CN115286791B - Inorganic salt@polypyrrole nano capsule and preparation method and application thereof - Google Patents

Inorganic salt@polypyrrole nano capsule and preparation method and application thereof Download PDF

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CN115286791B
CN115286791B CN202210980564.0A CN202210980564A CN115286791B CN 115286791 B CN115286791 B CN 115286791B CN 202210980564 A CN202210980564 A CN 202210980564A CN 115286791 B CN115286791 B CN 115286791B
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polypyrrole
inorganic salt
water
emulsion
capsule
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CN115286791A (en
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李丹
李欣
谭磊
郭生伟
邵欣
王固霞
闫骏
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North Minzu University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/14Polymerisation; cross-linking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • C08K2003/166Magnesium halide, e.g. magnesium chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • C08K2003/168Zinc halides

Abstract

The invention relates to a preparation method of an inorganic salt@polypyrrole capsule, which comprises the following steps of: (1) Mixing the water phase and the oil phase, and emulsifying to prepare water-in-oil emulsion; (2) Carrying out ultrasonic grinding and refining on the water-in-oil emulsion by using a cold water bath to obtain nano emulsion; (3) Placing the nano emulsion in a microwave reactor for pre-reaction; (4) Dripping pyrrole into the microwave reactor, and continuing to react to obtain the catalyst; the oil phase includes an emulsifier, an initiator, and a solvent, and the aqueous phase includes a core material, a dopant, and water. The invention also provides an inorganic salt@polypyrrole capsule prepared by the method and application thereof. The method provided by the invention can prepare the nanoscale capsule with uniform particle size and average particle size of 200-900nm, and has the advantages of simple preparation process, high efficiency, safety, low cost and good application prospect.

Description

Inorganic salt@polypyrrole nano capsule and preparation method and application thereof
Technical Field
The invention relates to the field of nanocapsules, in particular to an inorganic salt@polypyrrole nanocapsule, and a preparation method and application thereof.
The background technology is as follows:
the microcapsule technology has the effects of protecting core materials from environmental influences, shielding taste, color and smell, changing material state or surface properties, isolating active ingredients, reducing volatility and toxicity, controlling sustainable release of core materials and the like, and has been widely used. The technology for preparing microcapsules originated in the 30 s of the 20 th century and developed rapidly in the middle of the 70 s, during which many microencapsulated products and processes have emerged. The preparation technology of the microcapsule relates to the intersection of a plurality of disciplines, and mainly comprises physical and colloid chemistry, polymer chemistry and physics, material science and processing, dispersing and drying technology and the like. There are many methods for preparing microcapsules, about 200 being reported so far, which differ in details. The encapsulation process is mainly divided into three types, namely a chemical method, a physical method and a physicochemical method.
Microcapsule technology has applications in many areas, but mostly only to the micrometer scale, while nano-scale research or products are still relatively few for technical reasons. The concept of nanocapsules was first proposed by Narty et al at the end of the 70 s, and then research in the nanometer range was conducted, so that nanocapsules were found to have unique properties that enable new applications in many fields, particularly in research of pharmaceutical nanocapsules, good targeting and sustained release effects were found, and the nanocapsules can be applied to the fields of biomedical applications and the like. Along with the deep development of the nanocapsule technology, various techniques for preparing nanocapsules mainly comprise an emulsion polymerization method, an interfacial polymerization method, a drying bath method, a layer-by-layer nanometer self-assembly method, an electrostatic spraying method and the like. However, there are some problems in theory and application that are currently required to be studied intensively for the nanocapsule technology itself. Firstly, no convenient and feasible method or technical standard is available for preparing the nanocapsules. Secondly, the problems of high preparation cost and safety selection of wall materials and auxiliary materials are solved.
The solar cell is an electric device for directly converting light energy into electric energy through photovoltaic effect, and the perovskite solar cell which is the most popular in research at present has low exciton binding energy and charges are carried and are easy to separate at room temperature, so that the Photoelectric Conversion Efficiency (PCE) is not high, and the perovskite solar cell cannot be widely applied and developed. But by using polymer additives, PCE can be significantly improved and stability improved by controlling morphology. The growth rate of perovskite crystal grains is improved, meanwhile, the agglomeration phenomenon caused by the additives is reduced, and the uniformity and coverage of a perovskite layer can be improved. Polypyrrole is used as a conductive polymer for the perovskite layer, and polypyrrole is used as a conductive channel to promote the extraction of carriers and reduce the transportation of the carriers in the perovskite layer, so that a smooth perovskite layer with fewer gaps is formed, and the PCE of the perovskite solar cell can be improved. However, the PCE of perovskite solar cells cannot be greatly improved due to the lower conductivity of the conductive polymer. The conductive polymer microcapsule has the characteristics of conductivity and micron structure of the conductive polymer, so that the conductive polymer microcapsule has application value in the aspects of novel super capacitors, ion selective electrodes, biochemical sensors, biological medicines, solar cells and the like. Conductive polymer microcapsules have excellent properties such as controllable permeability, light weight, structural diversity, easy processing, good stability, and metal conductivity, and are receiving much attention. Among the conductive polymers, conductive polypyrrole has wide application range due to the advantages of easy preparation, no toxicity, strong stability, high hardness and the like.
Because the traditional treatment methods such as surgery, chemotherapy, radiotherapy and the like have unsatisfactory treatment effects on partially killing tumor cells, it is highly desirable to obtain efficient antitumor treatment. In recent years, microwave hyperthermia (MTT) has been widely considered as a promising clinical treatment method because of its simple operation, high efficiency, and small side effects. However, due to the limited ablation area of tumors, long microwave irradiation time and other problems, the recurrence rate after traditional MTT treatment is very high. Therefore, by introducing inorganic salt as a microwave sensitizer and coating the nano-capsule with polypyrrole, the wall material of the nano-capsule can be cleared through a self system due to lower cytotoxicity and good in vivo biocompatibility, so that no obvious side effect or drug resistance exists. Injecting into tumor area, performing microwave thermal therapy, and the microwave sensitizer promotes local rapid heating to high temperature, effectively inhibits tumor cell growth under mild microwave irradiation, kills tumor cells, and can improve heat diffusion and effective accumulation of the whole tumor area. The method is hopeful to become a promising biological safe therapeutic nano-drug for noninvasive treatment of deep tumors in vivo.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for preparing inorganic salt@polypyrrole nano capsules rapidly and efficiently, the prepared inorganic salt@polypyrrole nano capsules and application thereof.
In order to achieve the aim, the invention provides a preparation method of an inorganic salt@polypyrrole nano capsule, which comprises the following steps of:
(1) Mixing the water phase and the oil phase, and emulsifying to prepare water-in-oil emulsion;
(2) Carrying out ultrasonic grinding and refining on the water-in-oil emulsion by using a cold water bath to obtain nano emulsion;
(3) Placing the nano emulsion in a microwave reactor for pre-reaction;
(4) Dripping pyrrole into the microwave reactor, and continuing to react to obtain the catalyst;
the oil phase includes an emulsifier, an initiator, and a solvent, and the aqueous phase includes a core material, a dopant, and water.
Preferably or alternatively, the mass ratio of the aqueous phase to the oil phase is 1-5:40-50.
Preferably or alternatively, the mass ratio of the emulsifier, the initiator and the solvent in the oil phase is 0.5-2:1-3:45-50; preferably, the initiator is a peroxy-based initiator; preferably, the initiator is at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxybenzoate or di-tert-butyl peroxide; preferably, the emulsifier is at least one of span 80 and tween 80; preferably, the solvent is toluene.
Preferably or alternatively, the mass ratio of core material, dopant and water in the aqueous phase is 0.1-1:10-20:80-90; preferably, the core material is an inorganic salt; preferably, the core material is any one of sodium chloride, lithium chloride, magnesium chloride, zinc chloride and potassium chloride; preferably, the dopant is sodium dodecyl benzene sulfonate.
Preferably or alternatively, in step (1), the emulsification process is high shear emulsification.
Preferably or alternatively, the time of the cold water bath ultrasonic treatment in the step (2) is 1-10min, and the power is 15-105W; preferably, the ultrasonic time is 2min and the power is 45W.
The sheared micron-sized emulsion can be changed into nanometer-sized emulsion by cold water bath ultrasonic.
Preferably or alternatively, in the step (3), the pre-reaction time is 1-30min, the pre-reaction temperature is 40-70 ℃ and the microwave power is 100-700W; preferably, the pre-reaction time is 5min, the pre-reaction temperature is 50 ℃ and the microwave power is 500W.
Preferably or optionally, in the step (4), the mass ratio of pyrrole to the core material is 1:2, the reaction time is 1-30min, the reaction temperature is 40-70 ℃, and the microwave power is 100-700W; preferably, the reaction time is 5min, the reaction temperature is 50 ℃, and the microwave power is 500W.
The speed and efficiency of the hydrothermal polymerization reaction can be greatly accelerated by microwaves.
The invention also provides an inorganic salt@polypyrrole capsule which is prepared by adopting the preparation method of the inorganic salt@polypyrrole capsule.
On the other hand, the invention also provides application of the inorganic salt@polypyrrole capsule in preparing a solar cell and application of the inorganic salt@polypyrrole capsule in tumor treatment.
The inorganic salt@polypyrrole capsule and the preparation method and application thereof provided by the invention can be used for preparing the nanoscale capsule with uniform particle size and average particle size of 200-900nm, and the preparation process is simple, efficient, safe and low in cost, and the prepared inorganic salt@polypyrrole capsule can be applied to perovskite solar cells to improve the photoelectric conversion efficiency of the perovskite solar cells, and can be applied to tumor treatment to effectively inhibit the growth of tumor cells and kill the tumor cells under mild microwave irradiation.
Drawings
FIG. 1 is a scanning electron microscope image of inorganic salt @ polypyrrole nano capsule of example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of inorganic salt @ polypyrrole nano capsule of example 6 of the present invention.
Fig. 3 is a J-V plot of perovskite solar cells with addition of inorganic salts @ polypyrrole nano capsules and pure polypyrrole of examples 1-4 of this invention.
FIG. 4 is a graph of time temperature of inorganic salt @ polypyrrole nano capsule with different inorganic salt content.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of sodium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 5min at 50 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 2
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of zinc chloride, and 0.031g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 10min at 50 ℃ by using 600W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 3
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of magnesium chloride, and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and performing microwave reaction at 50 ℃ for 20min by using 700W to gradually darken the emulsion from milky white to dark brown to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 4
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of potassium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 10min at 60 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 5
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of lithium chloride, and 0.031g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 20min at 60 ℃ by using 600W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 6
Uniformly mixing an emulsifier compounded by 0.835g of span 80 and tween 80 in a mass ratio of 4:1 with 75mL of toluene, and adding 1.67g of benzoyl peroxide to prepare an oil phase;
5mL deionized water, 0.625g sodium chloride, and 0.063g sodium dodecylbenzenesulfonate were mixed to make an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 5min at 60 ℃ by using 700W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 7
Uniformly mixing an emulsifier compounded by 3g of span 80 and tween 80 according to a mass ratio of 4:1 and 75mL of toluene, and adding 4.5g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1.11g of zinc chloride, and 0.056g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 20min at 70 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark brown from milky white, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 8
Uniformly mixing an emulsifier compounded by 1.98g of span 80 and tween 80 according to a mass ratio of 4:1 and 75mL of toluene, and adding 3.16g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 0.9g of lithium chloride, and 0.033g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 5min at 70 ℃ by using 600W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 9
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of potassium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 10min at 70 ℃ by using 700W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 10
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 0.5g of sodium chloride, and 0.031g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 5min at 50 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 11
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1.4g of sodium chloride, and 0.031g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 10min at 50 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Example 12
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1.8g of sodium chloride, and 0.031g of sodium dodecylbenzenesulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 2min under the ultrasonic power of 45W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 10min at 50 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole nano capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Comparative example 1
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of sodium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a cold water bath, and performing ultrasonic treatment for 10min under the ultrasonic power of 105W to obtain the nano emulsion.
And (3) placing the nano emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 60min at 50 ℃ by using 200W microwaves, wherein the emulsion color gradually becomes dark brown from milky white, so as to prepare the inorganic salt@polypyrrole capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Comparative example 2
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of sodium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
And (3) placing the water-in-oil emulsion in a microwave reaction bottle, dropwise adding 2.5mL of pyrrole, and reacting for 5min at 50 ℃ by using 500W microwaves, wherein the emulsion color gradually becomes dark from milky white to dark brown, so as to prepare the inorganic salt@polypyrrole capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Comparative example 3
Uniformly mixing an emulsifier compounded by 1.25g of span 80 and tween 80 according to a mass ratio of 4:1 with 75mL of toluene, and adding 3g of benzoyl peroxide to prepare an oil phase;
5mL of deionized water, 1g of sodium chloride and 0.031g of sodium dodecyl benzene sulfonate were mixed to prepare an aqueous phase;
mixing the water phase and the oil phase, and shearing and emulsifying for 10min at 8000rpm to obtain water-in-oil emulsion.
Placing the water-in-oil emulsion into a round bottom flask, and stirring for 30min in a water bath kettle at 65 ℃ to realize the prepolymerization of the system;
2.5mL of pyrrole is added dropwise, the emulsion color gradually becomes dark brown from milky white, and the reaction is continued for 2 hours at 65 ℃ to prepare the inorganic salt@polypyrrole capsule.
The prepared inorganic salt@polypyrrole capsule is subjected to vacuum filtration, washing and drying to obtain a powdery fine particle product which can be practically applied.
Effect example 1
The products prepared in examples 1-9 and comparative examples 1-3 were characterized by scanning electron microscopy, projection electron microscopy, particle size analyzer, with the following results:
the capsules prepared in the example 1 are uniform in shape, full in particles, uniform in dispersion, spherical, 390nm in average particle size and nano-scale capsules with core-shell structures; the scanning electron microscope diagram of the product is shown in figure 1;
the capsules prepared in the example 2 are uniform in shape, full in particles, uniform in dispersion, spherical, 570nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in example 3 are uniform in shape, full in particles, uniform in dispersion, spherical, 920nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in example 4 are uniform in shape, full in particles, uniform in dispersion, spherical, 390nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in the example 5 are uniform in shape, full in particles, uniform in dispersion, spherical, 590nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in example 6 are uniform in shape, full in particles, uniform in dispersion, spherical, 430nm in average particle size and nano-scale capsules with core-shell structures; the transmission electron microscope diagram of the product is shown in figure 2;
the capsules prepared in example 7 are uniform in shape, full in particles, uniform in dispersion, spherical, 430nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in example 8 are uniform in shape, full in particles, uniform in dispersion, spherical, 440nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in example 9 are uniform in shape, full in particles, uniform in dispersion, spherical, 430nm in average particle size and nano-scale capsules with core-shell structures;
the capsules prepared in comparative example 1 have different shapes, are wrinkled and dispersed uniformly, have average particle size of 1540nm, are micron-sized capsules with a part of core-shell structure, and are not prepared into nano-sized capsules;
the capsule wall material prepared in comparative example 2 had wrinkles, was unevenly dispersed, was unevenly shaped, had an agglomeration phenomenon, had an average particle diameter of 2670nm, and was partially a core-shell structured micron-sized capsule, and was not prepared as a nano-sized capsule.
The capsules prepared in comparative example 3 are uniform in shape, are not smooth and uniformly dispersed, are spherical, have average particle diameters of 45000nm and are micron-sized capsules with core-shell structures;
effect example 2
2.0mg of the products prepared in examples 1 to 9 and comparative examples 1 to 2 and pure polypyrrole were weighed out respectively, dissolved in 1.0mL of isopropyl alcohol, stirred well and filtered to obtain a filtrate.
In the preparation process of the perovskite solar cell, after spin coating and annealing of the perovskite absorption layer, spin coating the prepared filtrate on the perovskite absorption layer, passivating the absorption layer, then preparing a hole transmission layer, evaporating a gold film with the thickness of 80nm on the hole transmission layer by using vacuum evaporation equipment to serve as an electrode, obtaining a perovskite solar cell product, and testing the photoelectric conversion efficiency of the perovskite solar cell product added with inorganic salt@polypyrrole capsules or pure polypyrrole.
The photoelectric conversion efficiency of the perovskite solar cell products to which the respective examples and comparative example products were added are shown in table 1.
Table 1 table of photoelectric conversion efficiency results of perovskite solar cell products to which each group of products was added
The J-V curves for perovskite solar cell products added with the products prepared in examples 1-4 and pure polypyrrole were plotted as shown in FIG. 3.
Effect example 3
35.0mg of the product prepared in example 1 and examples 10 to 12 and pure polypyrrole were weighed respectively, dissolved in 1.0mL of physiological saline, stirred and dissolved sufficiently, 0.5mL of the solution and the physiological saline were respectively compared, subjected to in vitro microwave irradiation, and observed by an infrared thermal imager to draw a time-temperature curve, as shown in FIG. 4.
The maximum temperatures of the in vitro microwave radiation products with the addition of the pure polypyrrole and physiological saline products of the examples are shown in Table 2.
TABLE 2 Table of the maximum temperature results for the in vitro microwave radiation products with the addition of the various groups of products
Group of Highest temperature (. Degree. C.)
Example 1 50.00
Example 10 42.40
Example 11 51.00
Example 12 52.00
Pure polypyrrole 39.30
Physiological saline 37.10
The results of the combination effect examples 1,2 and 3 show that the method further pulverizes the sheared micron-sized emulsion into the nanometer-sized emulsion by introducing cold water bath ultrasonic effect into the emulsion system and optimizing the parameters of the microwave process, thereby playing a good role in subsequent microwave polymerization to form the nano capsule and realizing the efficient preparation of the inorganic salt@polypyrrole nano capsule. Meanwhile, the prepared inorganic salt@polypyrrole nano capsule can remarkably improve the photoelectric conversion efficiency of the perovskite solar cell, has good application prospect, has local rapid heating and high temperature in microwave tumor treatment, and can improve the heat diffusion and effective accumulation of the whole tumor area. Is expected to become a promising biological safe therapeutic nano-drug for the noninvasive treatment of deep tumors in vivo.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (11)

1. The preparation method of the inorganic salt@polypyrrole nanocapsule is characterized by comprising the following steps of:
(1) Mixing the water phase and the oil phase, and emulsifying to prepare water-in-oil emulsion; the oil phase comprises an emulsifier, an initiator and a solvent, and the water phase comprises a core material, a doping agent and water; the mass ratio of the emulsifier to the initiator to the solvent in the oil phase is 0.5-2:1-3:45-50; the mass ratio of the core material to the doping agent to the water in the water phase is 10-20:0.1-1:80-90; the core material is any one of sodium chloride, lithium chloride, magnesium chloride, zinc chloride and potassium chloride; the doping agent is sodium dodecyl benzene sulfonate;
(2) Carrying out ultrasonic grinding and refining on the water-in-oil emulsion by using a cold water bath to obtain nano emulsion; the ultrasonic time is 2min, and the power is 45W;
(3) Placing the nano emulsion in a microwave reactor for pre-reaction; the pre-reaction time is 1-30min, the pre-reaction temperature is 40-70 ℃, and the microwave power is 100-700W;
(4) Dripping pyrrole into the microwave reactor, and continuing to react to obtain the catalyst; wherein the mass ratio of pyrrole to the core material is 1:2, the reaction time is 1-30min, the reaction temperature is 40-70 ℃, the microwave power is 100-700W, the reaction time is 5min, the reaction temperature is 50 ℃, and the microwave power is 500W.
2. The method for preparing inorganic salt@polypyrrole nanocapsules according to claim 1, wherein the mass ratio of the aqueous phase to the oil phase is 1-5:40-50.
3. The method for preparing inorganic salt@polypyrrole nanocapsules according to claim 1, wherein the initiator is a peroxy initiator.
4. The method for preparing inorganic salt@polypyrrole nanocapsules according to claim 3, wherein the initiator is at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxybenzoate or di-tert-butyl peroxide.
5. The method for preparing inorganic salt @ polypyrrole nanocapsules of claim 1, wherein the emulsifier is at least one of span 80 and tween 80.
6. The method for preparing inorganic salt @ polypyrrole nanocapsules of claim 1, wherein the solvent is toluene.
7. The method for preparing inorganic salt@polypyrrole nanocapsules according to claim 1, wherein in the step (1), the emulsifying process is high-speed shearing emulsification.
8. The method for preparing inorganic salt@polypyrrole nanocapsules according to claim 1, wherein in the step (3), the pre-reaction time is 5min, the pre-reaction temperature is 50 ℃, and the microwave power is 500W.
9. The inorganic salt@polypyrrole nanocapsule is characterized by being prepared by a preparation method of the inorganic salt@polypyrrole nanocapsule according to any one of claims 1-8.
10. Use of the inorganic salt @ polypyrrole nanocapsules of claim 9 in the preparation of solar cells.
11. The use of the inorganic salt @ polypyrrole nanocapsule of claim 9 in a medicament for treating tumors by microwaves.
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