CN110041675B - Preparation method of polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film - Google Patents
Preparation method of polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film Download PDFInfo
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Abstract
The invention provides a preparation method of polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which utilizes soluble Ag+The method comprises the following steps that (1) salt-initiated pyrrole Py performs a chemical oxidation reaction on the surface of layered clay LDHs, the newly formed PPy is chemically oxidized to combine and reduce silver ions into metal silver nano particles AgNP, and then polypyrrole PPy is formed to coat clay LDHs to obtain polypyrrole surface modified layered clay antibacterial powder LDHs @ PPy-Ag; and finally, preparing the LDHs @ PPy-Ag/PCL nano composite film by pouring the LDHs @ PPy-Ag and the polycaprolactone PCL in solution. According to the invention, the interface compatibility and the binding force between LDHs and the PCL are increased by the organic surface coating substance PPy, the mechanical property and the gas barrier property of the final nano composite material are improved, the composite film is endowed with excellent antibacterial property, the application of the composite material in the field of active packaging is finally expanded, the preparation method is simple, the conditions are easy to control, and the preparation method is suitable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, relates to the technical field of high polymer materials, and particularly relates to the field of active packaging application.
Background
Among high performance environmentally friendly degradable plastics, aliphatic polyester is one of the most potential polymer materials at present. Polycaprolactone (PCL) is used as aliphatic polyester with good application potential, is derived from epsilon-caprolactone (epsilon-CL) ring-opening polymerization, and is widely applied to the aspects of food and medical health product packaging, agricultural films and the like. Although PCL is the most biodegradable synthetic aliphatic polyester, its relatively poor structural and functional stability has hindered production applications, particularly the urgent need for higher barrier and antibacterial properties.
Layered double-hydroxy composite metal oxide clay (LDHs) has the excellent performances of controllable appearance, adjustable structure, easy dispersion and the like, and is widely used as functional nano-filler to prepare LDHs-polymer nano-composite materials. Layered clays, which extend the tortuous path of gas molecules through the nanocomposite due to the impermeable layered structure, are considered natural barriers. Theoretically, a high aspect ratio of each layered clay particle would result in a prolonged gas permeation path and increased tortuosity, resulting in decreased gas permeability and enhanced barrier properties. Therefore, the LDHs can be used for reinforcing and modifying the PCL, and the barrier property, the mechanical property and the like of the PCL are improved. Like other inorganic materials, the LDHs have different interfacial properties with the polymer base material and show poor compatibility, resulting in poor dispersibility of the LDHs in the polymer base material and poor interfacial interaction between the LDHs and the base material, and finally resulting in more interfacial defects, which is also an important reason why the composite material is often not remarkably improved. The search for a simpler, more effective and more green modification method is a hot spot of the clay surface modification research at present. It was found that pyrrole (Py) monomers can form polypyrrole (PPy) by chemical oxidative polymerization in aqueous media. As an important member of conductive polymer materials, PPy has received much attention due to its advantages of high conductivity, good thermal stability, easy synthesis, excellent biocompatibility, etc. No report of surface coating modification of LDHs by PPy has been retrieved. In addition, the PPy can also generate strong electrostatic combination effect with bacteria with negative electricity on the surface so as to achieve the bacteriostatic effect, which also prompts the PPy to be gradually paid attention to in the antibacterial field.
Meanwhile, silver series antibacterial materials are a class of inorganic antibacterial materials. The inorganic silver-carrying antibacterial material has the characteristics of sustainability, durability, broad spectrum, good heat resistance, high safety, difficult generation of drug resistance and the like. Silver ions have excellent biological bactericidal action and exhibit a remarkable broad-spectrum antibacterial property. The silver ion has the 'micro-action effect' of killing pathogens and preventing the pathogens from proliferating and has higher biological antibacterial activity. Meanwhile, the silver-based antibacterial agent has better biocompatibility and safety. Silver nanoparticles are currently the most promising inorganic antibacterial materials, and silver ions released from unstable silver nanoparticles have excellent biological bactericidal effect, however, silver nanoparticles are high in cost and prone to agglomeration due to high surface area to volume ratio.
Disclosure of Invention
One of the purposes of the invention is to prepare polypyrrole surface modified layered clay antibacterial powder (LDHs @ PPy-Ag), which is obtained by in-situ polymerization of soluble silver ions on the surface of layered clay, and the chemical oxidation of PPy can combine the polypyrrole surface modified layered clay antibacterial powder (LDHs @ PPy-Ag) on LDH and reduce the polypyrrole surface modified layered clay antibacterial powder (LDHs @ PPy-Ag) into metal nano-silver (AgNP) to obtain the polypyrrole surface modified layered clay antibacterial powder (LDHs @ PPy-Ag), which has the double antibacterial effects of PPy and AgNP. The invention provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, aiming at the defects and defects of the stability of the existing Polycaprolactone (PCL) in structure, function and antibacterial performance.
The invention comprises the following steps:
s1 by using soluble Ag+The method comprises the following steps that (1) pyrrole (Py) is initiated by salt to perform a chemical oxidation-reduction reaction on the surface of layered clay (LDHs) to form nanometer silver-containing polypyrrole (PPy) coated clay LDHs, and then polypyrrole surface modified layered clay antibacterial powder (LDHs @ PPy-Ag) is obtained;
s2, adopting solution pouring to perform film forming treatment on the LDHs @ PPy-Ag and Polycaprolactone (PCL) obtained by the treatment of S1, and preparing the polypyrrole surface modified layered clay-polycaprolactone antibacterial nano composite film (LDHs @ PPy-Ag/PCL).
In step S1, the (LDHs @ PPy-Ag) antibacterial powder preparation includes the steps of:
s11 dissolving Ag in water+Dissolving salt in LDHs dispersion liquid with solubility of 0.5g/L, stirring, adsorbing, heating to 60-80 deg.C to obtain the product containing Ag+A dispersion of ionic LDHs;
further, the soluble Ag+The salt is at least one of AgF, AgNO3 and AgClO 4.
Further, the stirring is at least one of ultrasonic stirring and magnetic stirring.
Further, the stirring time is 5-10min, and the adsorption time is 30-60 min.
S12 by controlling soluble Ag+Mass ratio of salt to Py, adding Py aqueous solution to Ag+And (3) fully stirring, oxidizing and reducing in the ionic LDHs dispersion liquid to obtain the LDHs @ PPy-Ag dispersion liquid.
Further, the soluble Ag+The mass ratio of the salt to the Py is 1: 5-20.
Further, the stirring is at least one of ultrasonic stirring and magnetic stirring.
Further, the stirring time is 50-150min, and the temperature is 60-80 ℃.
S13, carrying out centrifugal washing on the LDHs @ PPy-Ag dispersion liquid obtained in the step S12, and freeze-drying to obtain LDHs @ PPy-Ag powder.
In S2, the preparation of the (LDHs @ PPy-Ag/PCL) nanocomposite film comprises the steps of:
s21, dissolving the LDHs @ PPy-Ag powder and the pure PCL in dimethylformamide, fully stirring and uniformly mixing;
further, the mass ratio of the LDHs @ PPy-Ag to the pure PCL is 1-16: 200.
further, the stirring is at least one of ultrasonic stirring and magnetic stirring.
Further, the stirring reaction time is 50-150min, and the temperature is 35-50 ℃.
S22, heating the mixed solution obtained in S21, and carrying out full magnetic stirring and ultrasonic stirring under the condition of heat preservation.
Further, the heat preservation temperature is 70-90 ℃.
Further, the stirring time is 100-.
S23, pouring the solution obtained in the step S22 in a horizontally placed polytetrafluoroethylene mold in a heat preservation drying oven to form a film, and obtaining the polypyrrole surface modified layered clay-polycaprolactone antibacterial nano composite film (LDHs @ PPy-Ag/PCL).
Further, the heat preservation temperature is 50-70 ℃.
The invention has the following advantages:
1) the interface compatibility and the binding force between the LDHs and the PCL substrate are increased by the organic surface coating substance PPy, so that the barrier property, the mechanical property and the like of the nano composite film are finally improved, and the composite film is endowed with antibacterial property.
2) The antibacterial rate of the LDHs @ PPy powder reaches 100%, the LDHs @ PPy powder has good interface compatibility with the PCL of the base material, and the LDHs @ PPy powder also has a heterogeneous nucleation effect in the base material. The tensile strength, the elongation at break and the oxygen permeability of the LDHs @ PPy/PCL nano composite material are greatly improved.
3) The preparation method of the polypyrrole/silver surface modified layered clay polycaprolactone antibacterial nano composite film provided by the invention is simple, the conditions are easy to control, and the preparation method is suitable for large-scale production.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an X-ray diffraction pattern of LDHs @ PPy-Ag and LDHs in example 1 of the present invention;
FIG. 2 is a Fourier infrared absorption spectrum of LDHs @ PPy-Ag in example 1 of the present invention;
FIG. 3 is a TEM micrograph of LDHs @ PPy-Ag in example 1 of the present invention;
FIG. 4 is an EDS spectrum of LDHs @ PPy-Ag in example 1 of the present invention;
FIG. 5 is a graph showing the antibacterial effect of LDHs @ PPy-Ag in example 1 of the present invention;
FIG. 6 is a graph showing the antibacterial effect of LDHs @ PPy-Ag/PCL in example 1 of the present invention;
Detailed Description
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which is prepared according to the following steps.
1) Preparation of LDHs @ PPy-Ag
0.05g of LDHs are weighed and dispersed in 50mL of deionized H2In O, ultrasonic stirring is carried out for 30min to obtain 0.5g/L LDHs dispersion. Then 0.12g of AgNO3 is weighed and dissolved in the LDHs dispersion liquid, ultrasonic stirring is carried out for 5min, magnetic stirring is carried out, adsorption is carried out for 30min, and the temperature is raised to 70 ℃. 1.2g Py were then metered in and added to 50mL of deionized H2And O, performing ultrasonic treatment for 10min until Py is completely dissolved. And finally, adding the Py aqueous solution into the LDHs dispersion liquid, magnetically stirring for 60min at the temperature of 70 ℃, and gradually turning the reaction liquid black. After the reaction is finished, performing centrifugal washing for three times, and freeze-drying to obtain black LDHs @ PPy-Ag powder.
2) Preparation of LDHs @ PPy-Ag/PCL composite film
Dissolving 0.014g of LDHs @ PPy-Ag and 1.4g of pure PCL in dimethylformamide, stirring for 90min at 40 ℃, continuously heating to 80 ℃, magnetically stirring for 100min, then carrying out ultrasonic treatment for 15min, pouring the mixture in a horizontally placed polytetrafluoroethylene mold in a drying oven at 60 ℃ to form a film, and obtaining the LDHs @ PPy-Ag/PCL composite antibacterial film after 90 min.
A flat plate colony counting method is adopted as an antibacterial performance test method, the antibacterial rate of the LDHs @ PPy-Ag antibacterial test result is 100 percent, see figure 5, and the antibacterial rate of the LDHs @ PPy-Ag/PCL antibacterial test result is 100 percent, see figure 6; LDHs @ PPy-Ag and LDHs diffraction patterns are shown in figure 1; and performing Fourier infrared absorption spectrogram analysis on the LDHs @ PPy-Ag, which is shown in figure 2; TEM micro-morphology analysis is carried out on the LDHs @ PPy-Ag, and the figure is shown in figure 3; EDS map analysis is carried out on the LDHs @ PPy-Ag, and the figure is shown in figure 4; the mechanical property analysis of the LDHs @ PPy-Ag/PCL nano composite film shows that when the addition amount of the LDHs @ PPy is only 1 wt%, the tensile strength and the elongation at break of the nano composite film are respectively increased by 35% and 23%, and the reduction amplitude of the oxygen permeability is also up to 44%.
Example 2
The embodiment provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which is prepared according to the following steps.
1) Preparation of LDHs @ PPy-Ag
0.05g of LDHs are weighed and dispersed in 50mL of deionized H2In O, ultrasonic stirring is carried out for 30min to obtain 0.5g/L LDHs dispersion. Then 0.05g of AgNO3 is weighed and dissolved in the LDHs dispersion liquid, ultrasonic stirring is carried out for 5min, magnetic stirring is carried out, adsorption is carried out for 20min, and the temperature is raised to 60 ℃. Then 1.0g Py was measured and added to 50mL deionised H2And O, performing ultrasonic treatment for 5min until Py is completely dissolved. And finally, adding the Py aqueous solution into the LDHs dispersion liquid, magnetically stirring for 120min at the temperature of 60 ℃, and gradually turning the reaction liquid black. After the reaction is finished, performing centrifugal washing for three times, and freeze-drying to obtain black LDHs @ PPy-Ag powder.
2) Preparation of LDHs @ PPy-Ag/PCL composite film
Dissolving 0.014g of LDHs @ PPy-Ag and 1.4g of pure PCL in dimethylformamide, stirring for 150min at 50 ℃, continuously heating to 70 ℃, magnetically stirring for 100min, then carrying out ultrasonic treatment for 20min, pouring the mixture in a horizontally placed polytetrafluoroethylene mold in a drying oven at 70 ℃ to form a film, and obtaining the LDHs @ PPy-Ag/PCL composite antibacterial film after 120 min.
Example 3
The embodiment provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which is prepared according to the following steps.
1) Preparation of LDHs @ PPy-Ag
0.05g of LDHs are weighed and dispersed in 50mL of deionized H2In O, ultrasonic stirring is carried out for 30min to obtain 0.5g/L LDHs dispersion. Then 0.075g of AgNO3 is weighed and dissolved in the LDHs dispersion liquid, the mixture is ultrasonically stirred for 5min, then the mixture is magnetically stirred and adsorbed for 30min, and the temperature is raised to 80 ℃. Then 0.375g Py was measured and added to 50mL deionised H2And O, performing ultrasonic treatment for 20min until Py is completely dissolved. And finally, adding the Py aqueous solution into the LDHs dispersion liquid, magnetically stirring for 200min at the temperature of 80 ℃, and gradually turning the reaction liquid black. After the reaction is finished, 5 times of centrifugal washing is carried out, and black LDHs @ PPy-Ag powder is obtained by freeze-drying.
2) Preparation of LDHs @ PPy-Ag/PCL composite film
Dissolving 0.10g of LDHs @ PPy-Ag and 1.4g of pure PCL in dimethylformamide, stirring for 120min at 35 ℃, continuously heating to 90 ℃, magnetically stirring for 100min, then carrying out ultrasonic treatment for 15min, pouring the mixture in a horizontally placed polytetrafluoroethylene mold in a drying oven at 50 ℃ to form a film, and obtaining the LDHs @ PPy-Ag/PCL composite antibacterial film after 60 min.
Example 4
The embodiment provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which is prepared according to the following steps.
1) Preparation of LDHs @ PPy-Ag
0.05g of LDHs are weighed and dispersed in 50mL of deionized H2In O, ultrasonic stirring is carried out for 30min to obtain 0.5g/L LDHs dispersion. Then 0.06g of AgF is weighed and dissolved in the LDHs dispersion liquid, ultrasonic stirring is carried out for 5min, magnetic stirring is carried out, adsorption is carried out for 30min, and the temperature is increased to 68 ℃. 0.825g of Py were subsequently metered in and added to 50mL of deionized H2And O, performing ultrasonic treatment for 20min until Py is completely dissolved. And finally, adding the Py aqueous solution into the LDHs dispersion liquid, magnetically stirring for 200min at the temperature of 68 ℃, and gradually turning the reaction liquid black. After the reaction is finished, centrifuging and washing for 3 times, and freeze-drying to obtain black LDHs @ PPy-Ag powder.
2) Preparation of LDHs @ PPy-Ag/PCL composite film
Dissolving 0.08g of LDHs @ PPy-Ag and 1.4g of pure PCL in dimethylformamide, stirring for 120min at 35 ℃, continuously heating to 90 ℃, magnetically stirring for 100min, then carrying out ultrasonic treatment for 15min, pouring the mixture in a horizontally placed polytetrafluoroethylene mold in a drying oven at 50 ℃ to form a film, and obtaining the LDHs @ PPy-Ag/PCL composite antibacterial film after 120 min.
Example 5
The embodiment provides a preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film, which is prepared according to the following steps.
1) Preparation of LDHs @ PPy-Ag
0.05g of LDHs are weighed and dispersed in 50mL of deionized H2In O, ultrasonic stirring is carried out for 30min to obtain 0.5g/L LDHs dispersion. Then 0.08g of AgClO4 is weighed and dissolved in LDHs dispersion liquid, ultrasonic stirring is carried out for 10min, then magnetic stirring is carried out, adsorption is carried out for 20min, and the temperature is raised to 75 ℃. Then 0.725g Py was measured and added to 50mL of deionized H2And O, performing ultrasonic treatment for 20min until Py is completely dissolved. And finally, adding the Py aqueous solution into the LDHs dispersion liquid, magnetically stirring for 120min at the temperature of 75 ℃, and gradually turning the reaction liquid black. After the reaction is finished, centrifuging and washing for 3 times, and freeze-drying to obtain black LDHs @ PPy-Ag powder.
2) Preparation of LDHs @ PPy-Ag/PCL composite film
Dissolving 0.09g of LDHs @ PPy-Ag and 1.4g of pure PCL in dimethylformamide, stirring for 120min at 35 ℃, continuously heating to 80 ℃, magnetically stirring for 100min, then carrying out ultrasonic treatment for 20min, pouring the mixture in a horizontally placed polytetrafluoroethylene mold in a drying oven at 60 ℃ to form a film, and obtaining the LDHs @ PPy-Ag/PCL composite antibacterial film after 90 min.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film is characterized by comprising the following steps:
s1 by using soluble Ag+The method comprises the following steps that (1) salt-initiated pyrrole Py performs a chemical oxidation-reduction reaction on the surface of layered clay LDHs to form nano-silver-containing polypyrrole PPy coated clay LDHs, so that polypyrrole surface modified layered clay antibacterial powder LDHs @ PPy-Ag is obtained;
the preparation method of the LDHs @ PPy-Ag antibacterial powder comprises the following steps:
s11 dissolving Ag in water+Dissolving salt in LDHs dispersion liquid with solubility of 0.5g/L, stirring, adsorbing, heating to 60-80 deg.C to obtain the product containing Ag+A dispersion of ionic LDHs;
s12 by controlling soluble Ag+Mass ratio of salt to Py, adding Py aqueous solution to Ag+Fully stirring, oxidizing and reducing in an ionic LDHs dispersion liquid to obtain an LDHs @ PPy-Ag dispersion liquid;
s13, carrying out centrifugal washing on the LDHs @ PPy-Ag dispersion liquid obtained in the step S12, and freeze-drying to obtain LDHs @ PPy-Ag powder; the stirring reaction time is 50-150min, and the temperature is 60-80 ℃;
s2, adopting solution pouring to perform film forming on the LDHs @ PPy-Ag and the polycaprolactone PCL which are obtained through the processing of S1, and preparing the polypyrrole surface modified layered clay and polycaprolactone antibacterial nano composite film LDHs @ PPy-Ag/PCL.
2. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film according to claim 1, wherein in step S2, the preparation of the LDHs @ PPy-Ag/PCL nano composite film comprises the following steps:
s21, dissolving the LDHs @ PPy-Ag powder and the pure PCL in dimethylformamide, fully stirring and uniformly mixing;
s22, heating the mixed solution obtained in the step S21, carrying out full magnetic stirring and ultrasonic stirring under the condition of heat preservation;
s23, pouring the solution obtained in the step S22 in a horizontally placed polytetrafluoroethylene mold in an insulation drying oven to form a film, and obtaining the polypyrrole surface modified layered clay-polycaprolactone antibacterial nano composite film LDHs @ PPy-Ag/PCL.
3. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film according to claim 1, wherein in step S11, the soluble Ag+The salt is AgF or AgNO3、AgClO4At least one of (1).
4. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nanocomposite film according to claim 1, wherein in step S11, the stirring is at least one of ultrasonic stirring and magnetic stirring, the stirring time is 5-10min, and the adsorption time is 30-60 min.
5. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nano composite film according to claim 1, wherein in step S12, the soluble Ag+The mass ratio of the salt to the Py is 1:5-20, and the stirring is at least one of ultrasonic stirring and magnetic stirring.
6. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nanocomposite film according to claim 2, wherein in step S21, the mass ratio of the LDHs @ PPy-Ag to pure PCL is 1-16: 200 of a carrier; the stirring is at least one of ultrasonic stirring and magnetic stirring, the stirring time is 50-150min, and the temperature is 35-50 ℃.
7. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nanocomposite film as claimed in claim 2, wherein in step S22, the heat preservation is performed under the process conditions of 70-90 ℃, magnetic stirring time of 100-200min, and then ultrasonic stirring time of 10-20 min.
8. The method for preparing polypyrrole/silver surface modified layered clay-polycaprolactone antibacterial nanocomposite film according to claim 2, wherein in step S23, the heat preservation is performed under the process conditions of 50-70 ℃ and 60-120 min.
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