PET antibacterial material as well as preparation method and application thereof

Abstract

The invention provides a PET antibacterial material as well as a preparation method and application thereof. The PET antibacterial material at least comprises polyethylene glycol terephthalate and an antibacterial agent; the addition amount of the antibacterial agent is 0.5 to 1.5 wt%; by adopting the technical scheme, the PET antibacterial material provided by the invention has excellent antibacterial performance, and particularly, the added antibacterial agent contains a benzene ring or furan ring structure and can form a pi-pi conjugation effect with a benzene ring in PET, so that the antibacterial agent can be better combined with a PET matrix material, and the antibacterial performance of the PET antibacterial material is improved. The PET antibacterial material is not easy to fall off from a matrix material, so that the antibacterial aging of the PET antibacterial material is prolonged; on the other hand, the water solubility of the antibacterial agent is poor, the antibacterial agent can be repeatedly used when being used as a container, the antibacterial activity of the antibacterial agent can still be kept, and therefore the use field of the PET antibacterial material is expanded.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial polyester materials, and in particular to a PET antibacterial material and a preparation method and application thereof. Background Art

[0002] Polyethylene terephthalate (PET) is a thermoplastic resin, which is obtained by the dehydration condensation reaction of ethylene terephthalate. It is a milky white or light yellow, highly crystalline polymer. PET material has good mechanical properties, and its impact strength is 3 to 5 times that of other plastic products. It also has good corrosion resistance, especially acid and alkali resistance and most solvent resistance. Moreover, PET material also has excellent high and low temperature resistance, and can be used for a long time in the temperature range of -70℃ to 120℃, and the influence of high or low temperature conditions on its mechanical properties is very small. At the same time, due to its high transparency, UV blocking and good gloss, it is used in the technical fields such as film. When PET is used as a food-grade packaging material, it is generally necessary to add an antibacterial agent to give it a certain antibacterial property. The addition of antibacterial agents enables the PET material to inhibit or kill bacteria, molds and even viruses on its surface in the use environment, and keep the surface of the material clean by inhibiting the reproduction of microorganisms.

[0003] Antibacterial plastic refers to a plastic that has one or more specific antibacterial agents added to it, making it inherently antibacterial. It is a new type of material with antibacterial and bactericidal properties, which can kill or inhibit the reproduction of bacteria on the surface of plastics and their products within a certain period of time. However, the antibacterial agents commonly used in the prior art generally have poor compatibility with PET, which makes them very easy to fall out during use; moreover, antibacterial agents generally have extremely high water solubility. When PET antibacterial materials need to be frequently washed with water or acted on high temperature and humid conditions, the antibacterial agents are easily dissolved in water or decomposed, causing the antibacterial properties of PET to decay rapidly and causing the material to lose its antibacterial properties.

[0004] On the other hand, the requirements for safety performance of antimicrobial agents that can be selected for food-grade materials are becoming increasingly higher. For example, after triclosan, triclocarban, benzethonium chloride and chloroxylenol were banned due to safety issues, polyhexamethyleneguanidine hydrochloride (PHMG) with safety and environmental advantages has been widely used as an antimicrobial agent, especially in the fields of medicine, plant protection and daily necessities. However, due to the high water solubility of polyhexamethyleneguanidine hydrochloride (PHMG) and inorganic antimicrobial agents, their use in antimicrobial plastics, textiles and other products has been greatly restricted. When PHMG is directly added to PET and mixed with PET to give PET antimicrobial properties to prepare antimicrobial materials and applied to food packaging materials, the antimicrobial properties rapidly decrease due to frequent use of water for washing, and the antimicrobial time is greatly shortened. The main reason is that frequent contact with water causes the antimicrobial agent to dissolve rapidly and then hydrolyze the antimicrobial agent.

[0005] Therefore, how to provide a long-lasting PET antibacterial material for PET packaging products, especially food-grade packaging, has become a technical problem that urgently needs to be solved in the prior art. Summary of the invention

[0006] In order to overcome the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a PET antibacterial material and a preparation method and application thereof, so as to overcome the deficiencies of the prior art such as the short antibacterial effect of the product due to its high water solubility and the limited use thereof, and the production method is simple, the cost is low, and the application forms are flexible and diverse.

[0007] To achieve the above objectives, the present invention provides the following technical solutions.

[0008] One aspect of the present invention provides an antibacterial polyethylene terephthalate material, comprising at least polyethylene terephthalate and an antibacterial agent; the antibacterial agent is added in an amount of 0.5 to 1.5 wt % of the base material; the antibacterial agent is a diguanidine carboxylate containing a benzene ring or a furan ring, and the structural formula is shown in formula (I):

[0009]

[0010] Wherein, n is an integer of 40-60, R is a residue of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodicyclohexylmethane, etc., and X is a benzene ring or a furan ring.

[0011] In some preferred embodiments, the antimicrobial polyethylene terephthalate material may further include an antioxidant and / or an acid scavenger.

[0012] Preferably, the added amount of the antioxidant is 0.1-0.3wt% of the base material; the added amount of the acid scavenger is 0.01-0.05wt% of the base material.

[0013] Preferably, the antioxidant includes any one or more combinations of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[triethylene glycol tert-butyl-4-hydroxy-5-methylphenyl)propionate], N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid.

[0014] Preferably, the acid scavenger comprises any one or more combinations of zinc stearate, calcium stearate and hydrotalcite.

[0015] Another aspect of the present invention also provides a method for preparing the PET antibacterial, comprising mixing polyethylene terephthalate and the antibacterial agent and then melt-extruding the mixture. More specifically, the PET antibacterial comprises mixing polyethylene terephthalate, the antibacterial agent, the antioxidant and the acid scavenger and then melt-extruding the mixture.

[0016] Preferably, the method for preparing the PET antibacterial material comprises the following steps:

[0017] S1. Providing the antimicrobial agent;

[0018] S2. It includes at least adding the antibacterial agent and polyethylene terephthalate into a high temperature mixture and mixing them evenly, and then using a twin-screw extruder to melt extrude and then injection mold to prepare the PET antibacterial agent at 240N280℃.

[0019] Preferably, the preparation steps of the antibacterial agent include:

[0020] (1) heating guanidine hydrochloride and diamine until they are completely dissolved and then fully mixed, and heating treatment is performed under an inert gas atmosphere to allow guanidine hydrochloride and diamine to react to obtain an antibacterial agent intermediate as shown in formula (II);

[0021]

[0022] wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4′-diaminodicyclohexylmethane;

[0023] (2) dissolving the antibacterial agent intermediate and sodium salt obtained in step (1) in a water / alcohol mixed system, stirring and reacting under an inert gas atmosphere to obtain the antibacterial agent.

[0024] Preferably, the heating treatment in step (1) adopts a staged heating method; the staged heating method includes a first stage, a second stage, and a third stage, the heating temperature is increased sequentially, and each stage is heated to the reaction temperature and then subjected to insulation treatment; the first stage includes raising the temperature to 130-140°C and keeping it warm for 0.5-1.5h; the second stage includes raising the temperature to 150N160°C and keeping it warm for 0.5-1.5h; the third stage includes raising the temperature to 170-180°C, vacuuming to remove the ammonia produced by the reaction, and keeping it warm for 0.5h.

[0025] Preferably, the diamine includes at least one of hexamethylenediamine, p-phenylenediamine, m-phenylenediamine and 4,4′-diaminodicyclohexylmethane.

[0026] Preferably, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:1.

[0027] Preferably, the sodium salt comprises sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate or sodium adipic acid.

[0028] Preferably, the molar ratio of the antibacterial agent intermediate to the sodium salt is 1:0.1 to 1:1.

[0029] Preferably, the temperature for reacting the antibacterial agent intermediate with the sodium salt ranges from room temperature to 60°C.

[0030] Preferably, the reaction solvent of the antibacterial agent intermediate and the sodium salt is water / ethanol, water / isopropanol, water / glycerol, water / n-butanol, or water / isobutanol.

[0031] As one aspect of the present invention, a PET antibacterial film is also provided, which is prepared using the above-mentioned PET antibacterial material; the preparation method comprises: injecting all raw materials including at least polyethylene terephthalate and an antibacterial agent into a twin-screw extruder, melt-extruded into a sheet, and then stretching and shaping to obtain the PET antibacterial film; the extrusion temperature is 240-280°C.

[0032] As one aspect of the present invention, an antibacterial plastic container is also provided, which comprises at least mixing all raw materials for preparing the above-mentioned PET antibacterial material uniformly, and then melt-extruding at 240-280°C and then injection molding by an injection molding machine to obtain the antibacterial plastic container.

[0033] The technical effects of the technical solution of the present invention are as follows:

[0034] 1. By adopting the technical solution of the present invention, the provided PET antibacterial material has excellent antibacterial properties. In particular, the added antibacterial agent contains a benzene ring or a furan ring structure, which can form a π-π conjugated effect with the benzene ring in PET, so that the antibacterial agent can be better combined with the PET matrix material, and is not easy to escape from the matrix material, thereby extending the antibacterial time of the PET antibacterial material; on the other hand, the water solubility of the antibacterial agent itself is poor, and when used as a container, it can be used repeatedly, and the antibacterial agent can still maintain antibacterial activity, thereby expanding the use field of PET antibacterial materials.

[0035] 2. The antibacterial agent has good thermal stability and will not decompose due to heat during the injection molding process with PET resin, which can meet the product's requirements for long-term antibacterial performance of the antibacterial agent; in particular, the antibacterial PET material can maintain more than 90% of its antibacterial performance after being boiled in water at 100°C for two hours, expanding the use scenarios of PET materials.

[0036] 3. The PET antibacterial material provided by the technical solution of the present invention, wherein the antibacterial agent is an organic salt, has the characteristics of being non-toxic and safe, so that it can be used as an antibacterial packaging material in the fields of food packaging, medical materials, etc.

[0037] 4. The PET antibacterial material provided by the technical solution of the present invention has broad-spectrum antibacterial properties, high antibacterial efficiency, good mechanical properties, safety and reliability, no odor, low harm and pollution to the human body and the environment, and long-term antibacterial properties. Its effective antibacterial time is basically the same as the service life of the antibacterial material. DETAILED DESCRIPTION

[0038] To make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the protection scope of the present invention.

[0039] The disclosures of all patent and non-patent literature cited herein are incorporated herein by reference in their entirety.

[0040] As used in the invention, the terms "comprises," "includes," "contains," "covers," "has," "with," or any other variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, article, or apparatus that includes a list of elements need not be limited to only those elements, but may include other elements that are not explicitly listed or that are inherent to the process, method, article, or apparatus. In addition, unless expressly indicated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or." For example, conditions A or B satisfy any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). The phrase "one or more" is intended to cover non-exclusive inclusions. For example, one or more of A, B, and C, means any of the following: A alone, B alone, C alone, a combination of A and B, a combination of B and C, a combination of A and C, or a combination of A, B, and C.

[0041] In addition, "a" or "an" is used to describe the elements and components described herein. This is done only for convenience and to provide a general sense of the scope of the invention. This description should be understood to include one or at least one, one or at least one, and the singular also includes the plural, unless it is obvious that it is intended otherwise.

[0042] Some embodiments of the present invention provide a PET antibacterial material, which at least includes polyethylene terephthalate and an antibacterial agent; the added amount of the antibacterial agent is 0.5-1.5wt% based on the polyethylene terephthalate.

[0043] The structural formula of the antibacterial agent is shown in formula (I): Wherein, n is an integer of 40-60, R is a residue of hexamethylenediamine, meta-phenylenediamine, para-phenylenediamine, 4,4′-diaminodicyclohexylmethane, etc., and X includes a benzene ring or a furan ring.

[0044] Some embodiments of the present invention provide a method for preparing antibacterial PET, comprising the following steps:

[0045] S1. Provide antimicrobial intermediates;

[0046] After the guanidine hydrochloride and the diamine are heated until they are completely dissolved and fully mixed, they are heated in an inert gas atmosphere to react with the guanidine hydrochloride and the diamine to obtain an antibacterial agent intermediate as shown in formula (II);

[0047]

[0048] wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4′-diaminodicyclohexylmethane;

[0049] S2. Provide antimicrobial agent

[0050] The antibacterial agent intermediate and the sodium salt are dissolved in a water / alcohol mixed system, stirred and reacted at room temperature to 60° C. to obtain an antibacterial agent; the antibacterial agent includes a compound represented by formula (I):

[0051]

[0052] Wherein, n is an integer of 40-60, R is a residue of any one of hexylene diamine, m-phenylenediamine, p-phenylenediamine or 4,4′-diaminodicyclohexylmethane, and X is a benzene ring or a furan ring.

[0053] S3. Provide PET antibacterial materials;

[0054] The method comprises at least adding an antibacterial agent, an antioxidant, an acid scavenger and polyethylene terephthalate into a high-speed mixer and mixing them evenly, and then adopting a twin-screw extruder to melt-extrude and then injection-mold to prepare the PET antibacterial agent at 240-280 DEG C.

[0055] In some embodiments, in S1, the heating treatment adopts a staged heating method; the staged heating method includes a first stage-a second stage-a third stage, the heating temperature increases sequentially, and each stage is heated to the reaction temperature and then subjected to insulation treatment.

[0056] More specifically, the first stage includes raising the temperature to 130-140°C and keeping it warm for 0.5-1.5 hours; the second stage includes raising the temperature to 150-160°C and keeping it warm for 0.5-1.5 hours; the third stage includes raising the temperature to 170-180°C, vacuuming to remove the ammonia that should be produced, and keeping it warm for 0.5 hours.

[0057] In some embodiments, the diamine includes at least one of hexamethylenediamine, p-xylylenediamine, m-xylylenediamine, and 4,4′-diaminodicyclohexylmethane.

[0058] In some embodiments, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:1.

[0059] In some embodiments, the sodium salt comprises sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate, or sodium adipate.

[0060] In other embodiments, the molar ratio of the antibacterial agent intermediate to the sodium salt is 1:0.2 to 1:2.

[0061] In other embodiments, the reaction of guanidine hydrochloride and diamine, and the reaction of the antibacterial agent intermediate and the sodium salt are both carried out under the protection of an inert gas.

[0062] In some embodiments, the antibacterial agent provided by the above technical solution can be uniformly mixed with a thermoplastic plastic, and then melt-extruded at 240-280° C. and injection molded to prepare the antibacterial material.

[0063] In some specific embodiments, the antibacterial agent prepared by the technical solution of the present invention is added to polyolefin to obtain a polyolefin material product with antibacterial function, which is prepared by twin-screw melt extrusion and injection molding, and the processing temperature is between 240 and 280°C.

[0064] In some embodiments, the antibacterial agent prepared by the technical solution of the present invention is added to PET to obtain a polyester material product with antibacterial function, which is produced by twin-screw melt extrusion and injection molding, and the processing temperature is between 240 and 280°C.

[0065] In the process of co-processing with polyethylene terephthalate and antimicrobial agents, processing aids and modifiers conventional in the art, such as plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, fillers, etc., are also used.

[0066] Specifically, the plasticizer includes, but is not limited to, one or more mixtures of dioctyl phthalate, didecyl phthalate, liquid paraffin, wax, dimethyl phthalate, diethyl phthalate, phosphate ester, and the like.

[0067] And / or, the flame retardant includes, but is not limited to, one or more mixtures of bis(hexachlorocyclopentadiene), cyclooctane, ammonium polyphosphate, decabromodiphenyl ether, bis(hydroxyethyl)methylphosphine oxide, cyanuric acid, melamine, and the like.

[0068] And / or, the lubricant includes, but is not limited to, one or more mixtures of vinyl bisstearamide, butyl stearate, and the like.

[0069] And / or, the UV absorber includes, but is not limited to, one or more mixtures of 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, ethylene-2-cyano-3,3-diphenylacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, and the like.

[0070] And / or, the antioxidant includes but is not limited to: one or more mixtures of 4-hydroxymethyl-2,6-di-tert-butylphenol, 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate, 1,1-thiobis-(2-naphthol), 4,4-butylene-bis(6-tert-butyl-m-cresol), 2,2-thiobis-(4-methyl-6-tert-butylphenol), etc.

[0071] And / or, the filler includes, but is not limited to, one or more mixtures of glass fiber, asbestos, wollastonite, calcium silicate, talc, montmorillonite, etc.

[0072] Some embodiments of the present invention also provide a PET antibacterial film, wherein at least all raw materials including polyethylene terephthalate and an antibacterial agent are injected into a twin-screw extruder, melt-extruded into a sheet, and then stretched and shaped to obtain the PET antibacterial film; the extrusion temperature is 220 to 260°C.

[0073] Some embodiments of the present invention also provide a method for producing an antibacterial plastic container, which comprises: uniformly mixing all raw materials of the antibacterial polyolefin, and then forming the antibacterial plastic container by injection molding at 240-280° C. by an injection molding machine. The container can be various regular or irregular shapes such as bottles, bowls, basins, plates, boards, barrels, troughs, etc., but is not limited thereto.

[0074] Unless otherwise defined, the meaning of all technical and scientific terms used herein is the same as that generally understood by those of ordinary skill in the art to which the present disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. Unless citing a specific paragraph, all publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety. If a conflict occurs, this specification and the definitions included therein shall prevail. In addition, materials, methods and examples are illustrative only, and not restrictive.

[0075] The technical scheme of the present invention, its implementation process and principle, etc. will be further explained through specific embodiments as follows. It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. The described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. Unless otherwise specified, the reagents and raw materials used in the following examples are commercially available, and the test methods for which specific conditions are not specified are usually carried out under conventional conditions or according to the conditions recommended by the manufacturers. In addition, unless otherwise specified, the experimental methods, detection methods, and preparation methods disclosed in the present invention all adopt conventional techniques in the art. These technologies have been fully described in the existing literature.

[0076] The test items, standards or methods involved in the embodiments and / or comparative examples are as follows:

[0077] 1. Molecular weight test

[0078] The number average molecular weight and weight average molecular weight of the product were determined using a GPC column.

[0079] Specifically, the size exclusion chromatography system Alliance 2695™ (Waters Corporation, Milford, MA) was equipped with a Waters 414™ differential refractive index detector, a multi-angle light scattering photometer DAWN Heleos II (Wyatt Technologies, Santa Barbara, CA), and a ViscoStar™ differential capillary viscometer detector (Wyatt). The software used for data acquisition and simplification was version 5.4 from Wyatt. The columns used were 2×10 7 and two Shodex GPC HFIP-806M TM styrene-divinylbenzene columns with a theoretical plate of 8,000 / 30 cm; and an exclusion limit of 2×10 5 And a Shodex GPC HFIP-804M ™ styrene-divinylbenzene column with a theoretical plate of 10,000 / 30 cm.

[0080] The sample was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) containing 0.01 M sodium trifluoroacetate, mixed with moderate stirring at 50° C. for four hours, and then filtered using a 0.45 μm PTFE filter. The concentration of the solution was approximately 2 mg / mL.

[0081] The chromatograph was set at 35°C; the flow rate was 0.5 mL / min and the data was collected; the injection volume was 100 μL; and the run time was 80 min. Data were imported from all three detectors mentioned above and data reduction was performed. The light scattering detector used eight scattering angles. No column calibration benchmark was involved in the data processing.

[0082] 2. Antibacterial test

[0083] The antibacterial test method is carried out according to the test method of "GBT 31402-2015 Plastics Antibacterial Properties of Plastic Surfaces". The test bacteria selected for the antibacterial test include one or two of Escherichia coli and Staphylococcus aureus.

[0084] The technical solution of the present invention is described in detail below through specific embodiments.

[0085] Example 1

[0086] The method for preparing the antibacterial material provided in this embodiment specifically comprises the following steps:

[0087] (1) Provide antimicrobial agents.

[0088] Guanidine hydrochloride After being fully mixed with hexamethylenediamine or p-phenylenediamine or 4,4′-diaminodicyclohexylmethane in a molar ratio of 1.1 to 1:1, stepwise heating is performed under a nitrogen atmosphere, and the heating steps include: in the first stage, the temperature is raised to 140°C and kept warm for 1 hour; in the second stage, the temperature is raised to 160°C and kept warm for 1 hour; in the third stage, the temperature is raised to 180°C, and ammonia generated by the reaction is removed by vacuum, and the temperature is kept warm for 0.5 hour.

[0089] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II).

[0090] Among them, R of antibacterial agent 1# is the residue of hexamethylenediamine.

[0091] Then, the obtained antibacterial agent intermediate and the corresponding sodium salt of the diacid are dissolved in a mixed solution of water and ethanol at a molar ratio B of 1:0.15, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I).

[0092] Wherein, X is a furan ring, n=40-50; the molecular weight of the antibacterial agent is 16000-19000. The antibacterial agent prepared in this example is recorded as antibacterial agent #1.

[0093] Example 2

[0094] The difference between this embodiment and embodiment 1 is that:

[0095] The antibacterial agent intermediate prepared in Example 1 is used and mixed with the same sodium diacid salt as in Example 1 at a molar ratio B of 1:0.25. The obtained antibacterial agent has the same structural formula as that in Example 1 and a molecular weight of 15000-19000. The antibacterial agent prepared in this example is recorded as antibacterial agent 2#.

[0096] Example 3

[0097] The difference between this embodiment and embodiment 1 is that:

[0098] The antibacterial agent intermediate prepared in Example 1 was mixed with the corresponding sodium salt of a diacid at a molar ratio of B of 1:0.25 to obtain an antibacterial agent. In formula (I), R is the residue of hexamethylenediamine, X is a benzene ring, and n=30-40; the molecular weight of the above antibacterial agent is 12000-16000, and the antibacterial agent prepared in this embodiment is recorded as 3# antibacterial agent.

[0099] Example 4

[0100] The difference between this embodiment and embodiment 1 is that:

[0101] The prepared antibacterial agent intermediate has the structural formula Where R is the residue of p-phenylenediamine.

[0102] After the antibacterial agent intermediate and the sodium salt of the diacid are mixed and reacted at a molar ratio B of 1:0.25, the antibacterial agent structural formula is obtained. In the formula (I), R is the residue of p-phenylenediamine, X is a furan ring, and n=30-40; the molecular weight of the above antibacterial agent is 13000-17000, and the antibacterial agent prepared in this example is recorded as antibacterial agent 4#.

[0103] Example 5

[0104] The difference between this embodiment and embodiment 1 is that:

[0105] The prepared antibacterial agent intermediate has the structural formula Wherein R is a 4,4'-diaminodicyclohexylmethane residue.

[0106] After the antibacterial agent intermediate and the sodium salt of the diacid are mixed and reacted at a molar ratio B of 1:0.15, the antibacterial agent structural formula is obtained. In the formula (I), R is a 4,4′-diaminodicyclohexylmethane residue, X is a furan ring, and n=40N50; the molecular weight of the above antibacterial agent is 16000-18000, and the antibacterial agent prepared in this example is recorded as antibacterial agent #5.

[0107] Embodiment 6-15

[0108] Examples 7-16 all use the above-mentioned 1#N6# antibacterial agent to prepare PET antibacterial materials, and the preparation method includes: adding the antibacterial agent, antioxidant and acid scavenger to a high mixer and mixing for 10-15 minutes, and then adding the mixed materials to a twin-screw extruder for mixing and extrusion to obtain an antibacterial poly, wherein the twin-screw extrusion processing temperature used is 260-280°C. The dosage ratio of PET resin, antibacterial agent, antioxidant and acid scavenger, the types of resin, antioxidant and acid scavenger, and the extrusion temperature can be adjusted according to actual production needs.

[0109] Furthermore, the inventors prepared a series of antibacterial products using the aforementioned antibacterial agent products according to the process conditions shown in Table 1. The antibacterial properties, mechanical properties, etc. of the products can also be seen in Table 1.

[0110] Table 1 Preparation process, composition and antibacterial results of the antibacterial products provided by Examples 6-15

[0111]

[0112]

[0113] Note: The data shown in columns D and E in Table 1 are the average values ​​after testing multiple samples.

[0114] Comparative Example

[0115] The present invention prepares an antibacterial PET product by adding an existing antibacterial agent in the prior art, and characterizes the antibacterial effect. The results are shown in Table 2. The added antibacterial agent includes any one of polyhexamethylguanidine hydrochloride, silver ions, and zinc chloride, and the antibacterial performance of the obtained PET product is compared with the PET product of the embodiment of the present invention.

[0116] The preparation methods of the PET products of Comparative Examples 1-6 are the same as those of the examples. In addition, without adding any of the aforementioned antimicrobial products or adding a commercial antimicrobial agent (Comparative Example 5), the test results of the antimicrobial properties, mechanical properties, etc. of a series of PET products prepared under the process conditions shown can also be found in Table 2.

[0117] Table 2 Preparation process, composition and antibacterial results of the antibacterial products provided in the comparative examples

[0118]

[0119]

[0120] Note: The data shown in columns D and E in Table 2 are the average values ​​after testing multiple samples.

[0121] The results shown in Table 1 and Table 2 show that the antibacterial activity of the PET antibacterial material provided by the technical solution of the present invention is significantly better than that of the antibacterial material with other antibacterial agents added. First, after boiling at 100°C for 2h, the antibacterial performance of the present invention is almost unaffected, while the antibacterial performance of the polyhexamethylguanidine hydrochloride, silver ions and zinc chloride used in the comparative example is significantly reduced, or even loses the antibacterial performance. In particular, the antibacterial performance of the PET material provided by the present invention has very beneficial thermal stability, the added antibacterial agent component can not be decomposed under the processing conditions of 260-280°C, and due to the poor water solubility, it can be boiled at 100°C for 2h without dissolving or decomposing, and still maintain an antibacterial rate of more than 90%, indicating that the antibacterial agent in the antibacterial PET material of the present invention has good compatibility with the matrix material, and can be integrated without adding a compatibilizer, so that the antibacterial agent is not easy to escape from the PET material during service, and a long-term antibacterial performance is achieved.

[0122] The above are only preferred embodiments of the present invention, which do not limit the protection scope of the present invention. For those skilled in the art, the present invention may have various modifications and changes. Within the spirit and principle of the present invention, changes, modifications, replacements, integrations and parameter changes to these embodiments by conventional substitutions or by being able to achieve the same functions without departing from the principles and spirit of the present invention all fall within the protection scope of the present invention.

Claims

1. A PET antibacterial material, characterized in that: At least comprising polyethylene terephthalate and an antibacterial agent; the PET antibacterial material uses PET as a base material, and the amount of the antibacterial agent added is 0.5-1.5wt% of the base material; The antibacterial agent is an organic salt with a double bond, a benzene ring or a furan ring structure and having hydrophobic properties.

2. The PET antibacterial material according to claim 1, characterized in that: The structural formula of the antibacterial agent is shown below: Wherein, n is an integer of 40-60, R is a residue of hexamethylenediamine, meta-phenylenediamine, para-phenylenediamine, 4,4'-diaminodicyclohexylmethane, etc., and X is a benzene ring or a furan ring.

3. The PET antibacterial material according to claim 1, characterized in that: It may also include an antioxidant and / or an acid scavenger; the antioxidant is added in an amount of 0.1 to 0.3 wt % of the base material; the acid scavenger is added in an amount of 0.01 to 0.05 wt % of the base material.

4. The PET antibacterial material according to claim 3, characterized in that: The antioxidant includes any one or more of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, triethylene glycol bis[triethylene glycol tert-butyl-4-hydroxy-5-methylphenyl)propionate], N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid; And / or, the acid scavenger includes any one or more combinations of zinc stearate, calcium stearate and hydrotalcite.

5. A method for preparing a PET antibacterial material, characterized in that: The method comprises at least mixing polyethylene terephthalate and an antibacterial agent uniformly and then melt-extruding the mixture to obtain the product; The antibacterial agent is a compound represented by formula (I): Wherein, n is an integer of 40-60, R is a residue of hexamethylenediamine, meta-phenylenediamine, para-phenylenediamine, 4,4'-diaminodicyclohexylmethane, etc., and X is a benzene ring or a furan ring.

6. The preparation method according to claim 5, characterized in that: The following steps are involved: S1. Providing the antimicrobial agent; S2. After all the raw materials are added into a high-speed mixer and mixed evenly, the PET antibacterial material is prepared by melt extrusion using a twin-screw extruder at 240-280°C and injection molding.

7. The preparation method according to claim 6, characterized in that: The preparation steps of the antibacterial agent include: (1) heating guanidine hydrochloride and diamine until they are completely dissolved and then fully mixed, and heating treatment is performed under an inert gas atmosphere to allow guanidine hydrochloride and diamine to react to obtain an antibacterial agent intermediate as shown in formula (II); wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4'-diaminodicyclohexylmethane; (2) dissolving the antibacterial agent intermediate and sodium salt obtained in step (1) in a reaction solvent, stirring and reacting under an inert gas atmosphere to obtain the antibacterial agent.

8. The preparation method according to claim 7, characterized in that: The heating treatment in step (1) adopts a staged heating method; the staged heating method includes a first stage, a second stage, and a third stage, the heating temperature is increased in sequence, and each stage is heated to the reaction temperature and then subjected to a heat preservation treatment; the first stage includes heating the temperature to 130-140° C. and keeping the temperature for 0.5-1.5 h; the second stage includes heating the temperature to 150-160° C. and keeping the temperature for 0.5-1.5 h; the third stage includes heating the temperature to 170-180° C., vacuuming to remove ammonia generated by the reaction, and keeping the temperature for 0.5 h; The diamine includes at least one of hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, and 4,4'-diaminodicyclohexylmethane; And / or, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:

1. and / or, the sodium salt comprises sodium furandicarboxylate or sodium terephthalate; and / or, the molar ratio of the antimicrobial agent intermediate to the sodium salt is 1:0.1 to 1:1; And / or, the temperature at which the antibacterial agent intermediate reacts with the sodium salt includes room temperature to 60°C; And / or, the reaction solvent is any one of water / ethanol, water / isopropanol, water / glycerol, water / n-butanol, and water / isobutanol.

9. A PET antibacterial film, prepared by using the PET antibacterial material according to any one of claims 1 to 3; the preparation method comprises: At least all raw materials including polyethylene terephthalate and antibacterial agent are injected into a twin-screw extruder, melt-extruded into sheets, and then stretched and shaped to obtain the PET antibacterial film; the extrusion temperature is 240-280°C.

10. An antibacterial plastic container, characterized in that: The method at least comprises the steps of uniformly mixing all raw materials for preparing the antibacterial PET as claimed in any one of claims 1 to 3, and then performing melt extrusion at 240 to 280° C. and then performing injection molding by an injection molding machine to obtain the antibacterial plastic container.

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