminated quaternary ammonium salt polymer material is used in the epoxy resin, and the amount of the amino-terminated quaternary ammonium salt polymer material is 10-30% of the epoxy resin.

[0016] The technical effect of the present invention is that: the present invention uses potassium hydroxide as a catalyst and polyethylene glycol 400 as a phase transfer catalyst to carry out an etherification reaction on tert-butyl (4-hydroxyphenyl)carbamate and epichlorohydrin, and then carries out a quaternization reaction with N,N-dimethylalkylamine and HCl to obtain a novel Boc aminophenyl quaternary ammonium salt compound containing a hydroxyl group.

[0017] The invention uses toluene-2,4-diisocyanate, isophorone diisocyanate and the like as isocyanate monomers, and carries out polymerization reaction with polyols such as polyether polyol and polyester polyol to obtain an isocyanate-terminated polyurethane prepolymer, which is then reacted with the hydroxyl group of a Boc aminophenyl quaternary ammonium salt compound. Finally, the Boc protecting group is removed by trifluoroacetic acid to obtain a polyurethane-based polymer material containing amino groups and quaternary ammonium salt groups at the terminal positions.

[0018] The present invention uses an amino-terminated quaternary ammonium salt polymer material as a toughening agent and adds it to the epoxy resin. The polyurethane itself has the advantages of high elasticity and good toughness, and contains amino groups at both ends, which can undergo a thermal curing reaction with the epoxy resin, thereby grafting the polyurethane flexible molecular chains into the epoxy resin to form a flexible cured cross-linked network, achieving a good toughening effect and improving the elongation at break and impact strength of the epoxy resin.

[0019] The amino-terminated quaternary ammonium salt polymer material of the present invention contains a unique quaternary ammonium salt group, which can interact with the negatively charged bacterial cell membrane, change the permeability of the cell membrane, and allow substances inside the bacterial cell membrane to overflow, thereby killing the bacteria and making the epoxy resin material exhibit good antibacterial properties. DETAILED DESCRIPTION

[0020] In order to make the purpose, implementation methods and advantages of the present application clearer, the exemplary implementation methods of the present application will be clearly and completely described below in combination with the exemplary embodiments of the present application. Obviously, the described exemplary embodiments are only part of the embodiments of the present application, not all of the embodiments.

[0021] Example 1

[0022] Step (1), add 40mmol (4-hydroxyphenyl) tert-butyl carbamate, 10mL water, 1.8mmol polyethylene glycol 400 into a flask, stir and dropwise add 128mmol epichlorohydrin, stir and dropwise add 40mL aqueous solution containing 128mmol potassium hydroxide, heat to 95°C, react for 6h, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, and wash with petroleum ether to obtain Boc aminophenyl glycidyl ether.

[0023] Step (2) is to add 80 mL of isopropyl alcohol, 70 mL of water, and 40 mmol of Boc aminophenyl glycidyl ether to a flask, dropwise add 4 mL of a 10 mol / L aqueous solution of HCl, stir, add 44 mmol of N,N-dimethyl-n-octylamine, heat to 55° C., react for 2 h, remove isopropyl alcohol by rotary evaporation, precipitate, filter, wash with petroleum ether, and recrystallize the product from ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound. The structural formula is:

[0024] Step (3) adds 10mmol polyethylene glycol 1000 as polyether polyol to a flask, vacuum-dries and dehydrates, introduces nitrogen, adds 23mmol toluene-2,4-diisocyanate, heats to 85°C, stirs and reacts for 4h, then adds acetone as a viscosity reducer, the amount of which is 20% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 40°C, 23mmol Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate are added, reacted for 3h, rotary evaporated, then 300mL dichloromethane is added, stirred and dispersed, and then 120mL trifluoroacetic acid is added, stirred and reacted at room temperature for 24h, rotary evaporated, washed with sodium bicarbonate solution and ethanol in sequence, and dried to obtain an amino-terminated quaternary ammonium salt polymer material. The reaction formula is:

[0025]

[0026] Step (4), add 100g epoxy resin E44, 5g ethylenediamine curing agent, and 10g terminal amino quaternary ammonium salt polymer material to the container, stir and mix, then cast into a mold, vacuum degassing, place in a heating box, first cure at 80°C for 4h, then cure at 130°C for 5h, demould to obtain an epoxy resin material.

[0027] Example 2

[0028] Step (1), add 40mmol (4-hydroxyphenyl) tert-butyl carbamate, 10mL water, 2mmol polyethylene glycol 400 into a flask, stir and dropwise add 128mmol epichlorohydrin, stir and dropwise add 40mL aqueous solution containing 128mmol potassium hydroxide, heat to 85°C, react for 10h, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, and wash with petroleum ether to obtain Boc aminophenyl glycidyl ether.

[0029] Step (2) is to add 80 mL of isopropanol, 70 mL of water, and 40 mmol of Boc aminophenyl glycidyl ether to a flask, dropwise add 4 mL of a 10 mol / L aqueous solution of HCl, stir, add 36 mmol of dodecyldimethylamine, heat to 70°C, react for 1 hour, remove isopropanol by rotary evaporation, precipitate, filter, wash with petroleum ether, and recrystallize the product in ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound. The structural formula is

[0030] Step (3) adds 10mmol polycarbonate diol 1000 as polyester polyol into a flask, vacuum-dries and dehydrates, introduces nitrogen, adds 26mmol isophorone diisocyanate, heats to 85°C, stirs and reacts for 4h, then adds dichloromethane as a viscosity reducer, the amount of the viscosity reducer added is 20% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 35°C, 26mmol Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate are added, reacted for 3h, rotary evaporated, then 300mL dichloromethane is added, stirred and dispersed, and then 120mL trifluoroacetic acid is added, stirred and reacted at room temperature for 24h, rotary evaporated, washed with sodium bicarbonate solution and ethanol in sequence, and dried to obtain an amino-terminated quaternary ammonium salt polymer material.

[0031] Step (4) adds 100g epoxy resin E44, 5g ethylenediamine curing agent, and 15g terminal amino quaternary ammonium salt polymer material to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, and demolds to obtain an epoxy resin material.

[0032] Example 3

[0033] Step (1), add 40mmol (4-hydroxyphenyl) tert-butyl carbamate, 10mL water, 2mmol polyethylene glycol 400 into a flask, stir and dropwise add 100mmol epichlorohydrin, stir and dropwise add 40mL aqueous solution containing 100mmol potassium hydroxide, heat to 95°C, react for 4h, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, and wash with petroleum ether to obtain Boc aminophenyl glycidyl ether.

[0034] Step (2) is to add 80 mL of isopropanol, 70 mL of water, and 40 mmol of Boc aminophenyl glycidyl ether to a flask, dropwise add 4 mL of a 10 mol / L aqueous HCl solution, stir, add 44 mmol of dodecyldimethyl tertiary amine, heat to 60° C., react for 2 h, and rotary evaporation to remove isopropanol. The precipitate is filtered, washed with petroleum ether, and the product is recrystallized from ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound.

[0035] Step (3), adding 10mmol of polytetrahydrofuran ether diol as a polyether polyol into a flask, vacuum drying and dehydration, introducing nitrogen, adding 30mmol of diphenylmethane-4,4'-diisocyanate, heating to 90°C, stirring and reacting for 2h, then adding a viscosity reducer, ethyl acetate, the amount of the viscosity reducer added is 20% of the total mass of the polyol and isocyanate monomers; the temperature is reduced to 60°C, 26mmol of Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate are added, reacting for 2h, rotary evaporation, then adding 300mL of dichloromethane, stirring and dispersing, and then adding 120mL of trifluoroacetic acid, stirring and reacting at room temperature for 18h, rotary evaporation, washing with sodium bicarbonate solution and ethanol in sequence, and drying to obtain an amino-terminated quaternary ammonium salt polymer material.

[0036] Step (4) adds 100g epoxy resin E44, 5g ethylenediamine curing agent, and 20g terminal amino quaternary ammonium salt polymer material to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, and demolds to obtain an epoxy resin material.

[0037] Example 4

[0038] Step (1), add 40mmol (4-hydroxyphenyl) tert-butyl carbamate, 10mL water, 2mmol polyethylene glycol 400 into a flask, stir and dropwise add 110mmol epichlorohydrin, stir and dropwise add 40mL aqueous solution containing 110mmol potassium hydroxide, heat to 80°C, react for 10h, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, and wash with petroleum ether to obtain Boc aminophenyl glycidyl ether.

[0039] Step (2) is to add 80 mL of isopropanol, 70 mL of water, and 40 mmol of Boc aminophenyl glycidyl ether to a flask, dropwise add 4 mL of a 10 mol / L aqueous HCl solution, stir, add 40 mmol of hexadecyldimethyl tertiary amine, heat to 55° C., react for 2 h, and rotary evaporation to remove isopropanol. The precipitate is filtered, washed with petroleum ether, and the product is recrystallized from ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound.

[0040] Step (3), adding 10mmol polyethylene glycol 1000 as a polyether polyol into a flask, vacuum drying and dehydration, introducing nitrogen, adding 23mmol toluene-2,4-diisocyanate, heating to 80°C, stirring and reacting for 5h, then adding a viscosity reducer xylene, the addition amount of the viscosity reducer being 10% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 60°C, adding 23mmol Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate, reacting for 3h, rotary evaporation, then adding 300mL dichloromethane, stirring and dispersing, then adding 120mL trifluoroacetic acid, stirring and reacting at room temperature for 24h, rotary evaporation, washing with sodium bicarbonate solution and ethanol in sequence, and drying to obtain an amino-terminated quaternary ammonium salt polymer material.

[0041] Step (4) adds 100g epoxy resin E44, 5g ethylenediamine curing agent, and 25g terminal amino quaternary ammonium salt polymer material to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, and demolds to obtain an epoxy resin material.

[0042] Example 5

[0043] Step (1), add 40mmol (4-hydroxyphenyl) tert-butyl carbamate, 10mL water, 1.8mmol polyethylene glycol 400 into a flask, stir and dropwise add 128mmol epichlorohydrin, stir and dropwise add 40mL aqueous solution containing 128mmol potassium hydroxide, heat to 85°C, react for 8h, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, and wash with petroleum ether to obtain Boc aminophenyl glycidyl ether.

[0044] Step (2) is to add 80 mL of isopropyl alcohol, 70 mL of water, and 40 mmol of Boc aminophenyl glycidyl ether to a flask, dropwise add 4 mL of a 10 mol / L aqueous solution of HCl, stir, add 40 mmol of hexadecyldimethylamine, heat to 65° C., react for 1 hour, remove isopropyl alcohol by rotary evaporation, precipitate, filter, wash with petroleum ether, and recrystallize the product in ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound. The structural formula is

[0045] Step (3) adds 10mmol polycaprolactone diol 1000 as polyester polyol into a flask, vacuum-dries and dehydrates, introduces nitrogen, adds 20mmol isophorone diisocyanate, heats to 80°C, stirs and reacts for 4h, then adds dichloromethane as a viscosity reducer, wherein the amount of the viscosity reducer added is 10% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 35°C, 20mmol Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate are added, reacted for 2h, rotary evaporated, then 300mL dichloromethane is added, stirred and dispersed, and then 120mL trifluoroacetic acid is added, stirred and reacted at room temperature for 24h, rotary evaporated, washed with sodium bicarbonate solution and ethanol in sequence, and dried to obtain an amino-terminated quaternary ammonium salt polymer material.

[0046] Step (4) adds 100g epoxy resin E44, 5g ethylenediamine curing agent, and 30g terminal amino quaternary ammonium salt polymer material to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, and demolds to obtain an epoxy resin material.

[0047] The difference between Comparative Example 1 and Example 1 is that no amino-terminated quaternary ammonium salt polymer material is added to the epoxy resin material. Specifically:

[0048] Step (1) adds 100g epoxy resin E44 and 5g ethylenediamine curing agent to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, demolds, and obtains an epoxy resin material.

[0049] The difference between Comparative Example 2 and Example 1 is that trifluoroacetic acid is not used to remove the Boc protecting group when preparing the quaternary ammonium salt polymer material. Specifically:

[0050] Step (1) adds 10 mmol of polyethylene glycol 1000 as a polyether polyol into a flask, vacuum-dries and dehydrates, introduces nitrogen, adds 23 mmol of toluene-2,4-diisocyanate, heats to 85° C., stirs and reacts for 4 hours, then adds acetone as a viscosity reducer, wherein the amount of the viscosity reducer added is 20% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 40° C., 23 mmol of Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate are added, reacts for 3 hours, rotary evaporates, washes with ethanol, and dries to obtain a quaternary ammonium salt polymer material.

[0051] Step (2) adds 100g epoxy resin E44, 5g ethylenediamine curing agent, and 10g quaternary ammonium salt polymer material to a container, stirs and mixes, then casts into a mold, vacuum degasses, places in a heating box, first cures at 80°C for 4h, then cures at 130°C for 5h, and demolds to obtain an epoxy resin material.

[0052] The difference between Comparative Example 3 and Example 1 is that when preparing the amino-terminated polymer material, N-Boc-ethanolamine (structural formula: ) replaces the Boc aminophenyl quaternary ammonium salt compound, specifically:

[0053] Step (1) adds 10 mmol of polyethylene glycol 1000 as a polyether polyol into a flask, vacuum-dries and dehydrates, introduces nitrogen, adds 23 mmol of toluene-2,4-diisocyanate, heats to 85° C., stirs and reacts for 4 hours, then adds acetone as a viscosity reducer, wherein the amount of the viscosity reducer added is 20% of the total mass of the polyol and isocyanate monomers; the temperature is lowered to 40° C., 23 mmol of N-Boc-ethanolamine and dibutyltin dilaurate are added, reacted for 3 hours, rotary evaporated, then 300 mL of dichloromethane is added, stirred and dispersed, and then 120 mL of trifluoroacetic acid is added, stirred and reacted at room temperature for 24 hours, rotary evaporated, washed with sodium bicarbonate solution and ethanol in sequence, and dried to obtain an amino-terminated polymer material.

[0054] Step (2), add 100g of epoxy resin E44, 5g of ethylenediamine curing agent, and 10g of terminal amino polymer material to the container, stir and mix, then cast into a mold, vacuum degas, place in a heating box, first cure at 80°C for 4h, then cure at 130°C for 5h, demold to obtain the epoxy resin material.

[0055] The tensile properties, flexural strength, and impact strength of epoxy resin materials were tested according to GB / T 2567-2021. The test results are shown in the table below.

[0056]

[0057]

[0058] As can be seen from the table above, compared with Comparative Example 1, the epoxy resins of Examples 1-5 are added with amino-terminated polyurethane-based polymers. The polyurethane itself has the advantages of high elasticity and good toughness, and it contains amino groups at both ends, which can undergo a thermal curing reaction with the epoxy resin, thereby grafting the polyurethane flexible molecular chains into the epoxy resin to form a flexible cured cross-linked network, which has a good toughening effect. The elongation at break reaches 10.1-23.5%, and the impact strength reaches 13.6-26.4 kJ / m 2 .

[0059] In Comparative Example 2, when preparing a quaternary ammonium salt polymer material, trifluoroacetic acid is not used to remove the Boc protecting group. The resulting polyurethane-based polymer does not contain terminal amino groups and cannot undergo a curing reaction with the epoxy resin. The particles have poor compatibility, poor toughening effect on the epoxy resin, and low elongation at break and impact strength.

[0060] In Comparative Example 3, when preparing the amino-terminated polymer material, N-Boc-ethanolamine was used instead of the Boc aminophenyl quaternary ammonium salt compound. The obtained polyurethane-based polymer contained an amino group and could undergo a thermal curing reaction with the epoxy resin to form a flexible cured cross-linked network, which had a good toughening effect and significantly improved the elongation at break and impact strength of the epoxy resin.

[0061] The epoxy resin material was poured onto the tinplate surface, first cured at 80℃ for 4h, then cured at 130℃ for 5h to make an epoxy resin film, and then sterilized by ultraviolet light; Staphylococcus aureus, Escherichia coli, and Candida albicans were cultured and activated at 37℃ for 24h to make bacterial suspension (concentration of 10 6 cfu / mL); 0.1 mL of the bacterial suspension was spread on the surface of the agar medium, and then an epoxy resin film was attached to the surface of the agar medium. The culture was placed in an incubator and incubated at 37°C for 24 hours. The diameter of the inhibition zone was measured. Each sample group was tested three times, and the average value was taken. The test results are shown in the table below.

[0062]

[0063] As can be seen from the table above, the epoxy resin film materials of Examples 1-5 all showed obvious inhibition zone diameters against Staphylococcus aureus, Escherichia coli, and Candida albicans, and had excellent antibacterial properties. This is because the added amino-terminated quaternary ammonium salt polymer material contains unique quaternary ammonium salt groups, which can interact with the negatively charged cell membrane of bacteria, change the permeability of the cell membrane, and allow substances inside the bacterial cell membrane to overflow, thereby killing the bacteria and showing excellent antibacterial properties.

[0064] In Comparative Example 1, no amino-terminated quaternary ammonium salt polymer material was added, and the epoxy resin material did not exhibit the inhibition zone diameter and antibacterial performance.

[0065] The quaternary ammonium salt polymer material added in Comparative Example 2 can also improve the antibacterial properties of the epoxy resin material, showing an obvious inhibition zone diameter.

[0066] In Comparative Example 3, when preparing the amino-terminated polymer material, N-Boc-ethanolamine was used instead of the Boc aminophenyl quaternary ammonium salt compound. The obtained amino-terminated polymer material did not contain an antibacterial quaternary ammonium salt group, and the epoxy resin material did not show an inhibition zone diameter and antibacterial performance.

[0067] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing an amino-terminated quaternary ammonium salt polymer material, characterized in that: The preparation method is as follows: add polyol to a flask, vacuum dry and dehydrate, introduce nitrogen, add isocyanate monomer, heat to 80-90° C., stir and react for 2-5 hours, then add viscosity reducer, reduce the temperature to 35-60° C., add Boc aminophenyl quaternary ammonium salt compound and dibutyltin dilaurate, react for 2-3 hours, rotary evaporate, then add dichloromethane, stir and disperse, then add trifluoroacetic acid, stir and react at room temperature for 18-24 hours, rotary evaporate, wash with sodium bicarbonate solution and ethanol in sequence, and dry to obtain an amino-terminated quaternary ammonium salt polymer material; The chemical formula of the Boc aminophenyl quaternary ammonium salt compound is shown in formula (I): Where n=8-16.

2. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 1, wherein The molar ratio of the polyol, the isocyanate monomer and the Boc aminophenyl quaternary ammonium salt compound is 1:(2-3):(2-2.6).

3. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 1, wherein The polyol is polyether polyol, polyester polyol or vegetable oil polyol; the molecular weight of the polyol is 1000-3000.

4. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 1, wherein The isocyanate monomer is toluene-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate or isophorone diisocyanate.

5. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 1, characterized in that: The added amount of the viscosity reducer is 10-20% of the total mass of the polyol and the isocyanate monomer.

6. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 5, characterized in that: The viscosity reducing agent is one or a combination of acetone, ethyl acetate, dichloromethane, 1,2-dichloroethane, benzene, toluene and xylene.

7. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 2, characterized in that: The preparation method of the Boc aminophenyl quaternary ammonium salt compound is: Step (1), add tert-butyl (4-hydroxyphenyl)carbamate, water, polyethylene glycol 400 into a flask, add epichlorohydrin dropwise after stirring, add potassium hydroxide aqueous solution dropwise after stirring, heat to 80-95° C., react for 4-10 hours, cool, add hydrochloric acid solution to neutralize, then add dichloromethane to extract, collect the organic phase, dry over anhydrous sodium sulfate, rotary evaporate, wash with petroleum ether to obtain Boc aminophenyl glycidyl ether; Step (2), add isopropanol, water, Boc aminophenyl glycidyl ether into a flask, add HCl aqueous solution dropwise, add N,N-dimethylalkylamine after stirring, heat to 55-70° C., react for 1-2 hours, remove isopropanol by rotary evaporation, precipitate, filter, wash with petroleum ether, and recrystallize the product in ethanol to obtain a Boc aminophenyl quaternary ammonium salt compound.

8. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 7, characterized in that: In the step (1), the molar ratio of (4-hydroxyphenyl)carbamic acid tert-butyl ester, polyethylene glycol 400, epichlorohydrin and potassium hydroxide is 1:(0.045-0.05):(2.5-3.2):(2.5-3.2).

9. The method for preparing the amino-terminated quaternary ammonium salt polymer material according to claim 7, characterized in that: In the step (2), the molar ratio of Boc aminophenyl glycidyl ether, HCl, and N,N-dimethylalkylamine is 1:1:(0.9-1.1); the structural formula of N,N-dimethylalkylamine is Where n=8-16.

10. An application of an amino-terminated quaternary ammonium salt polymer material obtained by the preparation method according to any one of claims 1 to 9 in epoxy resin, characterized in that: The amount of the amino-terminated quaternary ammonium salt polymer material is 10-30% of the epoxy resin.

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