阅读说明：本技术 复合抗菌材料及其制备方法 (Composite antibacterial material and preparation method thereof ) 是由 张萍 高德 骆双灵 于 2018-06-12 设计创作，主要内容包括：本发明提供了一种复合抗菌材料,包括如下重量百分比的组分：抗菌剂0～5％,PBAT95～100％,上述复合抗菌材料的制备方法为S1.将PBAT和抗菌剂按照配比溶解于三氯甲烷得混合溶液；S2.将混合溶液进行搅拌、超声,成型后干燥得复合材料；S3.将复合材料真空干燥即得复合抗菌材料。本发明的有益效果是：(1)本发明的复合抗菌材料属于可生物降解材料,符合可持续发展理念；(2)无机抗菌剂添加到PBAT基质中,不仅提升了PBAT复合抗菌材料的抗菌性能,同时提升了复合材料的机械性能和阻隔性能；(3)复合抗菌材料具有良好的抗菌性能,可应用于医药、食品包装领域。(The invention provides a composite antibacterial material, which comprises the following components in percentage by weight: 0-5% of an antibacterial agent and 95-100% of PBAT, wherein the preparation method of the composite antibacterial material comprises the following steps of S1, dissolving PBAT and the antibacterial agent in chloroform according to a ratio to obtain a mixed solution; s2, stirring and ultrasonically treating the mixed solution, and drying after forming to obtain a composite material; and S3, drying the composite material in vacuum to obtain the composite antibacterial material. The invention has the beneficial effects that: (1) the composite antibacterial material belongs to biodegradable materials, and accords with the sustainable development concept; (2) the inorganic antibacterial agent is added into the PBAT matrix, so that the antibacterial performance of the PBAT composite antibacterial material is improved, and the mechanical performance and the barrier performance of the composite material are improved; (3) the composite antibacterial material has good antibacterial performance and can be applied to the fields of medicines and food packaging.)

1. The composite antibacterial material is characterized by comprising the following components in percentage by weight: 95-100% of poly (terephthalic acid) -adipic acid-butanediol ester and 0-5% of antibacterial agent.

2. The composite antimicrobial material of claim 1, wherein the antimicrobial agent is an inorganic antimicrobial agent that is nano-TiO₂Nano Ag-TiO₂One or two of them, or modified nano TiO₂Modified nano Ag-TiO₂One or two of them.

3. The composite antibacterial material according to claim 3, wherein the modified nano TiO is₂Modified nano Ag-TiO₂Silane coupling agent to nano TiO₂Nano Ag-TiO₂Modified to obtain; the silane coupling agent is at least one of KH-560, KH-570, KH-151 and KH-171.

4. A method for preparing the composite antibacterial material according to any one of claims 1 to 3, characterized by comprising the steps of:

s1, dissolving poly (terephthalic acid) -adipate-butylene glycol ester and an antibacterial agent into a mixed solution of trichloromethane according to a ratio;

s2, stirring and ultrasonically treating the mixed solution, and drying after forming to obtain a composite material;

and S3, drying the composite material in vacuum to obtain the composite antibacterial material.

5. The method for preparing the composite antibacterial material according to claim 4, wherein the polybutylene terephthalate-adipate and the antibacterial agent in the step S1 are pretreated, that is, the polybutylene terephthalate-adipate and the antibacterial agent are vacuum-dried under the following conditions: the temperature is 60 ℃ and the time is 10-12 hours.

6. The method for preparing a composite antibacterial material according to claim 4, wherein the mass fraction of the polybutylene terephthalate-adipate-butylene glycol in the mixed solution of the step S1 is 2.5-2.6%, and the mass fraction of the antibacterial agent in the solution is 0.03-0.13%.

7. The preparation method of the composite antibacterial material according to claim 4, wherein the stirring temperature in the step S2 is room temperature, and the stirring time is 10-15 hours; the ultrasonic condition is ice-water bath protection, and the time is 20-30 min; the drying condition is drying for 10-15 h at room temperature.

8. The preparation method of the composite antibacterial material according to claim 4, wherein the vacuum drying temperature in the step S3 is 55-70 ℃ and the time is 24-48 h.

9. The method for preparing the composite antibacterial material according to claim 4, wherein the antibacterial agent in the step S1 is modified nano TiO₂Or modified nano Ag-TiO₂At least one of the antibacterial agents, and the modification method comprises the following steps: adding silane coupling agent hydrolysate into nano TiO₂Or nano Ag-TiO₂Carrying out modification reaction in the dispersion liquid, centrifuging, washing, drying and sieving after the reaction is finished to obtain the modified nano TiO₂Modified nano Ag-TiO₂。

10. The preparation method of the composite antibacterial material according to claim 9, characterized in that the reaction temperature in the modification process is controlled to be 70-85 ℃, the reaction time is 12-24 h, the centrifugation condition is 8000-10000 r/min, and the centrifugation time is 10-20 min.

Technical Field

The invention relates to a high molecular resin material, in particular to a blending modified antibacterial resin material and a preparation method thereof.

Background

In recent years, the application of plastic products in large quantities leads to the gradual shortage of petroleum resources and the increasing severity of ecological environment problems. With the increasing awareness of environmental protection, the development of new biodegradable materials to replace petroleum-based plastic materials has become a hot research topic, and for example, poly (β -hydroxybutyrate- β -hydroxyvalerate) (PHBV), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polybutylene terephthalate-adipate (PBAT), etc. are biodegradable plastics. The poly (butylene adipate terephthalate) (PBAT) is polyester biodegradable plastic, is prepared by copolymerizing butylene adipate and butylene terephthalate, and focuses on gradual temperature rise in recent years, but the PBAT has relatively slow degradation rate and poor mechanical property and barrier property, so that the popularization and application of the PBAT in the market are limited, and the current research mainly focuses on blending and modifying the PBAT with other degradable plastics or adding a modifier to improve the property of the PBAT.

With the popularization and application of plastic products and the increase of human health consciousness, the safety and sanitation problems of plastic products are becoming one of the focuses of people's common attention. In the field of high-frequency use of polymer materials such as textile fibers, biomedicine, food packaging and the like, whether the material has excellent antibacterial performance or not is one of important indexes for determining the practicability and the long-term effect of the material. The antibacterial plastic is a functional material with bacteriostatic or bactericidal activity, which is prepared by an antibacterial agent and a polymer antibacterial carrier by a certain method and technology. The antibacterial agent is mainly divided into an organic antibacterial agent and an inorganic antibacterial agent, and although the organic antibacterial agent has strong antibacterial action, fast aging, stable color and low cost, the organic antibacterial agent is easy to decompose, has high toxicity and poor heat resistance; inorganic antibacterial agents have good stability, little or almost no toxicity, and good heat resistance, and thus have become an important research direction at present. However, the inorganic antibacterial agent has poor performance and poor processability due to the large difference between the physical and chemical properties such as polarity, molecular weight and the like of the inorganic antibacterial agent and the polymer antibacterial carrier.

Disclosure of Invention

In order to solve the technical problems, the invention provides a degradable composite polymer antibacterial material.

The technical scheme of the invention is to provide a composite antibacterial material, which comprises the following components in percentage by weight: 0-5% of an antibacterial agent and 95-100% of PBAT.

Wherein the antibacterial agent is inorganic antibacterial agent, and is one or more of metal silver, copper, titanium and zinc series, or silver-zinc composite system and silver-titanium composite system.

Further, the inorganic antibacterial agent is nano TiO₂Or nano Ag-TiO₂One or two of them, or modified nano TiO₂Or modified nano Ag-TiO₂One or two of them.

Further, modified nano TiO₂Modified nano Ag-TiO₂Silane coupling agent to nano TiO₂Nano Ag-TiO₂Modified to obtain; the silane coupling agent is at least one of KH-560, KH-570, KH-151 and KH-171; nanometer TiO is coupled by silane coupling agent₂Modification of antibacterial agent to improve nano TiO content₂Lipophilicity of, i.e. upgrading of, nano TiO₂Dispersibility in PBAT matrix.

The invention also provides a preparation method of the composite antibacterial material, which comprises the following steps:

s1, dissolving PBAT and an antibacterial agent in chloroform according to a ratio to obtain a mixed solution;

s2, stirring and ultrasonically treating the mixed solution, and drying after forming to obtain a composite material;

and S3, drying the composite material in vacuum to obtain the composite antibacterial material.

Further, the mass fraction of PBAT in the mixed solution of step S1 is 2.5% to 2.6%, and the mass fraction of the antibacterial agent is 0.03% to 0.13%.

Further, in the step S2, the stirring temperature is room temperature, and the stirring time is 10-15 hours; the ultrasonic condition is ice-water bath protection, and the time is 20-30 min; the drying condition is drying for 10-15 h at room temperature.

Further, the molding in step S2 is performed such that the mixed solution is cast in a mold.

Further, in the step S3, the vacuum drying temperature is 55-70 ℃, and the time is 24-48 h.

Further, the antibacterial agent is nano TiO₂Including changingNano TiO 2₂Or modified nano Ag-TiO₂One or two of the above-mentioned materials, modified nano TiO₂Modified nano Ag-TiO₂The preparation process is as follows: adding silane coupling agent hydrolysate into nano TiO₂Nano Ag-TiO₂Mixing the dispersion, stirring, centrifuging, washing, drying and sieving to obtain the modified nano TiO₂Modified nano Ag-TiO₂。

Further, the reaction temperature is controlled to be 70-85 ℃ in the modification process, the reaction time is 12-24 hours, the stirring mode is condensation reflux stirring, the centrifugation condition is 8000-10000 r/min, and the centrifugation time is 10-20 min.

Further, the preparation process of the silane coupling agent hydrolysate comprises the steps of mixing the silane coupling agent, anhydrous ethanol and deionized water according to the weight ratio of 5:18:2, adjusting the pH value to 3.5-4.0 by using glacial acetic acid, and stirring for 30-45 min.

Further, nano TiO₂Nano Ag-TiO₂The dispersion liquid is composed of nano TiO₂Nano Ag-TiO₂The weight ratio of the absolute ethyl alcohol to the deionized water is 3.7: 59.0: 37.3, mixing the components and performing ultrasonic treatment for 1h, wherein the ultrasonic treatment is ice-water bath protection.

Further, step S1 includes applying PBAT and TiO nanoparticles₂Carrying out pretreatment, namely carrying out vacuum drying on the raw materials, wherein the vacuum drying conditions are as follows: the temperature is 60 ℃ and the time is 10-12 hours.

The composite antibacterial material can be made into films for medicine and food packaging.

The invention has the advantages and beneficial effects that:

(1) the composite antibacterial material belongs to biodegradable materials, and accords with the sustainable development concept;

(2) the inorganic antibacterial agent is added into the PBAT matrix, so that the antibacterial performance of the PBAT composite antibacterial material is improved, and the mechanical performance and the barrier performance of the composite material are improved;

(3) the composite antibacterial material has good antibacterial performance and can be applied to the fields of medicines and food packaging.

Drawings

FIG. 1 shows the micro-morphology (TiO) of the composite antibacterial material under a field emission scanning electron microscope (FE-SEM) according to the invention₂The content is 3 percent, wherein (a) is PBAT and nano TiO₂The composite film of (1); (b) is PBAT and modified nano TiO₂The composite film of (1).

FIG. 2 is a graph showing the results of the inhibition zone experiment on Escherichia coli, in which (a) is PBAT/TiO of example 2 of the present invention₂Test results of the composite antibacterial film, (b) is a test result of the PBAT film of comparative example 1.

Detailed Description

The present invention will be further described with reference to the following embodiments.

The principle of the composite antibacterial material is that firstly, the poly (terephthalic acid) -adipate-butylene glycol ester (PBAT) has the performances of complete biodegradability, thermoplasticity, high flexibility and the like, so the composite antibacterial material has a very bright prospect in the application of packaging materials and various film materials; the inorganic antibacterial agent has good stability, little or almost no toxicity and good heat resistance, and is suitable for resin materials needing thermal processing, especially suitable for packaging materials of foods and medicines. Nano TiO in inorganic antiseptic₂Has good photocatalytic activity, high chemical stability, no harm to human body and low cost, but because of the nanometer TiO₂The polarity is strong, the free energy of the particle surface is high, the particles are easy to agglomerate, the interfacial property with the PBAT matrix is different, the compatibility is poor, and the particles are difficult to be uniformly dispersed in the organic matrix, so although the PBAT can be used for PABT, the application of the PBAT is limited by the above dissimilarity. Nanometer TiO is coupled by silane coupling agent₂The antibacterial agent is added into PBAT matrix after being lipophilically modified, so that nano TiO is improved₂The agglomeration of the antibacterial agent in the PBAT improves the PBAT/TiO₂Mechanical property and barrier property of nano composite antibacterial material, in particular to silane coupling agent in TiO₂Grafting the surface of the nano-particles to form a monomolecular layer, and preparing nano TiO₂When added to PBAT, the monomolecular silane coupling agent layer can be in a nano TiO₂Plays a role in coupling with a PBAT interface, improves the compatibility of the interface and increasesInterface adhesive force is improved, so that nano TiO can be improved₂The dispersibility of the particles in the PBAT matrix is improved, the interface is not easy to be debonded under the action of external force, and stress concentration is avoided, so that the mechanical property of the composite antibacterial material is improved, and on the other hand, the nano TiO is used for improving the mechanical property of the composite antibacterial material₂Can increase the crystallinity of PBAT matrix, and simultaneously, the nano TiO₂The particles are uniformly distributed in the PBAT matrix, so that the obtained PABT/TiO₂Molecular chains in the nano composite material are closely arranged, so that the barrier property of the composite antibacterial material is improved.

The following composite materials are prepared into films, and the inorganic antibacterial agent is selected from nano TiO₂The composite antibacterial material of the present invention is specifically described for examples.