Application of antibacterial agent in poly (ethylene 2, 5-furandicarboxylate) material

Abstract

The invention provides an application of an antibacterial agent in a poly (ethylene 2, 5-furandicarboxylate) material. The antibacterial agent adopted by the invention is hydrophobic organic salt with a double-bond, benzene ring or furan ring structure, and the antibacterial agent contains the double-bond, benzene ring or furan ring structure, so that the antibacterial agent has good compatibility with a material also containing a furan ring, and the antibacterial agent is not easy to dissolve out from a polyester main body; on the other hand, the water solubility of the organic salt is poor, and the stability of the organic salt can be kept without dissolving when the organic salt is boiled in high-temperature water, so that the antibacterial material can keep efficient and long-acting antibacterial performance when serving under high-temperature and humid conditions.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial polyester materials, in particular to the application of an antibacterial agent in polyethylene 2,5-furandicarboxylate materials. Background Art

[0002] Polyethylene 2,5-furandicarboxylate (PEF) is a bio-based polyester composed of aliphatic hydrocarbons and cyclic conjugated dihydroxy aromatic compounds. Since it is a 100% bio-based material, it can be used as a degradable polymer material. At the same time, it has the advantages of strong rigidity and high mechanical strength, making it widely used in packaging, textiles, films and other products. Compared with petroleum-based polyester PET, it has better physical-mechanical properties, and its oxygen barrier capacity is 10 times that of PET, its CO2 penetration resistance capacity is 4 times that of PET, and its H2O penetration resistance capacity is 2 times that of PET, making it have broad application prospects in the fields of high-barrier packaging materials, high-performance fibers and engineering plastics, especially in the field of sealed food packaging materials. Furthermore, due to the damage to the environment caused by white pollution caused by the use of plastic products such as packaging bags made of polymer compounds such as polystyrene, polypropylene, polyvinyl chloride, agricultural mulch, disposable tableware, plastic bottles, etc., polyethylene 2,5-furandicarboxylate is used as a packaging material for food packaging for degradation treatment, thereby alleviating environmental pressure. When it is used as food packaging and container materials, polyethylene 2,5-furandicarboxylate is generally modified to give it certain antibacterial properties to prevent it from breeding bacteria and thus have better performance. The usual modification method is to add antibacterial agents to polyethylene 2,5-furandicarboxylate so that it can inhibit or kill bacteria, molds, yeasts, algae and even viruses contaminated on its surface in the use environment, and keep itself clean by inhibiting the reproduction of microorganisms, thereby improving the antibacterial performance and action time of the product. Choosing a suitable antibacterial agent can extend the antibacterial effectiveness of the product to its own service life. Chinese invention patent CN115197546A discloses a mildew-proof and antibacterial PET sheet. Modified zinc oxide and polyhexamethylene biguanide hydrochloride are added to the PET material to achieve mildew-proof and bactericidal effects. However, the compatibility of zinc oxide and polyhexamethylene biguanide hydrochloride is poor. On the one hand, a compatibilizer needs to be added to solve the problem. On the other hand, due to the compatibility problem, the addition amounts of the two antibacterial agents are very low, and the addition amount of polyhexamethylene biguanide hydrochloride is less than 0.15wt%.

[0003] On the other hand, from the selection of antimicrobial agents, with the banning of about 1,000 antimicrobial agents with bactericidal activity, including triclosan, triclocarban, benzethonium chloride and chloroxylenol, the market's requirements for the safe use of antimicrobial agents have risen to a new height. Among them, polyhexamethyleneguanidine hydrochloride (PHMG), which has the advantages of safety and environmental protection, 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), the related antimicrobial plastics, textiles and other products often come into contact with water, which causes the antimicrobial agent to dissolve rapidly, resulting in the rapid attenuation of the antimicrobial effect of the product, resulting in a rapid decrease in the antimicrobial performance of the product. When PHMG is directly added to polyethylene 2,5-furandicarboxylate to give antimicrobial properties to the mixed use to prepare antimicrobial materials and applied to food packaging materials, the antimicrobial performance decreases rapidly due to the frequent use of water for washing, and the antimicrobial time is greatly shortened. Chinese invention patent CN111393638A discloses a dissolution-resistant guanidine antibacterial agent and a preparation method thereof. The patent grafts an organic acid salt containing an ester group and having 6 to 8 or 12 to 20 carbon atoms in the main chain with a guanidine antibacterial material, and grafts the entire anion group of the organic acid salt to the side chain of the polymer molecule of the guanidine antibacterial material, thereby preparing a high molecular weight antibacterial material that is insoluble in water, namely, the dissolution-resistant guanidine salt antibacterial agent of the present invention. However, the grafting reaction process is cumbersome, and the grafting rate is low. The obtained dissolution-resistant guanidine salt antibacterial agent still cannot meet the long-term antibacterial requirements of polyester materials during use. Other antibacterial agents, such as silver-based and zinc-based antibacterial agents, are added to polyester materials. Due to their poor compatibility with polyester materials, they are easily detached from polyester, which also leads to a decrease in antibacterial effect and cannot meet the long-term antibacterial performance of polyester materials.

[0004] Therefore, how to maintain the antibacterial properties of antibacterial products such as packaging and containers made of polyethylene 2,5-furandicarboxylate materials for a long time, especially to maintain long-term antibacterial properties in a humid environment, has become a technical problem that needs to be solved urgently. Summary of the invention

[0005] In order to overcome the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide an application of an antibacterial agent in polyethylene 2,5-furandicarboxylate material, so as to overcome the deficiencies of the antibacterial agent used in polyethylene 2,5-furandicarboxylate material in the prior art, such as the short antibacterial effect of the polyester product resulting from the high water solubility and poor compatibility, which limits the use of the polyester product, and the production method is simple, the cost is low, and the application forms are flexible and diverse.

[0006] To achieve the above objectives, the present invention provides the following technical solutions.

[0007] One aspect of the present invention provides an application of an antibacterial agent in a polyethylene 2,5-furandicarboxylate material.

[0008] The antibacterial agent used in the present invention is a hydrophobic organic salt with a double bond, a benzene ring or a furan ring structure. The double bond, the benzene ring or the furan ring structure enables it to have good compatibility with materials that also contain a furan ring, making it difficult to dissolve from the polyester body; on the other hand, the organic salt has poor solubility and can maintain its stability without dissolving even when boiled in high-temperature water, so that the antibacterial material can serve under high-temperature and humid conditions and can also maintain high-efficiency and long-lasting antibacterial properties.

[0009] Compared with other antibacterial agents in the prior art, due to its high water solubility, when applied to polyethylene 2,5-furandicarboxylate, the antibacterial performance is significantly reduced or even lost in a humid environment. In addition, the processing temperature of polyethylene 2,5-furandicarboxylate is 260-280°C, and some antibacterial agents in the prior art cannot maintain stability at this temperature, while the antibacterial agent provided by the present invention can maintain the stability under the processing conditions of 260-280°C without decomposition.

[0010] In a specific embodiment of the present invention, the antibacterial agent is a compound represented by formula (I):

[0011] Wherein, n is an integer of 40-60, R is a residue of hexamethylenediamine, meta-phenylenediamine, para-phenylenediamine, 4,4′-diaminodicyclohexylmethane, etc., X is a benzene ring or a furan ring, and a is an integer of 4-6.

[0012] Preferably, the antibacterial agent is added to the polyethylene 2,5-furandicarboxylate material in an amount of 0.5 to 1.5 wt %.

[0013] As another aspect of the present invention, an antibacterial polyethylene 2,5-furandicarboxylate material is also provided, comprising at least polyethylene 2,5-furandicarboxylate and an antibacterial agent. In a specific embodiment of the present invention, the antibacterial polyethylene 2,5-furandicarboxylate comprises 100 parts of polyethylene 2,5-furandicarboxylate, 0.5-1.5 parts of an antibacterial agent, 0.1-0.3 parts of an antioxidant, and 0.01-0.05 parts of an acid scavenger, by weight.

[0014] Preferably, the antioxidant includes any one or more combinations of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, 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.

[0015] Preferably, the acid scavenger comprises any one or more combinations of zinc stearate, calcium stearate and hydrotalcite.

[0016] Another aspect of the present invention also provides a method for preparing the antibacterial polyethylene 2,5-furandicarboxylate material, comprising mixing polyethylene 2,5-furandicarboxylate and the antibacterial agent and then melt-extruding the mixture. More specifically, the antibacterial material comprises mixing polyethylene 2,5-furandicarboxylate, the antibacterial agent, the antioxidant and the acid scavenger and then melt-extruding the mixture.

[0017] Preferably, a method for preparing an antibacterial polyethylene 2,5-furandicarboxylate material comprises the following steps:

[0018] S1. Provide antimicrobial agent;

[0019] S2. It comprises at least adding the antibacterial agent and polyethylene 2,5-furandicarboxylate into a high temperature mixture and mixing them evenly, and then melt-extruding by a twin-screw extruder at 220 to 260° C. and then injection molding to prepare the antibacterial agent.

[0020] Preferably, the preparation steps of the antibacterial agent include:

[0021] (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);

[0022]

[0023] 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;

[0024] (2) dissolving the antibacterial agent intermediate obtained in step (1) and sodium dicarboxylate in a water / alcohol mixture, stirring and reacting in an inert gas atmosphere to obtain the antibacterial agent.

[0025] 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 150-160°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.

[0026] Preferably, the diamine includes at least one of hexamethylenediamine, p-phenylenediamine, m-phenylenediamine and 4,4'-diaminodicyclohexylmethane.

[0027] Preferably, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:1.

[0028] Preferably, the sodium salt comprises sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate or sodium adipic acid.

[0029] Preferably, the molar ratio of the antibacterial agent intermediate to the dicarboxylic acid sodium salt is 1:0.1 to 1:1.

[0030] Preferably, the temperature for reacting the antibacterial agent intermediate with the dicarboxylic acid sodium salt is from room temperature to 60°C.

[0031] Preferably, the reaction solvent of the antibacterial agent intermediate and the dicarboxylic acid sodium salt is water / ethanol, water / isopropanol, water / glycerol, water / n-butanol, or water / isobutanol.

[0032] As one aspect of the present invention, an antibacterial film is also provided, which is prepared using the above-mentioned antibacterial polyethylene 2,5-furandicarboxylate material; the preparation method comprises: injecting all raw materials including at least polyethylene 2,5-furandicarboxylate and an antibacterial agent into a twin-screw extruder, melt-extruded into a sheet, and then stretching and shaping to obtain the antibacterial film; the extrusion temperature is 260-280°C.

[0033] 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 antibacterial polyethylene 2,5-furandicarboxylate material uniformly, and then melt-extruding at 260-280°C and then injection molding by an injection molding machine to obtain the antibacterial plastic container.

[0034] The technical effects of the technical solution of the present invention are as follows:

[0035] 1. By adopting the technical solution of the present invention, the provided antibacterial material has excellent antibacterial performance and thermal stability, and can meet the requirement that it will not be thermally decomposed during the injection molding process. Moreover, the added antibacterial agent is an organic salt with a double bond, a benzene ring or a furan ring structure, which contains a double bond, a benzene ring or a furan ring structure and can form a π-π conjugation with the furan ring in 2,5-furandicarboxylic acid ethylene glycol ester, so that the antibacterial agent has good compatibility with the polyester material and the antibacterial agent is not easily dissolved from the polyester body; on the other hand, the organic salt has poor solubility and can maintain its stability without dissolving even under high-temperature boiling water, so that the antibacterial material can be used under high temperature and humid conditions, and can also maintain high-efficiency and long-lasting antibacterial performance, which can meet the requirements of the product for the long-lasting antibacterial performance of the antibacterial agent while effectively ensuring the antibacterial performance and mechanical properties of the formed antibacterial material.

[0036] 2. The antibacterial material provided by the technical solution of the present invention, as a bio-based polyester, has good degradation performance and a lower processing temperature, which can significantly reduce the processing and production costs. The preparation method is simple and has a high yield. The material is safe, environmentally friendly and low in cost. The preparation process is easy to control and is suitable for industrial production, thereby achieving a combination of environment and benefits.

[0037] 3. The antibacterial raw materials provided by the technical solution of the present invention are 100% bio-based materials, have good degradation properties, can significantly reduce the harm of white pollution to the environment, and are applied to food packaging materials, especially sealed packaging containers, which have excellent antibacterial and barrier properties.

[0038] 4. The antibacterial material provided by the technical solution of the present invention, wherein the antibacterial agent is an organic salt, on the one hand, has the characteristics of non-toxicity and safety, so that it can be used as an antibacterial packaging material in the fields of food packaging, medical materials, etc.; on the other hand, since the antibacterial agent has good compatibility with polyester materials, it is not easy to dissolve from the polyester body compared with silver-based and zinc-based antibacterial agents, and its water solubility is significantly lower than that of polyhexamethylene guanidine hydrochloride in the prior art, thereby giving the antibacterial polyester material a longer antibacterial effect, which can be close to the service life of the polyester material itself.

[0039] 5. The 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, and low harm and pollution to the human body and the environment.

[0040] 6. The antibacterial material provided by the present invention has long-lasting antibacterial properties, and its effective antibacterial time is substantially the same as the service life of the antibacterial material. DETAILED DESCRIPTION

[0041] 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.

[0042] The disclosures of all patent and non-patent literature cited herein are incorporated herein by reference in their entirety.

[0043] 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.

[0044] 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.

[0045] Some embodiments of the present invention provide an antibacterial material, comprising at least polyethylene 2,5-furandicarboxylate and an antibacterial agent; the amount of the antibacterial agent added is 0.5 to 1.5 wt % based on the polyethylene 2,5-furandicarboxylate.

[0046] 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, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, etc., and X is a benzene ring, a furan ring, a is an integer from 4 to 6.

[0047] Some embodiments of the present invention provide an antibacterial preparation method, comprising the following steps:

[0048] S1. Provide antimicrobial intermediates;

[0049] 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);

[0050]

[0051] 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;

[0052] S2. Provide antimicrobial agent

[0053] The antibacterial agent intermediate and dicarboxylic acid 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):

[0054]

[0055] wherein n is an integer of 40 to 60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring or Any one of , a is an integer from 4 to 6.

[0056] S3. Provide antibacterial properties;

[0057] The method comprises at least adding an antibacterial agent, an antioxidant, an acid scavenger and polyethylene 2,5-furandicarboxylate into a high-speed mixer and mixing them evenly, and then using a twin-screw extruder to melt extrude and then injection mold to prepare the antibacterial agent at 220-260°C.

[0058] 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.

[0059] 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.

[0060] In some embodiments, the diamine includes at least one of hexamethylenediamine, p-xylylenediamine, m-xylylenediamine, and 4,4′-diaminodicyclohexylmethane.

[0061] In some embodiments, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:1.

[0062] In some embodiments, the sodium salt comprises sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate, or sodium adipate.

[0063] In other embodiments, the molar ratio of the antibacterial agent intermediate to the dicarboxylic acid sodium salt is 1:0.2 to 1:2.

[0064] In other embodiments, the reaction of guanidine hydrochloride and diamine, and the reaction of the antibacterial agent intermediate and the dicarboxylic acid sodium salt are both carried out under the protection of an inert gas.

[0065] 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 260-280° C. and injection molded to prepare the antibacterial material.

[0066] In some specific embodiments, the antibacterial agent prepared by the technical solution of the present invention is added to PEF to obtain a PEF material product with antibacterial function, which is obtained by twin-screw melt extrusion and injection molding, and the processing temperature is between 260 and 280°C.

[0067] In some embodiments, the antibacterial agent prepared by the technical solution of the present invention is added to PEF to obtain a polyester material product with antibacterial function, which is prepared by twin-screw melt extrusion and injection molding, and the processing temperature is between 260 and 280°C.

[0068] In the process of co-processing with polyethylene 2,5-furandicarboxylate and antimicrobial agents, processing aids and modifiers commonly used in the art, such as plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, fillers, etc., are also used.

[0069] 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.

[0070] 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.

[0071] And / or, the lubricant includes, but is not limited to, one or more mixtures of vinyl bisstearamide, butyl stearate, etc.

[0072] 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.

[0073] 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.

[0074] And / or, the filler includes, but is not limited to, one or more mixtures of glass fiber, asbestos, wollastonite, calcium silicate, talc, montmorillonite, etc.

[0075] Some embodiments of the present invention also provide an antibacterial film, comprising at least injecting all raw materials including polyethylene 2,5-furandicarboxylate and an antibacterial agent into a twin-screw extruder, and then melt-extruded into a sheet, and then stretching and shaping to obtain the antibacterial film; the extrusion temperature is 260-280°C.

[0076] Some embodiments of the present invention also provide a method for producing an antibacterial plastic container, which comprises: uniformly mixing all the raw materials of the antibacterial PEF, and then molding the antibacterial plastic container by injection molding at 260-280° 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.

[0077] 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.

[0078] 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.

[0079] The test items, standards or methods involved in the embodiments and / or comparative examples are as follows:

[0080] 1. Molecular weight test

[0081] The number average molecular weight and weight average molecular weight of the product were determined using a GPC column.

[0082] 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 Helos 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-804MTM styrene-divinylbenzene column with a theoretical plate of 10,000 / 30 cm.

[0083] 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.

[0084] 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.

[0085] 2. Antibacterial test

[0086] According to the above results, the antibacterial performance of the antibacterial polyethylene 2,5-furandicarboxylate composite material provided by the present invention has good thermal stability, the added antibacterial agent component can not be decomposed under the processing conditions of 200-220°C, and the hydrophobic property is good. Under the condition of boiling in water at 100°C for 2h, the antibacterial polyethylene 2,5-furandicarboxylate material will hardly fail due to dissolution or decomposition. The antibacterial polypropylene product has good thermal stability and antibacterial performance.

[0087] The technical solution of the present invention is described in detail below through specific embodiments.

[0088] Example 1

[0089] The preparation method of the antibacterial composite material provided in this embodiment specifically comprises the following steps:

[0090] (1) Provide antimicrobial agents.

[0091] 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.

[0092] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II).

[0093] Among them, R of antibacterial agent 1# is the residue of hexamethylenediamine.

[0094] 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).

[0095] 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.

[0096] Example 2

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

[0098] 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#.

[0099] Example 3

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

[0101] 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.

[0102] Example 4

[0103] The difference between this embodiment and embodiment 1 is that:

[0104] The prepared antibacterial agent intermediate has the structural formula Where R is the residue of p-phenylenediamine.

[0105] 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#.

[0106] Example 5

[0107] The difference between this embodiment and embodiment 1 is that:

[0108] The prepared antibacterial agent intermediate has the structural formula Wherein R is a 4,4'-diaminodicyclohexylmethane residue.

[0109] 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=40-50; 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.

[0110] Example 6

[0111] The difference between this embodiment and embodiment 1 is that:

[0112] The prepared antibacterial agent intermediate has the structural formula wherein R is a 4,4'-diaminodicyclohexylmethane residue.

[0113] 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 formula (I), R is a 4,4′-diaminodicyclohexylmethane residue; X is CH2CH2CH2, and n=30-40; the molecular weight of the above antibacterial agent is 15000-21000. The antibacterial agent prepared in this example is recorded as antibacterial agent #6.

[0114] Embodiment 7-16

[0115] Examples 7-16 all use the above-mentioned 1#~6# antibacterials to prepare antibacterial

[0116] (2) Preparation of antibacterial

[0117] The antibacterial agent products in this embodiment can be used to prepare antibacterial agents. The corresponding 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 uniformly mixed materials to a twin-screw extruder for mixing and extrusion to obtain an antibacterial polymer, wherein the twin-screw extrusion processing temperature used is 260-280°C. The dosage ratio of PEF 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.

[0118] 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.

[0119] Table 1 Preparation process, composition and antibacterial results of the antibacterial products provided in the examples

[0120]

[0121] Note: The data shown in columns D and E in Table 1 are the average values ​​after testing multiple samples.

[0122] Comparative Examples 1-6

[0123] The present invention prepares an antibacterial PEF 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 PEF product is compared with the PEF product of the embodiment of the present invention.

[0124] The preparation methods of the PEF 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 commercial antimicrobial agents (Comparative Example 5), the test results of the antimicrobial properties, mechanical properties, etc. of a series of PEF products prepared under the process conditions shown can also be referred to Table 2.

[0125] Table 2 Preparation process, composition and antibacterial results of the antibacterial products provided in the comparative examples of the present invention

[0126]

[0127] Note: The data shown in columns D and E in Table 2 are the average values ​​after testing multiple samples.

[0128] It can be seen from the results shown in Table 1 and Table 2 that the antibacterial activity of the PEF 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 being boiled in water at 100°C for 2h, the antibacterial performance of the present invention is almost not attenuated, 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 PEF material provided by the present invention has good thermal stability, the added antibacterial agent component can not be decomposed under the processing conditions of 260-280°C, and because it has good hydrophobicity, it can be boiled in water at 100°C for 2h without dissolving, so that the antibacterial PEF material can still maintain an antibacterial rate of more than 90%.

[0129] 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. Application of an antibacterial agent in polyethylene 2,5-furandicarboxylate material; The structural formula of the antibacterial agent is shown in formula (I): in, n is an integer of 40-60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, and 4,4′-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring, Any of, a is an integer from 4 to 6; The antibacterial agent is added in an amount of 0.5 to 1.5 wt % to the polyethylene 2,5-furandicarboxylate material.

2. An antibacterial polyethylene 2,5-furandicarboxylate composite material, characterized in that: Calculated by weight, it includes 100 parts of polyethylene 2,5-furandicarboxylate, 0.5 to 1.5 parts of antibacterial agent, 0.1 to 0.3 parts of antioxidant, and 0.01 to 0.05 parts of acid scavenger.

3. The antibacterial polyethylene 2,5-furandicarboxylate composite material according to claim 2, 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; Or, the acid scavenger includes any one or more combinations of zinc stearate, calcium stearate, and hydrotalcite.

4. The antibacterial polyethylene 2,5-furandicarboxylate composite material according to claim 2 or 3, characterized in that: After being boiled in water at 100° C. for 2 hours, the antibacterial rate of the antibacterial agent against Escherichia coli and Staphylococcus aureus is ≥90%.

5. A method for preparing the antibacterial polyethylene 2,5-furandicarboxylate composite material according to any one of claims 2 to 4, characterized in that: The invention is prepared by uniformly mixing all raw materials including polyethylene 2,5-furandicarboxylate, an antibacterial agent, an antioxidant and an acid scavenger and then melt-extruding the mixture.

6. The preparation method according to claim 5, characterized in that: The following steps are involved: S1. Provide antimicrobial agent; S2. After all the raw materials are added into a high-speed mixer and mixed evenly, a twin-screw extruder is used for melt extrusion at 260-280° C. and then injection molding is performed to prepare the antibacterial polyethylene 2,5-furandicarboxylate composite material.

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 obtained in step (1) and sodium dicarboxylate in a water / alcohol mixture, stirring and reacting in 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 it warm for 0.5N1.5h; the second stage includes heating the temperature to 150N160°C and keeping it warm for 0.5-1.5h; the third stage includes heating the temperature to 170-180°C, vacuuming to remove ammonia generated by the reaction, and keeping it warm for 0.5h; And / or, 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 of dicarboxylic acid includes sodium furandicarboxylate, sodium terephthalic acid, sodium succinate, sodium glutarate or sodium adipic acid; and / or, the molar ratio of the antibacterial agent intermediate to the dicarboxylic acid sodium salt is 1:0.3 to 1:2; And / or, the temperature for reacting the antibacterial agent intermediate with the dicarboxylic acid sodium salt is from room temperature to 60°C; And / or, the reaction solvent of the antibacterial agent intermediate and the dicarboxylic acid sodium salt is water / ethanol, water / isopropanol, water / glycerol, water / n-butanol, water / isobutanol.

9. An antibacterial film, comprising the antibacterial polyethylene 2,5-furandicarboxylate composite material according to any one of claims 2 to 4; the preparation method comprising: At least all raw materials including polyethylene 2,5-furandicarboxylate and an antibacterial agent are injected into a twin-screw extruder, melt-extruded into a sheet, and then stretched and shaped to obtain the antibacterial film; the extrusion temperature is 260-280°C.

10. An antibacterial plastic container, characterized in that: The method comprises at least mixing all raw materials for preparing the antibacterial product as claimed in any one of claims 2 to 4 uniformly, and then subjecting the mixture to melt extrusion at 260-280° C. and injection molding by an injection molding machine to obtain the product.

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