A flame retardant and antibacterial PETG material, preparation method and application thereof in pharmaceutical packaging

Abstract

The present application discloses a flame-retardant and antibacterial PETG material, a preparation method and its application in pharmaceutical packaging. The flame-retardant and antibacterial PETG material includes the following components: PETG, a new nitrogen silicon flame retardant M1, an antibacterial agent, and a silane coupling agent. Since the new nitrogen silicon flame retardant M1 prepared by the present application contains a large amount of organic silicon elements and organic nitrogen elements, and the silicon and nitrogen elements contained therein are covalently bonded and have a stable structure, under the action of the silane coupling agent, it can be effectively bonded with PETG, thereby significantly improving the flame retardant properties of the PETG material. In addition, in order to improve the antibacterial properties of the PETG material, the present application also adds an antibacterial agent, and finally prepares a PETG composite material with both flame retardant and antibacterial properties. Since the material has excellent mechanical properties, it can be used in fields such as pharmaceutical packaging.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite materials, and specifically relates to a flame-retardant and antibacterial PETG material, a preparation method and application in medical packaging. Background Art

[0002] PETG material has excellent processing and molding performance and can be designed into any shape according to the designer's intention; its excellent use characteristics fully meet the common requirements of processors and customers; at the same time, it has UV resistance, so it can be widely used in indoor and outdoor signs, point-of-sale displays, store shelves, outdoor installations, kiosks, industrial machine protection panels, game console panels, vending machine panels and many other fields.

[0003] In addition, due to the characteristics of high temperature resistance, chemical corrosion resistance and high transparency, PETG is very suitable for use in medical packaging and other fields. In the medical packaging industry, PETG can be used to make medical bottles, test tubes, infusion bags, etc. These packaging materials not only have excellent transparency, which is convenient for medical staff to observe the internal substances, but also their high temperature resistance and chemical corrosion resistance can effectively protect the efficacy and quality of drugs. With the improvement of people's awareness of product quality and environmental protection, the demand for PETG materials in the field of medical packaging continues to increase. Its excellent physical and chemical properties, as well as good processing properties, make PETG expected to become the preferred material in the field of medical packaging. However, due to its deficiencies in flame retardancy and antibacterial properties, its actual application scenarios are subject to certain restrictions. In order to improve the flame retardancy and antibacterial properties of PETG materials and further expand its scope of application, it is necessary to invent a flame retardant and antibacterial PETG material and its preparation method. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a flame retardant and antibacterial PETG material, a preparation method and application in medical packaging.

[0005] To achieve the above object, the present invention adopts the following technical solution:

[0006] On the one hand, the present application provides a flame retardant and antibacterial PETG material, characterized in that it comprises the following components in parts by weight:

[0007]

[0008] The structural formula of the novel nitrogen silicon flame retardant M1 is shown in formula (I):

[0009]

[0010] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 1-20 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts;

[0011] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 4-12 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts;

[0012] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 4-10 parts, the antibacterial agent is 1-2 parts, and the silane coupling agent is 4-6 parts;

[0013] Further, the antimicrobial agent includes one or more of a silver-containing compound and / or a zinc-containing compound;

[0014] Further, the silane coupling agent includes one or more of KH550, KH560, KH570, KH792, and DL602;

[0015] Further, the silver-containing compound includes one or more of silver thiocyanate, silver oxide, silver sulfate, silver chloride, silver bromide, silver iodide, C10-C20 fatty acid silver, C1-C4 alkylphenyl sulfonate silver, silver carbonate, silver sulfide, silver phosphoaniline, silver phosphate, silver hydroxide, silver hyaluronate, silver benzoate, silver tartrate, silver thiosulfate complex, silver laurate, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver gluconate, EDTA silver, silver laurate, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver iodate, silver oxalate, silver palmitate, silver perborate, silver stearate, silver succinate, silver thioglycolate, silver hydantoin complex, silver barbiturate, silver allantoate, silver salicylate, silver p-aminobenzoic acid, silver p-aminosalicylic acid, silver acetylsalicylate and silver gluconate;

[0016] Further, the zinc-containing compound includes one or more of zinc thiocyanate, zinc oxide, zinc sulfate, zinc chloride, zinc bromide, zinc iodide, C10-C20 fatty acid zinc, C1-C4 alkylphenyl sulfonate zinc, zinc carbonate, zinc sulfide, zinc phosphoanilide, zinc phosphate, zinc hydroxide, zinc hyaluronate, zinc benzoate, zinc tartrate, zinc thiosulfate complex, zinc laurate, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc gluconate, zinc EDTA, zinc laurate, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc iodate, zinc oxalate, zinc palmitate, zinc perborate, zinc stearate, zinc succinate, zinc thioglycolate, zinc hydantoin complex, zinc barbiturate, zinc allantoate, zinc salicylate, zinc p-aminobenzoate, zinc p-aminosalicylate, zinc acetylsalicylate and zinc gluconate;

[0017] Further, the zinc-containing compound includes one or more of silver myristate, silver hexadecanoate, silver stearate, silver oleate, silver palmitate and silver linoleate;

[0018] Furthermore, the silver-containing compound includes one or more of zinc myristate, zinc hexadecanoate, zinc stearate, zinc oleate, zinc palmitate and zinc linoleate.

[0019] On the other hand, the present application also provides a method for preparing a flame retardant and antibacterial PETG material, characterized in that it comprises the following steps:

[0020] Take PETG, new nitrogen silicon flame retardant M1, and antibacterial agent, disperse them evenly, then add silane coupling agent, mix them evenly and granulate them to obtain flame retardant and antibacterial PETG material;

[0021] The structural formula of the novel nitrogen silicon flame retardant M1 is shown in formula (I):

[0022]

[0023] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 1-20 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts;

[0024] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 4-12 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts;

[0025] Furthermore, the PETG is 100 parts, the novel nitrogen silicon flame retardant M1 is 4-10 parts, the antibacterial agent is 1-2 parts, and the silane coupling agent is 4-6 parts;

[0026] Further, the antimicrobial agent includes one or more of a silver-containing compound and / or a zinc-containing compound;

[0027] Further, the silane coupling agent includes one or more of KH550, KH560, KH570, KH792, and DL602;

[0028] Further, the antimicrobial agent includes one or more of a silver-containing compound and / or a zinc-containing compound;

[0029] Further, the silver-containing compound includes one or more of silver thiocyanate, silver oxide, silver sulfate, silver chloride, silver bromide, silver iodide, C10-C20 fatty acid silver, C1-C4 alkylphenyl sulfonate silver, silver carbonate, silver sulfide, silver phosphoaniline, silver phosphate, silver hydroxide, silver hyaluronate, silver benzoate, silver tartrate, silver thiosulfate complex, silver laurate, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver gluconate, EDTA silver, silver laurate, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver iodate, silver oxalate, silver palmitate, silver perborate, silver stearate, silver succinate, silver thioglycolate, silver hydantoin complex, silver barbiturate, silver allantoate, silver salicylate, silver p-aminobenzoic acid, silver p-aminosalicylic acid, silver acetylsalicylate and silver gluconate;

[0030] Further, the zinc-containing compound includes one or more of zinc thiocyanate, zinc oxide, zinc sulfate, zinc chloride, zinc bromide, zinc iodide, C10-C20 fatty acid zinc, C1-C4 alkylphenyl sulfonate zinc, zinc carbonate, zinc sulfide, zinc phosphoanilide, zinc phosphate, zinc hydroxide, zinc hyaluronate, zinc benzoate, zinc tartrate, zinc thiosulfate complex, zinc laurate, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc gluconate, zinc EDTA, zinc laurate, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc iodate, zinc oxalate, zinc palmitate, zinc perborate, zinc stearate, zinc succinate, zinc thioglycolate, zinc hydantoin complex, zinc barbiturate, zinc allantoate, zinc salicylate, zinc p-aminobenzoate, zinc p-aminosalicylate, zinc acetylsalicylate and zinc gluconate;

[0031] Further, the zinc-containing compound includes one or more of silver myristate, silver hexadecanoate, silver stearate, silver oleate, silver palmitate and silver linoleate;

[0032] Further, the silver-containing compound includes one or more of zinc myristate, zinc hexadecanoate, zinc stearate, zinc oleate, zinc palmitate and zinc linoleate;

[0033] Furthermore, the preparation method of the novel nitrogen silicon flame retardant M1 comprises the following steps:

[0034] Taking sodium melamine salt and adding it to a solvent, then adding 1,3,5-tris(dimethylchlorosilyl)benzene, reflux reaction, and purifying to obtain the novel nitrogen silicon flame retardant M1;

[0035] Further, the molar ratio of the melamine sodium salt to the 1,3,5-tris(dimethylchlorosilyl)benzene is 2-4:1;

[0036] Further, the molar ratio of the melamine sodium salt to the 1,3,5-tris(dimethylchlorosilyl)benzene is 3-4:1;

[0037] Furthermore, the reaction temperature of the reflux reaction is 60-200°C, and the reaction time is 4-12h;

[0038] Furthermore, the reaction temperature of the reflux reaction is 110-130°C, and the reaction time is 6-10h;

[0039] Further, the solvent includes at least one of 1,4-dioxane, acetonitrile, carbon tetrachloride, toluene, 1,2-dichloroethane, chlorobenzene, DMSO, DMF, and chloroform;

[0040] On the other hand, the present application also provides the use of the flame retardant and antibacterial PETG material in medical packaging.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The present application discloses a flame-retardant and antibacterial PETG material, a preparation method and its application in pharmaceutical packaging. The flame-retardant and antibacterial PETG material includes the following components: PETG, a new nitrogen silicon flame retardant M1, an antibacterial agent, and a silane coupling agent. Since the new nitrogen silicon flame retardant M1 prepared by the present application contains a large amount of organic silicon elements and organic nitrogen elements, and the silicon and nitrogen elements contained therein are covalently bonded and have a stable structure, under the action of the silane coupling agent, it can be effectively bonded with PETG, thereby significantly improving the flame retardant properties of the PETG material. In addition, in order to improve the antibacterial properties of the PETG material, the present application also adds an antibacterial agent, and finally prepares a PETG composite material with both flame retardant and antibacterial properties. Since the material also has excellent mechanical properties, it can be used in fields such as pharmaceutical packaging. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by technicians in the technical field of the present invention, and the terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. In the description of the present application, it should be understood that "and / or" describes the association relationship of associated objects, indicating that three relationships may exist, for example, A and / or B, which can represent: A exists alone, A and B exist at the same time, and B exists alone. Wherein A, B can be singular or plural. In the present application, "at least one" refers to one or more, and "multiple" refers to two or more. "At least one", "the following at least one (individual)" or similar expressions refer to any combination of these items, including any combination of single (individual) or plural (individual). For example, "at least one (individual) of a, b, or c", or "at least one (individual) of a, b, and c", can all represent: a, b, c, ab (i.e. a and b), ac, bc, or abc, wherein a, b, c can be single or multiple, respectively.

[0045] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and cannot be used as a limitation of the present application.

[0046] Example 1

[0047] This embodiment provides a novel nitrogen silicon flame retardant M1, which is prepared by the following steps:

[0048] At room temperature and under nitrogen protection, 500 mL of 1,4-dioxane and 0.70 mol of dried sodium melamine were added to a 1L four-necked flask equipped with a powerful mechanical stirrer, a spherical condenser and a thermometer. After stirring for 10 min, 0.2 mol of 1,3,5-tris(dimethylchlorosilyl)benzene was added to the reaction flask in batches within 30 min, the temperature was raised to 110°C, and the reaction was refluxed at a constant temperature for 8 h. After the temperature dropped to room temperature, the mixture was filtered under reduced pressure, and then washed with 500 mL of distilled water for 3 times. Finally, the mixture was placed in a vacuum drying oven and dried at 110°C for 24 h to obtain a white solid, which was the new nitrogen silicon flame retardant M1. The yield was 85.5%. Its nuclear magnetic resonance hydrogen spectrum data are as follows: 1 HNMR (400MHz, DMSO, δ / ppm): 7.42 (s, 3H), 7.02 (s, 12H), 4.82 (s, 3H), 0.89 (s, 18H).

[0049] The synthesis route of the new nitrogen silicon flame retardant M1 is as follows:

[0050]

[0051] Application Examples 1-4

[0052] Application Example 1-4 provides a flame retardant and antibacterial PETG material, which is prepared by the following steps:

[0053] PETG (polyethylene terephthalate-1,4-cyclohexane dimethanol ester), new nitrogen silicon flame retardant M1, silver stearate and zinc stearate were weighed and added into a high-speed mixer together, mixed at a speed of 400 rpm for 30 minutes, and after being evenly dispersed, silane coupling agent KH560 was added, and mixed at a speed of 400 rpm for 30 minutes. The mixed blend was extruded and granulated through a twin-screw extruder to obtain a flame-retardant and antibacterial PETG material.

[0054] The components of application examples 1-4 are shown in Table 1:

[0055] Table 1

[0056]

[0057] Comparative Example 1

[0058] Compared with Application Example 1, the only difference is that the new nitrogen silicon flame retardant M1 prepared in Example 1 is not added.

[0059] Comparative Example 2

[0060] Compared with Application Example 1, the only difference is that the silane coupling agent KH560 is not added.

[0061] Comparative Example 3

[0062] Compared with Application Example 1, the only difference is that silver stearate and zinc stearate are not added.

[0063] Flame retardant performance test:

[0064] (1) Oxygen index (LOI) test The oxygen index of the sample was tested according to the national standard GB / T 2406.2-2009, the determination method of the combustion performance of plastics. The average value of 5 samples after combustion was taken, which is the limit index of the flame retardant and antibacterial PETG material. The test results are shown in Table 2.

[0065] (2) Vertical burning grade test The vertical burning grade is a test method for the burning performance of plastics in accordance with the national standard GB / 2408-2008. The test results are shown in Table 2.

[0066] Mechanical properties test:

[0067] The tensile strength and elongation at break of the specimens were measured in accordance with the national standard GB / T 1040.2-2006 "Test Method for Tensile Properties of Plastics". The tensile speed was 50 mm / min. To ensure the accuracy of the experiment, 5 specimens were taken from each component and the average value method was used to process the data. The test results are shown in Table 2.

[0068] Antibacterial test:

[0069] The antibacterial performance test was carried out according to the GB15979-2002 standard film culture method, wherein the PETG flame retardant antibacterial film was obtained by a blow molding film making process. The test results are shown in Table 2 (the antibacterial rate in Table 2 refers to the antibacterial effect of the antibacterial film on Escherichia coli).

[0070] Table 2

[0071]

[0072]

[0073] Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for those skilled in the art, according to the idea of ​​the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application, and the scope of protection of the present invention shall be based on the scope defined by the claims. For those of ordinary skill in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be regarded as the scope of protection of the present invention. Those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A flame retardant and antibacterial PETG material, characterized in that: By weight, it includes the following components: PETG 100 parts; New nitrogen silicon flame retardant M1 0.1-20 parts; Antibacterial agent 0.1-4 parts; Silane coupling agent 1-10 parts; The structural formula of the novel nitrogen silicon flame retardant M1 is shown in formula (I): ； Formula (I).

2. The flame retardant and antibacterial PETG material according to claim 1, characterized in that: The PETG is 100 parts, the new nitrogen silicon flame retardant M1 is 1-20 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts; And / or, the silane coupling agent includes one or more of KH550, KH560, KH570, KH792, and DL602; And / or, the antimicrobial agent comprises one or more of a silver-containing compound and / or a zinc-containing compound.

3. The flame retardant and antibacterial PETG material according to claim 2, characterized in that: The silver-containing compound includes one or more of silver thiocyanate, silver oxide, silver sulfate, silver chloride, silver bromide, silver iodide, C10-C20 fatty acid silver, C1-C4 alkylphenyl sulfonate silver, silver carbonate, silver sulfide, silver phosphoanilide, silver phosphate, silver hydroxide, silver hyaluronate, silver benzoate, silver tartrate, silver thiosulfate complex, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver EDTA, silver iodate, silver oxalate, silver perborate, silver succinate, silver thioglycolate, silver hydantoin complex, silver barbiturate, silver allantoate, silver salicylate, silver p-aminobenzoic acid, silver p-aminosalicylic acid, silver acetylsalicylate and silver gluconate; And / or, the zinc-containing compound includes one or more of zinc thiocyanate, zinc oxide, zinc sulfate, zinc chloride, zinc bromide, zinc iodide, C10-C20 fatty acid zinc, C1-C4 alkylphenyl sulfonate zinc, zinc carbonate, zinc sulfide, zinc phosphanilide, zinc phosphate, zinc hydroxide, zinc hyaluronate, zinc benzoate, zinc tartrate, zinc thiosulfate complex, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc EDTA, zinc iodate, zinc oxalate, zinc perborate, zinc succinate, zinc thioglycolate, zinc hydantoin complex, zinc barbiturate, zinc allantoate, zinc salicylate, zinc p-aminobenzoate, zinc p-aminosalicylic acid, zinc acetylsalicylate and zinc gluconate.

4. The flame retardant and antibacterial PETG material according to claim 3, characterized in that: The silver-containing compound includes one or more of silver myristate, silver hexadecanoate, silver stearate, silver oleate, silver palmitate and silver linoleate; And / or, the zinc-containing compound includes one or more of zinc myristate, zinc hexadecanoate, zinc stearate, zinc oleate, zinc palmitate and zinc linoleate.

5. A method for preparing the flame retardant and antibacterial PETG material as claimed in claim 1, characterized in that: The steps include: Take PETG, new nitrogen silicon flame retardant M1, and antibacterial agent, disperse them evenly, then add silane coupling agent, mix them evenly and granulate them to obtain flame retardant and antibacterial PETG material; The structural formula of the novel nitrogen silicon flame retardant M1 is shown in formula (I): ； Formula (I).

6. The method for preparing the flame retardant and antibacterial PETG material according to claim 5, characterized in that: The PETG is 100 parts, the new nitrogen silicon flame retardant M1 is 1-20 parts, the antibacterial agent is 1-3 parts, and the silane coupling agent is 3-7 parts; And / or, the silane coupling agent includes one or more of KH550, KH560, KH570, KH792, and DL602; And / or, the antimicrobial agent comprises one or more of a silver-containing compound and / or a zinc-containing compound.

7. The method for preparing a flame retardant and antibacterial PETG material according to claim 6, wherein the silver-containing compound comprises silver thiocyanate, silver oxide, silver sulfate, silver chloride, silver bromide, silver iodide, C10-C20 fatty acid silver, C1-C4 alkylphenyl sulfonate silver, silver carbonate, silver sulfide, phosphoaniline silver, silver phosphate, silver hydroxide, silver hyaluronate, silver benzoate, silver tartrate, silver thiosulfate complex, silver zeolite, silver zirconium phosphate, silver alginate, silver ascorbate, silver folic acid, silver EDTA, silver iodate, silver oxalate, silver perborate, silver succinate, silver thioglycolate, silver hydantoin complex, silver barbiturate, silver allantoate, silver salicylate, silver p-aminobenzoic acid, silver p-aminosalicylic acid, silver acetylsalicylate and silver gluconate; And / or, the zinc-containing compound includes one or more of zinc thiocyanate, zinc oxide, zinc sulfate, zinc chloride, zinc bromide, zinc iodide, C10-C20 fatty acid zinc, C1-C4 alkylphenyl sulfonate zinc, zinc carbonate, zinc sulfide, zinc phosphanilide, zinc phosphate, zinc hydroxide, zinc hyaluronate, zinc benzoate, zinc tartrate, zinc thiosulfate complex, zinc zeolite, zinc zirconium phosphate, zinc alginate, zinc ascorbate, zinc folic acid, zinc EDTA, zinc iodate, zinc oxalate, zinc perborate, zinc succinate, zinc thioglycolate, zinc hydantoin complex, zinc barbiturate, zinc allantoate, zinc salicylate, zinc p-aminobenzoate, zinc p-aminosalicylic acid, zinc acetylsalicylate and zinc gluconate.

8. The method for preparing the flame retardant and antibacterial PETG material according to claim 5, characterized in that: The preparation method of the novel nitrogen silicon flame retardant M1 comprises the following steps: Melamine sodium salt is added to a solvent, and then 1,3,5-tris(dimethylchlorosilyl)benzene is added, refluxed and purified to obtain the novel nitrogen silicon flame retardant M1.

9. The method for preparing the flame retardant and antibacterial PETG material according to claim 8, characterized in that: The molar ratio of the melamine sodium salt to the 1,3,5-tris(dimethylchlorosilyl)benzene is 2-4:1; And / or, the reaction temperature of the reflux reaction is 60-200° C., and the reaction time is 4-12 h; And / or, the solvent includes at least one of 1,4-dioxane, acetonitrile, carbon tetrachloride, toluene, 1,2-dichloroethane, chlorobenzene, DMSO, DMF, and chloroform.

10. Use of the flame-retardant and antibacterial PETG material according to any one of claims 1 to 4 or the flame-retardant and antibacterial PETG material prepared by the preparation method according to any one of claims 5 to 9 in medical packaging.

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