Antibacterial material containing modified 3-aminofuran-2-methyl formate and preparation method thereof

Abstract

The invention relates to the technical field of materials, and discloses an antibacterial material containing modified 3-aminofuran-2-methyl formate and a preparation method thereof.The preparation method comprises the steps that modified 3-aminofuran-2-methyl formate, acrylic resin and talcum powder are extruded and granulated in a double-screw extruder, then granules are subjected to compression molding in a press vulcanizer, and the antibacterial material containing modified 3-aminofuran-2-methyl formate is obtained. The antibacterial material containing the modified 3-amino furan-2-methyl formate is obtained. Benzoxazine in the modified 3-aminofuran-2-methyl formate can form a heat-resistant phenolic resin structure at a high temperature, so that the modified 3-aminofuran-2-methyl formate has a relatively good flame-retardant effect; a three-dimensional network structure formed by boron-oxygen bonds contained in the flame retardant has high flame retardance of high oxygen index, low toxicity, low smoke and low calorific value; the carbon nano tube also has a relatively good flame-retardant effect; wherein the ferrocene group and the 3-aminofuran-2-methyl formate in the compound have a relatively good antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of materials, in particular to an antibacterial material containing modified 3-aminofuran-2-methyl carboxylate and a preparation method thereof. Background Art

[0002] 3-Aminofuran-2-carboxylic acid methyl ester is an organic compound with the chemical formula C6H7NO3. It is widely used in the fields of medicine and pesticides, especially in antibacterial properties, but its flame retardant effect has not been improved, which greatly limits its application in the field of materials.

[0003] Benzoxazine is a new type of thermosetting resin, which has attracted much attention due to its unique chemical structure and excellent performance. In terms of flame retardancy, benzoxazine itself has certain flame retardancy, and its application in the present invention improves its flame retardancy effect. Summary of the invention

[0004] 1. Technical issues to be solved

[0005] In view of the deficiencies of the prior art, the present invention provides an antibacterial material containing modified 3-aminofuran-2-methyl carboxylate and a preparation method thereof, which has good flame retardant and antibacterial effects.

[0006] (II) Technical solution

[0007] To achieve the above object, the present invention provides the following technical solution: an antibacterial material containing modified 3-aminofuran-2-methyl carboxylate, comprising the following components by weight: 4-8 parts by weight of modified 3-aminofuran-2-methyl carboxylate, 20-50 parts by weight of acrylic resin, and 2-3 parts by weight of talc.

[0008] Preferably, the preparation method of the modified benzoxazine is:

[0009] (1) adding 8-10 parts by weight of methyl 3-aminofuran-2-carboxylate, 16-25 parts by weight of an aqueous solution of formaldehyde, and 11-14 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75-95° C., and after completion, distilling under reduced pressure, washing with deionized water, and drying to obtain an olefinated benzoxazine;

[0010] (2) Add 1.6-3.4 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 85-110° C. for 6-10 h, dry after completion, continue to add 2.4-3.1 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01-0.03 g of triethylamine, and place in an oil bath at 50-70° C. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane;

[0011] (3) adding 0.2-0.4 parts by weight of an emulsifier sodium dodecyl sulfate and 2-4 parts by weight of vinyl carbon nanotubes to deionized water, and after uniform dispersion, adding 5-10 parts by weight of olefinic polyurethane, 4-8 parts by weight of acryl alcohol, 3-5 parts by weight of dimethyldiallylammonium chloride and 5-6 parts by weight of olefinic benzoxazine, stirring evenly, and then dropping 0.02-0.04 parts by weight of an initiator in a nitrogen atmosphere, reacting at 50-80° C. for 3-5 hours, filtering the solvent after the reaction, washing with deionized water and ethanol in turn and drying to obtain an intermediate 1;

[0012] (4) Add ferrocenylboric acid to toluene solvent, stir and disperse, then add N-methyl-2-hydroxyethylamine, react at 90-115° C. for 10-12 h, react for 20-40 min, distill under reduced pressure, filter and dry to obtain intermediate 2;

[0013] (5) Add chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, react at 50-75° C. for 3-5 hours, and then distill under reduced pressure and wash to obtain modified 3-aminofuran-2-carboxylic acid methyl ester.

[0014] Preferably, the reaction time in (1) is 4-7 hours.

[0015] Preferably, the oil bath time in (2) is 8-12 hours.

[0016] Preferably, the initiator in (3) is azobisisobutyronitrile.

[0017] Preferably, the mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine in (4) is 1:1.3-1.6.

[0018] Preferably, the mass ratio of chloroacetyl chloride, intermediate 1, and intermediate 2 in (5) is 1:0.8-1.2:1.1-1.3.

[0019] Preferably, the preparation method of the antibacterial material containing modified 3-aminofuran-2-methyl carboxylate is: modified 3-aminofuran-2-methyl carboxylate, acrylic resin, and talcum powder are extruded and granulated at 180-195° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at 185-190° C. under a pressure of 8-9 MPa to obtain the antibacterial material containing modified 3-aminofuran-2-methyl carboxylate.

[0020] (III) Beneficial technical effects

[0021] The invention obtains an antibacterial material containing modified 3-aminofuran-2-methyl carboxylate by extruding modified 3-aminofuran-2-methyl carboxylate, acrylic resin and talcum powder in a twin-screw extruder to form granules, and then molding the granules in a flat vulcanizer.

[0022] The benzoxazine in the modified 3-aminofuran-2-carboxylic acid methyl ester will form a heat-resistant phenolic resin structure at high temperature, making it have a good flame retardant effect; the three-dimensional network structure formed by the boron oxygen bonds contained therein has high flame retardancy with high oxygen index, low toxicity, low smoke and low calorific value; the carbon nanotubes therein also have a good flame retardant effect; the ferrocene group and 3-aminofuran-2-carboxylic acid methyl ester therein both have good antibacterial effects. DETAILED DESCRIPTION

[0023] Example 1

[0024] (1) adding 8 parts by weight of methyl 3-aminofuran-2-carboxylate, 16 parts by weight of an aqueous solution of formaldehyde, and 11 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75° C. for 4 hours. After the reaction, the mixture is distilled under reduced pressure, washed with deionized water, and dried to obtain an olefinated benzoxazine;

[0025] (2) Add 1.6 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 85° C. for 6-10 h, dry after completion, continue to add 2.4 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01 g of triethylamine, and place in an oil bath at 50° C. for 8 h. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane;

[0026] (3) Add 0.2 parts by weight of an emulsifier, sodium dodecyl sulfate, and 2 parts by weight of vinyl carbon nanotubes to deionized water, and after uniform dispersion, add 5 parts by weight of olefinic polyurethane, 4 parts by weight of acryl alcohol, 3 parts by weight of dimethyldiallylammonium chloride, and 5 parts by weight of olefinic benzoxazine, and after uniform stirring, add 0.02 parts by weight of azobisisobutyronitrile initiator dropwise in a nitrogen atmosphere, and react at 50° C. for 3 h. After the reaction, filter the solvent, wash with deionized water and ethanol in turn, and dry to obtain an intermediate 1;

[0027] (4) adding ferrocenylboric acid to toluene solvent, stirring and dispersing, and then adding N-methyl-2-hydroxyethylamine thereto, wherein the mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine is 1:1.3, reacting at 90° C. for 10 h, reacting for 20 min, distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0028] (5) adding chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of chloroacetyl chloride, intermediate 1 and intermediate 2 is 1:0.8:1.1, reacting at 50° C. for 3 h, and then distilling under reduced pressure and washing to obtain modified 3-aminofuran-2-carboxylic acid methyl ester;

[0029] (6) 4 parts by weight of modified 3-aminofuran-2-carboxylic acid methyl ester, 20 parts by weight of acrylic resin, and 2 parts by weight of talc are extruded and granulated at 180° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 8 MPa and at 185° C. to obtain an antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester.

[0030] Example 2

[0031] (1) adding 10 parts by weight of methyl 3-aminofuran-2-carboxylate, 25 parts by weight of an aqueous solution of formaldehyde, and 14 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 95° C. for 7 hours. After the reaction, the reaction is carried out under reduced pressure distillation, washed with deionized water, and dried to obtain an olefinated benzoxazine;

[0032] (2) Add 3.4 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 110° C. for 10 h, dry after completion, continue to add 3.1 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.03 g of triethylamine, and place in an oil bath at 70° C. for 12 h. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane;

[0033] (3) 0.4 parts by weight of an emulsifier, sodium dodecyl sulfate, and 4 parts by weight of vinyl carbon nanotubes were added to deionized water, and after being evenly dispersed, 10 parts by weight of olefinic polyurethane, 8 parts by weight of acryl alcohol, 5 parts by weight of dimethyldiallylammonium chloride, and 6 parts by weight of olefinic benzoxazine were added, and after being evenly stirred, 0.04 parts by weight of azobisisobutyronitrile initiator was added dropwise in a nitrogen atmosphere, and the reaction was carried out at 80° C. for 5 h. After the reaction was completed, the solvent was filtered, and the mixture was washed with deionized water and ethanol in sequence and dried to obtain an intermediate 1;

[0034] (4) adding ferrocenylboric acid to toluene solvent, stirring and dispersing, and then adding N-methyl-2-hydroxyethylamine thereto, wherein the mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine is 1:1.6, reacting at 115° C. for 12 h, reacting for 40 min, distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0035] (5) adding chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of chloroacetyl chloride, intermediate 1 and intermediate 2 is 1:1.2:1.3, reacting at 75° C. for 5 h, and then distilling under reduced pressure and washing to obtain modified 3-aminofuran-2-carboxylic acid methyl ester;

[0036] (6) 8 parts by weight of modified 3-aminofuran-2-carboxylic acid methyl ester, 50 parts by weight of acrylic resin, and 3 parts by weight of talc are extruded and granulated at 195° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 9 MPa and 190° C. to obtain an antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester.

[0037] Example 3

[0038] (1) adding 9 parts by weight of methyl 3-aminofuran-2-carboxylate, 20 parts by weight of an aqueous solution of formaldehyde, and 12 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 85° C. for 6 seconds. After the reaction, the reaction is carried out by vacuum distillation, washing with deionized water, and drying to obtain an olefinated benzoxazine;

[0039] (2) Add 2.4 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 100° C. for 8 h, dry after completion, continue to add 2.6 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.02 g of triethylamine, and place in an oil bath at 60° C. for 10 h. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane;

[0040] (3) Add 0.3 parts by weight of an emulsifier, sodium dodecyl sulfate, and 3 parts by weight of vinyl carbon nanotubes to deionized water, and after uniform dispersion, add 8 parts by weight of olefinic polyurethane, 6 parts by weight of acryl alcohol, 4 parts by weight of dimethyldiallylammonium chloride, and 5 parts by weight of olefinic benzoxazine, and after uniform stirring, add 0.03 parts by weight of azobisisobutyronitrile initiator dropwise in a nitrogen atmosphere, and react at 65° C. for 4 hours. After the reaction, filter the solvent, wash with deionized water and ethanol in turn, and dry to obtain an intermediate 1;

[0041] (4) adding ferrocenylboric acid to toluene solvent, stirring and dispersing, and then adding N-methyl-2-hydroxyethylamine thereto, wherein the mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine is 1:1.5, reacting at 110° C. for 11 h, reacting for 30 min, distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0042] (5) adding chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of chloroacetyl chloride, intermediate 1 and intermediate 2 is 1:0.9:1.2, reacting at 65° C. for 4 h, and then distilling under reduced pressure and washing to obtain modified 3-aminofuran-2-carboxylic acid methyl ester;

[0043] (6) 6 parts by weight of modified 3-aminofuran-2-carboxylic acid methyl ester, 30 parts by weight of acrylic resin, and 2 parts by weight of talc are extruded and granulated at 180° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 9 MPa and 185° C. to obtain an antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester.

[0044] Example 4

[0045] (1) adding 8 parts by weight of methyl 3-aminofuran-2-carboxylate, 16 parts by weight of an aqueous solution of formaldehyde, and 11 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75° C. for 4 hours. After the reaction, the mixture is distilled under reduced pressure, washed with deionized water, and dried to obtain an olefinated benzoxazine;

[0046] (2) Add 1.6 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 85° C. for 6-10 h, dry after completion, continue to add 2.4 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01 g of triethylamine, and place in an oil bath at 50° C. for 8 h. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane;

[0047] (3) 0.4 parts by weight of an emulsifier, sodium dodecyl sulfate, and 4 parts by weight of vinyl carbon nanotubes were added to deionized water, and after being evenly dispersed, 10 parts by weight of olefinic polyurethane, 8 parts by weight of acryl alcohol, 5 parts by weight of dimethyldiallylammonium chloride, and 6 parts by weight of olefinic benzoxazine were added, and after being evenly stirred, 0.04 parts by weight of azobisisobutyronitrile initiator was added dropwise in a nitrogen atmosphere, and the reaction was carried out at 80° C. for 5 h. After the reaction was completed, the solvent was filtered, and the mixture was washed with deionized water and ethanol in sequence and dried to obtain an intermediate 1;

[0048] (4) adding ferrocenylboric acid to toluene solvent, stirring and dispersing, and then adding N-methyl-2-hydroxyethylamine thereto, wherein the mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine is 1:1.6, reacting at 115° C. for 12 h, reacting for 40 min, distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0049] (5) adding chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of chloroacetyl chloride, intermediate 1 and intermediate 2 is 1:0.9:1.2, reacting at 65° C. for 4 h, and then distilling under reduced pressure and washing to obtain modified 3-aminofuran-2-carboxylic acid methyl ester;

[0050] (6) 6 parts by weight of modified 3-aminofuran-2-carboxylic acid methyl ester, 30 parts by weight of acrylic resin, and 2 parts by weight of talc are extruded and granulated at 180° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 9 MPa and 185° C. to obtain an antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester.

[0051] Comparative Example 1

[0052] Compared with Example 4, this comparative example differs in that no modified 3-aminofuran-2-carboxylic acid methyl ester is added.

[0053] A Staphylococcus aureus liquid with a concentration of 2×108 CFU / mL was added to a sterilized culture dish as a test strain, and then a solid agar medium was added and dissolved, cooled to 45°C, and then poured into the culture dish, 20 mL was poured into each plate with an inner diameter of 10 cm, and then the materials of the embodiments of the present invention and the comparative example (with a diameter of 3 cm and a thickness of 1 mm) were placed on the culture plate, and cultured in a constant temperature incubator for 12 hours at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.

[0054] Table 1: Antimicrobial testing.

[0055] project Diameter of inhibition zone (mm) Example 1 15.1 Example 2 16.3 Example 3 16.2 Example 4 16.3 Comparative Example 1 11.4

[0056] It can be seen from Table 1 that Examples 1-4 of the present invention have better antibacterial effects than Comparative Example 1.

[0057] Use an oxygen index meter to test the limiting oxygen index of the material; use a horizontal and vertical combustion instrument to test the combustion level of the material.

[0058] Table 2: Flame retardancy test.

[0059]

[0060]

[0061] It can be seen from Table 2 that Examples 1-4 have better flame retardant effects than Comparative Example 1.

[0062] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial material containing modified 3-aminofuran-2-methyl carboxylate, characterized in that: The invention comprises the following components by weight: 4-8 parts by weight of modified 3-aminofuran-2-methyl carboxylate, 20-50 parts by weight of acrylic resin and 2-3 parts by weight of talc.

2. The antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester according to claim 1, characterized in that: The preparation method of the modified benzoxazine is: (1) adding 8-10 parts by weight of methyl 3-aminofuran-2-carboxylate, 16-25 parts by weight of an aqueous solution of formaldehyde, and 11-14 parts by weight of magnolol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75-95° C., and after completion, distilling under reduced pressure, washing with deionized water, and drying to obtain an olefinated benzoxazine; (2) Add 1.6-3.4 g of purified polyurethane particles to N,N-dimethylformamide solvent, stir and dissolve at 85-110° C. for 6-10 h, dry after completion, continue to add 2.4-3.1 g of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01-0.03 g of triethylamine, and place in an oil bath at 50-70° C. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane; (3) adding 0.2-0.4 parts by weight of an emulsifier sodium dodecyl sulfate and 2-4 parts by weight of vinyl carbon nanotubes to deionized water, and after uniform dispersion, adding 5-10 parts by weight of olefinic polyurethane, 4-8 parts by weight of acryl alcohol, 3-5 parts by weight of dimethyldiallylammonium chloride and 5-6 parts by weight of olefinic benzoxazine, stirring evenly, and then dropping 0.02-0.04 parts by weight of an initiator in a nitrogen atmosphere, reacting at 50-80° C. for 3-5 hours, filtering the solvent after the reaction, washing with deionized water and ethanol in turn and drying to obtain an intermediate 1; (4) Add ferrocenylboric acid to toluene solvent, stir and disperse, then add N-methyl-2-hydroxyethylamine, react at 90-115° C. for 10-12 h, react for 20-40 min, distill under reduced pressure, filter and dry to obtain intermediate 2; (5) Add chloroacetyl chloride, intermediate 1 and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, react at 50-75° C. for 3-5 hours, and then distill under reduced pressure and wash to obtain modified 3-aminofuran-2-carboxylic acid methyl ester.

3. The antibacterial material containing modified 3-aminofuran-2-methyl carboxylate according to claim 2, characterized in that: The reaction time in (1) is 4-7h.

4. The antibacterial material containing modified 3-aminofuran-2-methyl carboxylate according to claim 2, characterized in that: The oil bath time in (2) is 8-12 hours.

5. The antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester according to claim 2, characterized in that: The initiator in (3) is azobisisobutyronitrile.

6. The antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester according to claim 2, characterized in that: The mass ratio of ferrocenylboric acid to N-methyl-2-hydroxyethylamine in (4) is 1:1.3-1.

6.

7. The antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester according to claim 2, characterized in that: The mass ratio of chloroacetyl chloride, intermediate 1 and intermediate 2 in (5) is 1:0.8-1.2:1.1-1.

3.

8. A method for preparing an antibacterial material containing modified 3-aminofuran-2-carboxylic acid methyl ester according to any one of claims 1 to 7, characterized in that: The preparation method of the antibacterial material containing modified 3-aminofuran-2-methyl carboxylate comprises the following steps: extruding and granulating the modified 3-aminofuran-2-methyl carboxylate, acrylic resin and talcum powder in a twin-screw extruder at 180-195° C., and then compression molding the granules in a flat vulcanizer at 185-190° C. under a pressure of 8-9 MPa to obtain the antibacterial material containing modified 3-aminofuran-2-methyl carboxylate.

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