CN113754931B - Chitosan microsphere bio-based flame retardant with core-shell structure and preparation method and application thereof - Google Patents
Chitosan microsphere bio-based flame retardant with core-shell structure and preparation method and application thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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Abstract
The invention discloses a chitosan microsphere bio-based flame retardant with a core-shell structure, which structurally comprises chitosan microspheres and phytic acid coated on the surfaces of the chitosan microspheres. The specific structure and composition of the flame retardant enable the flame retardant to have environment-friendly, good flame retardance and physical and mechanical properties. The invention also discloses a preparation method and application of the flame retardant.
Description
Technical Field
The present invention relates to the field of flame retardancy of polymers. More particularly, relates to a chitosan microsphere bio-based flame retardant with a core-shell structure, and a preparation method and application thereof.
Background
The flame retardant is used as an auxiliary agent for improving the combustion performance of polymer materials, and is widely applied to products of daily life products, electronic and electric products and the like. Conventional flame retardants are highly flame retardant and inexpensive, but may have adverse environmental effects and are generally derived from petrochemical resources. With the increasing deterioration of global environment and the exhaustion of non-renewable petrochemical resources, the development of environment-friendly green flame retardants has become an important direction for the development of flame retardants. Bio-based compounds are receiving increasing attention due to their environmental protection, safety, and abundant sources, among which natural substances that have been reported to be useful for flame retardancy of polymers include chitosan, isosorbide, tannic acid, phytic acid, lignin, and the like.
Polylactic acid is a biodegradable polymer, is completely degradable in natural environment, and is a recognized environment-friendly material. However, the flame retardants commonly used for flame retarding polylactic acid at present include phosphorus nitrogen compounds, intumescent flame retarding systems and the like, most of the components of the flame retardants are derived from petroleum-based resources, and the environmental friendliness of polylactic acid is damaged. In recent years, some biomass flame retardants have attracted attention, among which chitosan, phytic acid, proteins, amino acids, sodium alginate, etc. have been proven to be useful for polymer flame retardancy. The bio-based flame retardant is derived from natural animals and plants, is degradable in natural environment, and has the advantages of low price, easy obtainment and environmental friendliness.
Disclosure of Invention
Based on the defects of the prior art, the first object of the invention is to provide a chitosan microsphere bio-based flame retardant with a core-shell structure, wherein the specific structure and composition of the flame retardant enable the flame retardant to have environment-friendly, good flame retardancy and physical and mechanical properties.
The second purpose of the invention is to provide a preparation method of the chitosan microsphere bio-based flame retardant with the core-shell structure.
The second purpose of the invention is to provide the application of the chitosan microsphere bio-based flame retardant with the core-shell structure.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a chitosan microsphere bio-based flame retardant with a core-shell structure comprises chitosan microspheres and phytic acid coated on the surfaces of the chitosan microspheres.
Further, the particle size distribution of the flame retardant is between 2 and 6 μm.
Further, the chitosan microspheres and phytic acid are subjected to electrostatic adsorption.
Further, the mass ratio of the chitosan microspheres to the phytic acid is 1:1-1: 5.
Further, the chitosan microspheres are obtained by emulsifying and crosslinking chitosan, centrifuging and washing.
Further, the emulsifying method comprises the following steps: mixing liquid paraffin, chitosan solution and emulsifier, and stirring.
Further, the volume ratio of the chitosan solution to the liquid paraffin is 1:2-1:6, and the volume ratio of the chitosan solution to the emulsifier is 6:1-12: 1.
Furthermore, the rotating speed of the stirring is 300r/min-900 r/min.
Further, the time of emulsification is 1-5 hours.
Further, the cross-linking agent used for cross-linking is selected from one or more of glutaraldehyde, glyoxal and genipin.
Further, the volume ratio of the chitosan solution to the cross-linking agent is 3:1-6: 1.
Further, the temperature of the crosslinking is 40-90 ℃, and the time is 3-15 hours.
Furthermore, in the chitosan solution, the solvent is the mixture of glacial acetic acid and deionized water according to the volume ratio of 2% -5%.
Further, the concentration of the chitosan solution is 3mg/L-10 mg/L.
Further, the rotating speed of the centrifugation is 6000r/min-10000 r/min.
Further, the washing liquid used for washing is petroleum ether and isopropanol; wherein the washing speed of petroleum ether and isopropanol is 5000r/min-8000 r/min.
Further, the emulsifier is Span 80.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of a chitosan microsphere bio-based flame retardant with a core-shell structure comprises the following steps:
dispersing the chitosan microspheres in deionized water to obtain an aqueous solution of the chitosan microspheres;
and adding a phytic acid aqueous solution into the chitosan microsphere aqueous solution, reacting, vacuum-filtering, washing and drying to obtain the flame retardant.
Furthermore, in the aqueous solution of the chitosan microspheres, the concentration of the chitosan microspheres is 2.5 wt% -12.5 wt%.
Furthermore, the concentration of the phytic acid in the phytic acid aqueous solution is 3.5-14 wt%.
Further, the drying mode is freeze drying or vacuum drying at the temperature of 30-80 ℃.
In order to achieve the third purpose, the invention adopts the following technical scheme:
use of a flame retardant as described in the first object above for the manufacture of a plastic article.
Further, the matrix material of the plastic product is polylactic acid.
Further, the addition amount of the flame retardant in the base material is 1 to 15 wt%.
The invention has the following beneficial effects:
in the flame retardant provided by the invention, the chitosan and the phytic acid are derived from biomass, are abundant in storage and renewable, and do not cause pollution to the environment; in the flame retardant, phytic acid is coated on the surface of chitosan to form a core-shell structure, and the chitosan and the phytic acid are further combined together under the action of electrostatic force, so that the synthesis condition is mild and the efficiency is high; the diameter of the obtained flame retardant is distributed between 2 and 6 microns, and the specific structure and composition of the flame retardant endow the flame retardant with good flame retardance and higher mechanical properties. In addition, the flame retardant is used in a matrix such as polylactic acid and can be used as a nucleating agent to improve the crystallinity of materials, so that the problem of reduced mechanical properties caused by large addition amount of the flame retardant is solved.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows an infrared spectrum of the flame retardant prepared in example 1.
Fig. 2 shows SEM images of the chitosan microspheres (a) and the flame retardant (b) prepared in example 1.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar components in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
540mL of liquid paraffin, 18mLSpan80 and 180mL of chitosan acetic acid solution with the concentration of 4mg/L are added into a three-neck flask, wherein the volume concentration of acetic acid is 2% (V/V), the fixed stirring speed is 400r/min, and the mixture is emulsified for 1 hour at normal temperature; the temperature is raised to 60 ℃, 36mL of 25% glutaraldehyde solution is added, and the reaction is carried out for 6 hours. And centrifuging and demulsifying the product at 8000r/min, washing with petroleum ether twice at 6000r/min and washing with isopropanol twice at 5000r/min to obtain the yellow solid chitosan microspheres. Dispersing the yellow solid in a deionized water solution, wherein the mass concentration of the yellow solid is 2.5 wt%; and (3) dropwise adding 100mL of phytic acid solution with the concentration of 3.5%, fully reacting, and carrying out suction filtration and washing to obtain the flame retardant.
The infrared spectrum of the flame retardant is shown in figure 1, wherein CHTM is the infrared curve of the chitosan microsphere, PA is the infrared curve of phytic acid, and PA @ CHTM is the infrared curve of the phytic acid-coated chitosan microsphere flame retardant.
The SEM image of the obtained chitosan microspheres is shown as a in FIG. 2, and the SEM image of the obtained flame retardant is shown as b in FIG. 2.
Example 2
540mL of liquid paraffin, 18mL of SSPan 80 and 180mL of chitosan acetic acid solution with the concentration of 6mg/L are added into a three-neck flask, wherein the volume concentration of acetic acid is 2% (V/V), the fixed stirring speed is 400r/min, and emulsification is carried out for 1 hour at normal temperature; the temperature is raised to 60 ℃, 36mL of 25% glutaraldehyde solution is added, and the reaction is carried out for 6 hours. And centrifuging and demulsifying the product at 8000r/min, washing with petroleum ether twice at 6000r/min and washing with isopropanol twice at 5000r/min to obtain the yellow solid chitosan microspheres. Dispersing the yellow solid in a deionized water solution, wherein the mass concentration of the yellow solid is 2.5 wt%; and (3) dropwise adding 100mL of phytic acid solution with the concentration of 3.5%, fully reacting, and performing suction filtration and washing to obtain the flame retardant.
Example 3
540mL of liquid paraffin, 18mL of SSPan 80 and 180mL of chitosan acetic acid solution with the concentration of 4mg/L are added into a three-neck flask, wherein the volume concentration of acetic acid is 2% (V/V), the fixed stirring speed is 400r/min, and emulsification is carried out for 1 hour at normal temperature; the temperature was raised to 60 ℃ and then 40mL of a 25% glutaraldehyde solution was added and the reaction was carried out for 6 hours. And centrifuging the product at 8000r/min for demulsification, washing with petroleum ether twice at 6000r/min, and washing with isopropanol twice at 5000r/min to obtain yellow solid chitosan microspheres. Dispersing the yellow solid in a deionized water solution, wherein the mass concentration of the yellow solid is 2.5 wt%; and (3) dropwise adding 100mL of phytic acid solution with the concentration of 3.5%, fully reacting, and performing suction filtration and washing to obtain the flame retardant.
Example 4
540mL of liquid paraffin, 18mLSpan80 and 180mL of chitosan acetic acid solution with the concentration of 4mg/L are added into a three-neck flask, wherein the volume concentration of acetic acid is 2% (V/V), the fixed stirring speed is 400r/min, and the mixture is emulsified for 1 hour at normal temperature; the temperature is raised to 60 ℃, and then 36mL of 25% glutaraldehyde solution is added to react for 6 hours. And centrifuging the product at 8000r/min for demulsification, washing with petroleum ether twice at 6000r/min, and washing with isopropanol twice at 5000r/min to obtain yellow solid chitosan microspheres. Dispersing yellow solid in deionized water solution, wherein the mass concentration of the yellow solid is 5 wt%; and (3) dropwise adding 100mL of phytic acid solution with the concentration of 3.5%, fully reacting, and performing suction filtration and washing to obtain the flame retardant.
Example 5
540mL of liquid paraffin, 18mLSpan80 and 180mL of chitosan acetic acid solution with the concentration of 4mg/L are added into a three-neck flask, wherein the volume concentration of acetic acid is 2% (V/V), the fixed stirring speed is 400r/min, and the mixture is emulsified for 1 hour at normal temperature; the temperature is raised to 60 ℃, 36mL of 25% glutaraldehyde solution is added, and the reaction is carried out for 6 hours. And centrifuging the product at 8000r/min for demulsification, washing with petroleum ether twice at 6000r/min, and washing with isopropanol twice at 5000r/min to obtain yellow solid chitosan microspheres. Dispersing the yellow solid in a deionized water solution, wherein the mass concentration of the yellow solid is 2.5 wt%; and (3) dropwise adding 100mL of 5% phytic acid solution, fully reacting, and performing suction filtration and washing to obtain the flame retardant.
Comparative example 1
Example 1 was repeated except that phytic acid was changed to folic acid and the remaining conditions were not changed to prepare a flame retardant.
Comparative example 2
Example 1 was repeated except that the concentration of phytic acid was changed to 1% and the remaining conditions were not changed to prepare a flame retardant.
Melting and blending the flame retardant and polylactic acid in an internal mixer, controlling the temperature at 180 ℃, and mixing for 5min to obtain the chitosan microsphere flame-retardant polylactic acid material, wherein when the addition amount is 15%, the test results of various properties of the material are shown in table 1.
TABLE 1
It should be understood that the above-described embodiments of the present invention are examples for clearly illustrating the invention, and are not to be construed as limiting the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications can be made on the basis of the above description, and it is not intended to exhaust all embodiments, and obvious changes and modifications can be made on the basis of the technical solutions of the present invention.
Claims (17)
1. The chitosan microsphere bio-based flame retardant with the core-shell structure is characterized in that the structure of the flame retardant comprises chitosan microspheres and phytic acid coated on the surfaces of the chitosan microspheres;
the particle size distribution of the flame retardant is between 2 and 6 mu m;
the chitosan microspheres and phytic acid are electrostatically adsorbed;
the mass ratio of the chitosan microspheres to the phytic acid is 1:1-1: 5.
2. The flame retardant according to claim 1, wherein the chitosan microspheres are obtained by emulsifying, crosslinking, centrifuging and washing chitosan.
3. The flame retardant of claim 2, wherein the emulsifying method is: mixing liquid paraffin, chitosan solution and emulsifier, and stirring.
4. The flame retardant of claim 3, wherein the volume ratio of the chitosan solution to the liquid paraffin is 1:2 to 1:6, and the volume ratio of the chitosan solution to the emulsifier is 6:1 to 12: 1.
5. The flame retardant of claim 3, wherein the stirring speed is 300r/min to 900 r/min.
6. Flame retardant according to claim 3, wherein the time of emulsification is 1-5 hours.
7. The flame retardant according to claim 3, wherein the crosslinking agent used for crosslinking is one or more selected from glutaraldehyde, glyoxal and genipin.
8. The flame retardant of claim 7, wherein the volume ratio of the chitosan solution to the cross-linking agent is 3:1 to 6: 1.
9. Flame retardant according to claim 7, wherein the cross-linking is carried out at a temperature of 40 ℃ to 90 ℃ for a period of 3 to 15 hours.
10. The flame retardant of claim 3, wherein the solvent in the chitosan solution is a mixture of glacial acetic acid and deionized water in a volume ratio of 2-5%.
11. The flame retardant of claim 10, wherein the chitosan solution has a concentration of 3mg/L to 10 mg/L.
12. A process for the preparation of a flame retardant according to any of claims 1 to 11, comprising the steps of:
dispersing the chitosan microspheres in deionized water to obtain an aqueous solution of the chitosan microspheres;
and adding a phytic acid aqueous solution into the chitosan microsphere aqueous solution, reacting, vacuum-filtering, washing and drying to obtain the flame retardant.
13. The preparation method of claim 12, wherein the concentration of the chitosan microspheres in the aqueous solution of the chitosan microspheres is 2.5 wt% to 12.5 wt%; in the phytic acid aqueous solution, the concentration of the phytic acid is 3.5-14 wt%.
14. The method of claim 12, wherein the drying is by freeze-drying or vacuum-drying at a temperature of 30-80 ℃.
15. Use of a flame retardant according to any of claims 1-11 for the preparation of a plastic article.
16. Use according to claim 15, wherein the matrix material of the plastic article is polylactic acid.
17. Use according to claim 16, wherein the flame retardant is added in an amount of 1-15 wt% in the matrix material.
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| CN114214750B (en) * | 2022-01-13 | 2023-09-15 | 天津工业大学 | Flame-retardant polyacrylonitrile composite fiber and preparation method and application thereof |
| CN114539623B (en) * | 2022-02-24 | 2023-06-30 | 华北科技学院(中国煤矿安全技术培训中心) | Application of chitosan-based flame retardant in polyurethane |
| CN115433395B (en) * | 2022-07-12 | 2023-12-26 | 华南理工大学 | Chitosan-based N/P/B three-element synergistic flame retardant and preparation method and application thereof |
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