CN113429576B - Preparation method and application of biomass-based low-surface-energy bionic coating material - Google Patents
Preparation method and application of biomass-based low-surface-energy bionic coating material Download PDFInfo
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- CN113429576B CN113429576B CN202110756178.9A CN202110756178A CN113429576B CN 113429576 B CN113429576 B CN 113429576B CN 202110756178 A CN202110756178 A CN 202110756178A CN 113429576 B CN113429576 B CN 113429576B
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Abstract
The invention discloses a preparation method and application of a biomass-based low-surface-energy bionic coating material, wherein the preparation method comprises the following operation steps: 1) Pretreating biomass cellulose with alkali liquor or microwave, oxidizing pretreated biomass cellulose with Tempo, and C 6 Oxidizing hydroxyl on the position into carboxyl to prepare oxidized carboxyl cellulose; 2) Dispersing short fluorocarbon monomers into ultrafine particles by using an emulsifying agent, then adding an initiator to initiate monomer emulsion polymerization, and adding amino-containing acrylic acid salt to participate in polymerization in the later period of the polymerization reaction to prepare a short fluorocarbon oligomer with the polymerization degree of 50-60; 3) And (3) mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction for 1 hour at the reaction temperature of 50 ℃ to enable the short fluorocarbon oligomer to be grafted to the C6 position of the carboxyl cellulose to form a low-surface-energy micro-nano structure, thus obtaining the biomass-based low-surface-energy bionic coating material. The biomass-based low-surface-energy bionic coating material can better play the roles of super-hydrophobicity, pollution resistance and self-cleaning, and has good performance when being applied to the field of hydrophobic oleophobic pollution-resistance self-cleaning coatings.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a preparation method and application of a biomass-based low-surface-energy bionic coating material with a micro-nano structure.
Background
With the development of modern technological society and the change of natural environment, the demands of people for novel functionalized low-surface-energy materials are urgent, such as corrosion of natural stain pollution to houses outside cities, corrosion of marine fouling organisms to ships and marine drilling platforms, and when viruses are abused, the preparation of novel antibacterial spray, self-cleaning mask of novel paint, establishment of sterile antibacterial coating medical channels and the like, so that development of a low-surface-energy material with hydrophobic and oleophobic self-cleaning antibacterial property is urgent. In recent years, researchers prepare bionic lotus leaf hydrophobic surfaces by adopting various methods, such as a template method, an electrostatic spinning method, a spraying method, an etching method, a self-assembly method and the like, but the preparation methods have the defects of expensive equipment and materials, long production period, possibility of incapability of repeatedly obtaining some materials and the like in the process conditions, and have certain limitations. The chemical synthesis method has the advantages of simple operation, strong plasticity, low cost, high efficiency and the like, and becomes a research hotspot in the field. However, the long fluorocarbon chain compound (the number of fluorine atoms in the fluorine-containing monomer is more than 8) adopted in the traditional chemical synthesis has high synthesis cost, is difficult to degrade in nature, and is more and more limited in use.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a biomass-based low-surface-energy bionic coating material, and the bionic coating material obtained by the method is environment-friendly, can realize a hydrophobic and oleophobic effect, and has self-cleaning and antibacterial capabilities.
The invention solves the technical problems with the following technical proposal:
the invention discloses a preparation method of a biomass-based low-surface-energy bionic coating material, which comprises the following operation steps:
step 1: pretreating biomass cellulose with alkali liquor or microwave, oxidizing pretreated biomass cellulose with Tempo, and C 6 Oxidizing hydroxyl on the position into carboxyl to prepare oxidized carboxyl cellulose;
step 2: dispersing short fluorocarbon monomers into ultrafine particles by using an emulsifying agent, then adding an initiator to initiate monomer emulsion polymerization, and adding amino-containing acrylic acid salt to participate in polymerization in the later period of the polymerization reaction to prepare a short fluorocarbon oligomer with the polymerization degree of 50-60;
step 3: and (3) mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction for 1 hour at the reaction temperature of 50 ℃ to enable the short fluorocarbon oligomer to be grafted to the C6 position of the carboxyl cellulose to form a low-surface-energy micro-nano structure, thus obtaining the biomass-based low-surface-energy bionic coating material.
In the step 1, the biomass cellulose is pulp cellulose, microcrystalline cellulose, nano cellulose or pulp cellulose.
In the step 1, when the biomass cellulose is pretreated by alkali liquor, the biomass cellulose is soaked in the alkali liquor with the mass concentration of 9% so as to open a crystallization area of the biomass cellulose.
In the step 1, when biomass cellulose is pretreated by microwaves, the biomass cellulose is placed in microwave equipment with the microwave frequency of 2450MHz and the microwave power of 210W for microwave irradiation pretreatment so as to open a crystallization area of the biomass cellulose.
In the step 1, when the biomass cellulose is subjected to oxidation treatment, mixing the Tempo and the biomass cellulose according to the mass ratio of 0.5:1, then placing the mixture in an aqueous solution, carrying out oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃, and carrying out suction filtration to obtain the carboxyl cellulose.
In the step 2, the short fluorocarbon monomer is trifluoroethyl acrylate or hexafluorobutyl acrylate; the initiator is persulfate or Azobisisobutyronitrile (AIBN); the emulsifier is span 80; the mass ratio of the addition of the emulsifier to the fluorine-containing monomer is 3:5, the mass ratio of the addition of the initiator to the fluorine-containing monomer is 3:5, and the mass ratio of the addition of the amino-containing acrylate to the fluorine-containing monomer is 2:5.
In the step 2, the amino-containing acrylic acid salt is synthesized by mixing acrylic acid and dichloroethylenediamine hydrochloride according to the mass ratio of 1:1 through oxidation-reduction reaction.
The biomass-based low-surface-energy bionic coating material, namely the bionic lotus coating material with the hydrophobic and oleophobic properties, is used as an advanced multifunctional coating to be applied to paper and textile materials, and is coated on the surfaces of the paper, silk, nylon, cotton cloth, acrylic fiber and other materials when being applied, so that the hydrophobic, oleophobic and anti-pollution self-cleaning effects are achieved.
According to the invention, a principle of self-cleaning a hydrophobic layer of lotus leaves in bionic nature is adopted, and short fluorocarbon oligomers are grafted on carboxyl cellulose in a directional grafting mode to form a micro-nano structure, so that a biomass-based low-surface-energy bionic coating material is synthesized.
The invention has the following beneficial effects:
1) The method adopts short fluorocarbon oligomer (the number of fluorine atoms in the fluorine-containing monomer is not more than 6), has better environmental friendliness, and can become a substitute of long fluorocarbon chains.
2) The biomass-based low-surface-energy bionic coating material can better play the roles of super-hydrophobicity, pollution resistance and self-cleaning, and has good performance when being applied to the field of hydrophobic oleophobic pollution-resistance self-cleaning coatings.
Detailed Description
The following describes the technical scheme of the present invention further with reference to specific examples, but the examples are not intended to limit the present invention in any way.
EXAMPLE 1 preparation of Low surface energy cellulose functional coating Material
(1) Pulp cellulose is used as a base material, naOH alkali liquor with the mass concentration of 9% is selected to pretreat the cellulose for 4 hours in an auxiliary hydrolysis mode to open a crystallization area, then Tempo and the pretreated cellulose are respectively taken to be 0.5g and 1g according to the mass ratio of 0.5:1, and are mixed and placed in 100ml of aqueous solution for oxidation reaction for 0.5 hour, and the reaction temperature is 30 ℃ to prepare the carboxyl cellulose.
(2) The preparation method comprises the steps of adopting 25g of trifluoroethyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of Azodiisobutyronitrile (AIBN) as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylic acid salt (the synthetic process of the acrylic acid salt is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and synthesized by redox reaction) at the later synthesis stage of the short fluorocarbon oligomer (namely, 25-40 min), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 containing amino groups participates in polymerization.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction for 1 hour at the reaction temperature of 50 ℃ to enable the short fluorocarbon oligomer to be grafted to the C6 position of the carboxyl cellulose to form a low-surface-energy micro-nano structure, thus obtaining the biomass-based low-surface-energy bionic coating material.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 1.
TABLE 1
Example 2 preparation of a Low surface energy cellulose functional coating Material
(1) Microcrystalline cellulose is used as a base material, naOH alkali liquor with the mass concentration of 9% is selected to pretreat the cellulose for 4 hours in an auxiliary hydrolysis mode to open a crystallization area, and the Tempo and the cellulose are respectively mixed according to the mass ratio of 0.5 to 1, and then are placed in 100ml of aqueous solution for oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃ to prepare the carboxyl cellulose.
(2) The preparation method comprises the steps of adopting 25g of trifluoroethyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of Azodiisobutyronitrile (AIBN) as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylic acid salt (the synthetic process of the acrylic acid salt is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and are synthesized through oxidation-reduction reaction) at the later synthesis stage of the short fluorocarbon oligomer (namely, 25-40 min), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 amino groups is prepared.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction, wherein the reaction time is 1 hour, the reaction temperature is 50 ℃, and the short fluorocarbon oligomer is grafted to the C6 position of the carboxyl cellulose through amidation reaction to form a low surface energy micro-nano structure, so that the functional cellulose material with the hydrophobic and oleophobic effects on the principle of self-cleaning of the bionic lotus leaf is prepared.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 2.
TABLE 2
| Contact angle of coating surface | Maximum contact angle 151 ° | Oil resistant medium | 120 solvent oil, more than 50h |
| Sliding angle of coating surface | Sliding angle 15 DEG | Acid and alkali resistance | 5% acid-base solution, > 169h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 172h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 198h |
| Flexibility of the product | 1-1.5mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 72kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
Example 3 preparation of a Low surface energy cellulose functional coating Material
(1) The preparation method comprises the steps of taking nano cellulose as a base material, selecting NaOH alkali liquor with the mass concentration of 9% and adopting an auxiliary hydrolysis mode to pretreat the cellulose for 4 hours to open a crystallization area, respectively taking and mixing 0.5g and 1g of Tempo and cellulose according to the mass ratio of 0.5:1, and then placing the mixture into 100ml of aqueous solution for oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃ to prepare the carboxyl cellulose.
(2) The preparation method comprises the steps of adopting 25g of trifluoroethyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of Azodiisobutyronitrile (AIBN) as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylic acid salt (the synthetic process of the acrylic acid salt is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and are synthesized through oxidation-reduction reaction) at the later synthesis stage of the short fluorocarbon oligomer (namely, 25-40 min), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 amino groups is prepared.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction, wherein the reaction time is 1 hour, the reaction temperature is 50 ℃, and the short fluorocarbon oligomer is grafted to the C6 position of the carboxyl cellulose through amidation reaction to form a low surface energy micro-nano structure, so that the functional cellulose material with the hydrophobic and oleophobic effects on the principle of self-cleaning of the bionic lotus leaf is prepared.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 3.
TABLE 3 Table 3
| Contact angle of coating surface | Maximum contact angle 150 DEG | Oil resistant medium | 120 solvent oil, more than 48h |
| Sliding angle of coating surface | Sliding angle 20 DEG | Acid and alkali resistance | 5% acid-base solution > 168h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 172h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 196h |
| Flexibility of the product | 1-2mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 70kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
Example 4 preparation of a Low surface energy cellulose functional coating Material
(1) Pulp cellulose is used as a base material, microwave irradiation with 2450MHz microwave frequency and 210W power is adopted to treat cellulose for 2 hours to open a crystallization area, and the cellulose is prepared by mixing Tempo and cellulose according to the mass ratio of 0.5 to 1, and then placing the mixture into 100ml of aqueous solution for oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃.
(2) The preparation method comprises the steps of adopting 25g of hexafluorobutyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of Azodiisobutyronitrile (AIBN) as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylic acid salt (the synthetic process of the acrylic acid salt is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and are synthesized through oxidation-reduction reaction) at the later synthesis stage of the short fluorocarbon oligomer (namely, 25-40 min), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 amino groups is prepared.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction, wherein the reaction time is 1 hour, the reaction temperature is 50 ℃, and the short fluorocarbon oligomer is grafted to the C6 position of the carboxyl cellulose through amidation reaction to form a low surface energy micro-nano structure, so that the functional cellulose material with the hydrophobic and oleophobic effects on the principle of self-cleaning of the bionic lotus leaf is prepared.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 4.
TABLE 4 Table 4
| Contact angle of coating surface | Maximum contact angle 158 ° | Oil resistant medium | 120 solvent oil > 49h |
| Sliding angle of coating surface | Sliding angle 20 DEG | Acid and alkali resistance | 5% acid-base solution > 168h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 168h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 197h |
| Flexibility of the product | 1-1.5mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 70kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
EXAMPLE 5 preparation of Low surface energy cellulose functional coating Material
(1) Microcrystalline cellulose is used as a base material, microwave irradiation with 2450MHz microwave frequency and 210W power is adopted to treat cellulose for 2 hours to open a crystallization area, and the cellulose is prepared by mixing Tempo and cellulose according to the mass ratio of 0.5 to 1, and then placing the mixture into 100ml of aqueous solution for oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃.
(2) The preparation method comprises the steps of adopting 25g of hexafluorobutyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of Azodiisobutyronitrile (AIBN) as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylate (the synthetic process of the acrylate is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and are synthesized through oxidation-reduction reaction) in the later synthesis stage of the short fluorocarbon oligomer (namely, polymerization reaction for 25-40 min), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 is polymerized.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction, wherein the reaction time is 1 hour, the reaction temperature is 50 ℃, and the short fluorocarbon oligomer is grafted to the C6 position of the carboxyl cellulose through amidation reaction to form a low surface energy micro-nano structure, so that the functional cellulose material with the hydrophobic and oleophobic effects on the principle of self-cleaning of the bionic lotus leaf is prepared.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 5.
TABLE 5
| Contact angle of coating surface | Maximum contact angle 155 ° | Oil resistant medium | 120 solvent oil, more than 50h |
| Sliding angle of coating surface | Sliding angle 25 ° | Acid and alkali resistance | 5% acid-base solution > 168h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 170h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 200h |
| Flexibility of the product | 1-1.5mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 70kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
EXAMPLE 6 preparation of Low surface energy cellulose functional coating Material
(1) The method comprises the steps of adopting nano cellulose as a base material, adopting microwave with 2450MHz microwave frequency and 210W power to treat cellulose for 2 hours to open a crystallization area, respectively taking and mixing 0.5g and 1g of Tempo and cellulose according to the mass ratio of 0.5:1, and then placing the mixture into 100ml of aqueous solution for oxidation reaction for 0.5 hour, wherein the reaction temperature is 30 ℃ to prepare the carboxyl cellulose.
(2) The preparation method comprises the steps of adopting 25g of hexafluorobutyl acrylate monomer, adding 15g of emulsifier span 80, uniformly dispersing the fluorine-containing monomer into ultrafine particles under the high-efficiency dispersing action of a homogenizer to form a microemulsion system, adding 15g of persulfate as an initiator to initiate monomer emulsion polymerization, and adding 10g of amino-containing acrylate (the synthetic process of the acrylate is that acrylic acid and dichloroethylenediamine hydrochloride are mixed according to the mass ratio of 1:1 and synthesized through oxidation-reduction reaction) at the later synthesis stage of the short fluorocarbon oligomer (namely, 25-40min of polymerization reaction), so that the short fluorocarbon oligomer with the synthetic polymerization degree of 50-60 is prepared.
(3) Mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction, wherein the reaction time is 1 hour, the reaction temperature is 50 ℃, and the short fluorocarbon oligomer is grafted to the C6 position of the carboxyl cellulose through amidation reaction to form a low surface energy micro-nano structure, so that the functional cellulose material with the hydrophobic and oleophobic effects on the principle of self-cleaning of the bionic lotus leaf is prepared.
(4) Coating test is carried out on the obtained biomass-based low-surface-energy bionic coating material, the material is coated on paper, silk, nylon, cotton cloth and acrylic fiber in a machine coating mode for test, representative oil pumping, tap water and milk are selected and compared as water and oil repellency test simulants for test of surface wettability of the prepared material; testing the adhesive force of the obtained material by using a circling method; and then setting corresponding conditions to test the impact resistance, high temperature resistance (100 ℃), high and low temperature resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance and mortar resistance of the material. The test results are shown in Table 6.
TABLE 6
| Contact angle of coating surface | Maximum contact angle 152 DEG | Oil resistant medium | 120 solvent oil, more than 50h |
| Sliding angle of coating surface | Sliding angle 15 DEG | Acid and alkali resistance | 5% acid-base solution > 170h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 170h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 196h |
| Flexibility of the product | 1-2mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 70kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
In combination with the test results of examples 1-6, the lower data limit objectively reflects the performance results of the low surface energy cellulose functional coating material as follows:
| contact angle of coating surface | ≥150° | Oil resistant medium | 120 solvent oil, more than 48h |
| Sliding angle of coating surface | ≤25° | Acid and alkali resistance | 5% acid-base solution > 168h |
| Adhesion of coating | Circling method, 3 grade above | Salt water resistant saturated brine | Saturated brine > 168h |
| Hardness of the coating surface | Pencil hardness of 2H or more | Salt spray resistance | Neutral salt fog > 196h |
| Flexibility of the product | 1mm | Ultraviolet aging resistance | ＞500h |
| Impact resistance | 70kg | Mortar resistance | By passing through |
| High temperature resistance | At > 100 ℃ for 24 hours | High-low temperature alternating resistance | -40℃—100℃ |
The results show that: the material can be well adhered to the surface of a test material, and has excellent performances such as hydrophobicity, impact resistance, high temperature resistance (100 ℃), high and low temperature alternation resistance, oil resistance, acid and alkali resistance, salt water resistance, salt fog resistance, ultraviolet aging resistance, mortar resistance and the like.
Claims (7)
1. The preparation method of the biomass-based low-surface-energy bionic coating material is characterized by comprising the following operation steps:
step 1: pretreating biomass cellulose with alkali liquor or microwave, oxidizing pretreated biomass cellulose with Tempo, and C 6 Oxidizing hydroxyl on the position into carboxyl to prepare oxidized carboxyl cellulose;
step 2: dispersing short fluorocarbon monomers into ultrafine particles by using an emulsifying agent, then adding an initiator to initiate monomer emulsion polymerization, and adding amino-containing acrylic acid salt to participate in polymerization in the later period of the polymerization reaction to prepare a short fluorocarbon oligomer with the polymerization degree of 50-60; the short fluorocarbon monomer is trifluoroethyl acrylate or hexafluorobutyl acrylate; the initiator is persulfate or Azobisisobutyronitrile (AIBN); the emulsifying agent is span 80; the mass ratio of the addition of the emulsifying agent to the fluorine-containing monomer is 3:5, the mass ratio of the addition of the initiator to the fluorine-containing monomer is 3:5, and the mass ratio of the addition of the amino-containing acrylate to the fluorine-containing monomer is 2:5;
step 3: and (3) mixing the short fluorocarbon oligomer in the step (2) and the carboxyl cellulose in the step (1) according to the mass ratio of 1:2, and then placing the mixture in an aqueous solution for amidation reaction for 1 hour at the reaction temperature of 50 ℃ to enable the short fluorocarbon oligomer to be grafted to the C6 position of the carboxyl cellulose to form a low-surface-energy micro-nano structure, thus obtaining the biomass-based low-surface-energy bionic coating material.
2. The method for preparing a biomass-based low-surface-energy biomimetic coating material according to claim 1, wherein in the step 1, the biomass cellulose is microcrystalline cellulose, nanocellulose or pulp cellulose.
3. The method for preparing the biomass-based low-surface-energy bionic coating material according to claim 1, wherein in the step 1, when the biomass cellulose is pretreated with alkali liquor, the biomass cellulose is soaked in the alkali liquor with the mass concentration of 9% to open a crystallization area of the biomass cellulose.
4. The method for preparing the biomass-based low-surface-energy bionic coating material according to claim 1, wherein in the step 1, when biomass cellulose is subjected to microwave treatment, the biomass cellulose is placed in a microwave device with a microwave frequency of 2450MHz and a microwave power of 210W for microwave irradiation pretreatment so as to open a crystallization area of the biomass cellulose.
5. The method for preparing the biomass-based low-surface-energy bionic coating material according to claim 1, wherein in the step 1, when biomass cellulose is subjected to oxidation treatment, tempo and biomass cellulose are mixed according to a mass ratio of 0.5:1 and then placed in an aqueous solution for oxidation reaction for 0.5 hours, wherein the reaction temperature is 30 ℃, and carboxyl cellulose is obtained through suction filtration.
6. The method for preparing the biomass-based low-surface-energy bionic coating material according to claim 1, wherein in the step 2, the amino-containing acrylic acid salt is synthesized by mixing acrylic acid and dichloroethylenediamine hydrochloride according to a mass ratio of 1:1 through oxidation-reduction reaction.
7. The application of the biomass-based low-surface-energy bionic coating material prepared by the method according to claim 1 is characterized in that the biomass-based low-surface-energy bionic coating material is applied to paper and textile materials, and is coated on the surface of paper, silk, nylon, cotton cloth or acrylic fiber materials during application, so that the hydrophobic, oleophobic and anti-pollution self-cleaning effects are achieved.
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