CN115286958B

CN115286958B - Biomass-based antifouling material and application thereof

Info

Publication number: CN115286958B
Application number: CN202211055269.0A
Authority: CN
Inventors: 杨鹏; 冯娜
Original assignee: Shaanxi Normal University
Current assignee: Shaanxi Normal University
Priority date: 2022-08-31
Filing date: 2022-08-31
Publication date: 2023-04-07
Anticipated expiration: 2042-08-31
Also published as: CN115286958A

Abstract

The invention discloses a biomass-based antifouling material and application thereof, wherein the biomass-based antifouling material is an antifouling coating formed by modifying a safe and nontoxic biomass nano material on a protein phase-transition nano film obtained by protein under the action of a structure conversion agent. The biomass antifouling coating is simple in preparation method, can be adhered to the surface of any base material, has good mechanical stability and antifouling stability, and the biomass nano material serving as the raw material of the coating has the advantages of low cost, environmental friendliness, good dispersion and the like. The antifouling material can be used for modifying tableware (ceramic bowls, glass bowls, stainless steel bowls, plastic lunch boxes, pots and the like), and the obtained tableware can be cleaned of oil stains without using a detergent; modifying edible oil packaging materials (plastic bottles, glass bottles and the like) to obtain packaging materials which are easy to clean and can be recycled; the clothes are modified to obtain the underwater clothes with self-cleaning oil stains, and the underwater clothes can replace a detergent.

Description

Biomass-based antifouling material and application thereof

Technical Field

The invention belongs to the technical field of natural polymer materials and ecological environment materials, and particularly relates to a biomass-based antifouling material formed by modifying a safe and nontoxic biomass nano material on a protein phase transition nano film and application thereof.

Background

Detergents are widely used in our daily lives, of which the surfactant sodium linear alkyl benzene sulfonate (LAS) in household detergents is a non-degradable biodegradable substance, listed as a secondary pollutant in the chinese environmental standards. Surfactants in household detergents have deleterious negative effects on both the human body and the environment due to their toxicity. Post-treatment of surfactant wastewater can reduce the harm of surfactants, including adsorption, membrane filtration, biodegradation, and foam separation. Especially in some sewage treatment plants, biodegradation has been used to keep residual amounts of surfactants in the environment at a low level. Furthermore, the development of new surfactants is another strategy to reduce surfactant hazards. However, these methods can only reduce the hazards of surfactants to some extent and cannot eliminate them fundamentally. Therefore, a green and safe oil-proof coating needs to be constructed, and the use of the oil-proof coating is replaced by detergent from the source.

Inspired by the oil-resistant and antifouling properties of fish scales, the artificial underwater super-oleophilic surface is constructed and can be widely applied to marine environments to resist organic and biological pollution. However, most antifouling coatings currently being investigated have potential toxicity, opacity and poor stability, and few reports have been made of the use of such coatings in dishware and packaging materials to replace the use of detergents.

Disclosure of Invention

The invention aims to provide an antifouling material which has a simple preparation method, is environment-friendly, can be adhered to the surface of any base material, has good mechanical stability and oil stain resistance stability, and provides a new application for the antifouling material.

Aiming at the purposes, the biomass-based antifouling material adopted by the invention is an antifouling coating formed by modifying a safe and nontoxic biomass nano material on a protein phase transition nano film obtained by protein under the action of a structure conversion agent, and the biomass nano material has a closely arranged structure.

The biomass nano material is selected from any one of cellulose nanocrystals, microfibrillated cellulose, bacterial nanocellulose, chitosan nanocrystals, chitin nanocrystals, xylan nanocrystals and the like, or any one of the biomass nano material materials subjected to surface modification.

The protein is selected from lysozyme, lactalbumin, soy protein, serum albumin, lactoferrin, fibrinogen, collagen, keratin, casein, gastric protein, beta-lactoglobulin, myoglobin, lactalbumin, albumin, collagen, glycinin, zein, gliadin, barley protein, kidney bean protein, serum, chymotrypsin, hemoglobin, myosin, rice protein, fibroin, alpha-amylase, albumin, and skimmed milk.

The structure transforming agent is any one of cysteine, glutathione, mercaptoethanol, dithiothreitol, tris (2-carboxyethyl) phosphate, hydrogen peroxide, peroxyacetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, sodium percarbonate, sodium perborate, oxygen, chlorine, fluorine gas, ozone, trivalent cobalt salt, periodic acid, sodium ferrate and lead dioxide.

The biomass-based antifouling material can be prepared by the following two methods:

the method comprises the steps of firstly, adjusting 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 2-100 mg/mL structural transforming agent to pH 4-10 by NaOH, and then uniformly mixing the buffer solution with 2-100 mg/mL protein 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution according to the volume ratio of 1; modifying the obtained mixed solution on the surface of a substrate in a dip coating or spraying or dripping manner, culturing for 0.2-5 hours at room temperature, and obtaining a protein phase transition nano film with strong adhesion on the surface of the substrate; dispersing the biomass nano material in ultrapure water to form a biomass nano material dispersion liquid with the mass fraction of 0.06% -2%; and modifying the dispersion liquid on the protein phase transition nano film in a dip coating or spray coating or spin coating mode to obtain the protein phase transition nano film for modifying the biomass nano material, namely the biomass-based antifouling coating.

Adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-100 mg/mL structure transforming agent to 4-10 by using NaOH, then uniformly mixing the buffer solution with a 2-100 mg/mL protein 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution and a biomass nano-material dispersion solution with the mass fraction of 0.01-5% according to a volume ratio of 1.

In the above preparation method, preferably, the 4-hydroxyethylpiperazine ethanesulfonic acid buffer solution of 2 to 10mg/mL structural transformation agent is adjusted to pH 6 to 10 with NaOH, and then mixed uniformly with the 4-hydroxyethylpiperazine ethanesulfonic acid buffer solution of 2 to 10mg/mL protein in a volume ratio of 1.

In the preparation method, the base material comprises any one of common experimental materials, tableware materials, food packaging materials and the like; the material comprises any one of silicon, glass, quartz, mica, pottery, porcelain, polymethyl methacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyurethane, phenolic resin, rubber, polypropylene, polyethylene terephthalate, polycarbonate, various alloy materials and wood.

In the preparation method, the mass fraction of the biomass nano material in the biomass nano material dispersion liquid is preferably 0.06% -2%.

In the dip coating mode of the first preparation method, the time for soaking the protein phase transition nano film in the biomass nano material dispersion liquid is preferably 5-120 min.

In the dip coating method of the second preparation method, the time for soaking the substrate in the mixed solution is preferably 5 to 120min.

The biomass-based antifouling material is applied to any one of production and life as follows:

(1) The application in preparing the oil-stain-resistant packaging material with the oil-stain-resistant adhesion performance;

(2) Use in the preparation of a medical hygiene material resistant to adherence of microorganisms and proteins;

(3) The application in preparing the antifouling tableware of the self-cleaning greasy dirt;

(4) The application in the preparation of anti-oil articles for daily use;

(5) The application in the aspect of oil pollution prevention underwater optical devices;

(6) The application in preparing the self-cleaning greasy dirt fabric.

Compared with the prior art, the invention has the following beneficial effects:

the invention uses the structure transforming agent to effectively break the disulfide bond of the protein to induce the rapid self-assembly of the protein, so as to obtain the phase-transition nano film, and the obtained phase-transition nano film can be adhered to the surfaces of various base materials and has good chemical stability and mechanical stability. The protein phase transition nano-film is used as an adhesive to stabilize the biomass nano-material on various base materials, so as to form a natural antifouling coating with underwater super-oleophobic function. The antifouling coating has excellent mechanical stability, the preparation method is simple and green, and the obtained coating is non-toxic and harmless, and can solve the problem that a surfactant in life harms the natural environment, aquatic animals and plants and human bodies. The method comprises the following specific steps:

(1) The antifouling coating can be used for modifying tableware to obtain the tableware capable of self-cleaning underwater, and the tableware can resist the adhesion of various edible oils (rapeseed oil, sesame oil, peanut oil, walnut oil, olive oil, linseed oil, animal oil and the like) underwater under the condition of not using a detergent;

(2) The antifouling coating can be used for carrying out antifouling modification on a high molecular polymer packaging material to obtain an underwater self-cleaning packaging material, and is beneficial to recycling the packaging material;

(3) The antifouling coating can also modify clothes to obtain the underwater self-cleaning clothes without a detergent;

(4) The antifouling coating can also modify an underwater optical device to obtain the underwater oil-stain-resistant optical device;

(5) The antifouling coating can also modify the medical sanitary material to obtain the medical material with the antimicrobial adhesion.

Drawings

FIG. 1 is an atomic force microscope scanning image of phase transition nanofilm of lysozyme prepared in example 1.

FIG. 2 is an infrared spectrum of a lysozyme phase transition nano-film modified with cellulose nanocrystals in example 1.

FIG. 3 is an atomic force microscope scan of a lysozyme phase transition nanofilm of the modified cellulose nanocrystals of example 1.

FIG. 4 is an atomic force microscope scan of the underwater antifouling coating of example 2 after being rubbed with sandpaper.

FIG. 5 is an atomic force microscope scan of the underwater anti-fouling coating of example 2 after ultrasonic treatment.

FIG. 6 is the contact angle of the underwater oil of the underwater antifouling coating subjected to the bending test in example 2.

FIG. 7 is the contact angle of the underwater oil after the 180 ℃ treatment of the underwater antifouling coating in example 2.

FIG. 8 is the contact angle of underwater oil of different organic agents on the surface of the antifouling coating in example 9.

FIG. 9 shows the contact angles of underwater oils of various petroleum products on the surface of the antifouling coating in example 9.

FIG. 10 shows the underwater oil contact angles of different edible oils on the surface of the antifouling coating in example 9.

FIG. 11 is a confocal view of the anti-fouling coating surface of example 9 against bovine serum albumin adhesion.

FIG. 12 is a scanning electron micrograph of the surface of the antifouling coating layer resistant to adhesion of Escherichia coli in example 9.

FIG. 13 shows the oil stains on the sesame oil packaging bottle and the blank packaging bottle modified with the antifouling coating in example 11 after being washed with water only.

FIG. 14 is the contact angle of the bowl surface modified with the anti-fouling coating of example 12 against erosion by hot water.

FIG. 15 is the underwater oil contact angle of the underwater optical lens modified with the antifouling coating in example 13.

FIG. 16 is the underwater oil contact angle of the wood modified with the antifouling coating in example 15.

FIG. 17 shows the results of washing with water only the oil stains on the plastic packaging box and the blank packaging box modified with the stain-proofing coating in example 18.

FIG. 18 is the contact angle of underwater oil of stainless steel modified with the antifouling coating in example 19.

FIG. 19 shows the oil stains on the iron pan modified with the antifouling coating and the blank iron pan in example 20 after being washed with water only.

Detailed Description

The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.

Example 1

1. At room temperature, adding 50mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 50mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; soaking the silicon wafer in the mixed solution, and culturing at room temperature for 0.5h to form lysozyme phase transition nano-film on the surface of the silicon wafer (see figure 1).

2. And (3) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a cellulose nano-crystal suspension with the mass fraction of 0.1% for 2h to obtain the lysozyme phase-transition nano-film (shown in figures 2 and 3) for modifying the cellulose nano-crystal, namely the bio-based antifouling coating.

Example 2

1. At room temperature, adding 20mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 20mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; soaking the polyethylene glycol terephthalate substrate in the mixed solution, culturing for 0.5h at room temperature, and forming a lysozyme phase transition nano-film on the surface of the polyethylene glycol terephthalate.

2. And (3) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a cellulose nano-crystal suspension with the mass fraction of 0.5% for 1h to obtain the lysozyme phase-transition nano-film for modifying the cellulose nano-crystal, namely the biomass-based antifouling coating.

FIG. 4 shows that the biomass-based antifouling coating is placed between 400-mesh sand paper and a 200g sliding block, moves forwards for 5cm under the action of external force, and keeps the shape after 50 times of friction. FIG. 5 shows that the biomass-based antifouling coating does not fall off and the appearance is kept unchanged when the biomass-based antifouling coating is subjected to ultrasonic treatment for 20min in a 400W ultrasonic cleaning instrument. Fig. 6 shows that the biomass-based antifouling coating is cut into a rectangular shape of 1cm × 5cm, the surface of the antifouling coating is fixed in a tension machine jig, the surface of the antifouling coating is bent 180 degrees 3000 times, the antifouling coating does not fall off, and the contact angle of the underwater oil on the surface is still larger than 150 degrees. Fig. 7 shows that the biomass-based antifouling coating is placed in an oven at 180 ℃ and is subjected to heat treatment for 72 hours, and the contact angle of underwater oil of the antifouling coating is still kept above 150 degrees. The above data indicate that the biomass-based antifouling coating has excellent mechanical, thermal and adhesion stability.

Example 3

1. At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 9 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; and soaking the glass substrate in the mixed solution, and culturing for 0.5h at room temperature to form the lysozyme phase transition nano-film on the glass surface.

2. And (3) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a bacterial nano-cellulose suspension with the mass fraction of 0.5% for 2 hours to obtain the lysozyme phase-transition nano-film for modifying the bacterial nano-cellulose, namely the bio-based antifouling coating.

Example 4

1. At room temperature, 143mg of tris (2-carboxyethyl) phosphate hydrochloride was added to 10mL of a 4-hydroxyethylpiperazine ethanesulfonic acid buffer solution having a pH of 7.4 and adjusted to pH 7 with 5mol/L aqueous sodium hydroxide solution, 50mg of lysozyme was added to 10mL of a 4-hydroxyethylpiperazine ethanesulfonic acid buffer solution having a pH of 7.4, and then the two solutions were mixed uniformly to obtain a mixed solution. And soaking the mica sheet in the mixed solution, and culturing at room temperature for 1h to form the lysozyme phase transition nano-film on the surface of the mica sheet.

2. And (2) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a microfibrillated cellulose suspension with the mass fraction of 0.5% for 2 hours to obtain the lysozyme phase-transition nano-film for modifying microfibrillated cellulose, namely the biomass-based antifouling coating.

Example 5

1. At room temperature, 143mg of tris (2-carboxyethyl) phosphate hydrochloride is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, the pH value is adjusted to 6 by using 5mol/L sodium hydroxide aqueous solution, 20mg of lysozyme is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then the two solutions are uniformly mixed to obtain a mixed solution; and soaking the mica sheet in the mixed solution, and culturing at room temperature for 2h to form the lysozyme phase transition nano-film on the surface of the mica sheet.

2. And (3) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a cellulose nano-crystal suspension with the mass fraction of 0.5% for 2 hours to obtain the lysozyme phase-transition nano-film for modifying cellulose nano-crystals, namely the biomass-based antifouling coating.

Example 6

1. At room temperature, 143mg of tris (2-carboxyethyl) phosphate hydrochloride is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, the pH is adjusted to 8 by using 5mol/L sodium hydroxide aqueous solution, 20mg of bovine serum albumin is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, and then the two solutions are uniformly mixed to obtain a mixed solution; and soaking the silicon wafer in the mixed solution, culturing for 1h at room temperature, and forming a bovine serum albumin phase transition nano-film on the surface of the silicon wafer.

2. And (2) soaking the bovine serum albumin phase-transition nano-film obtained in the step (1) in a cellulose nanocrystalline suspension with the mass fraction of 0.5% for 2 hours to obtain the bovine serum albumin phase-transition nano-film for modifying the cellulose nanocrystalline, namely the bio-based antifouling coating.

Example 7

1. At room temperature, adding 20mg of glutathione into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 20mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; soaking the silicon wafer in the mixed solution, and culturing at room temperature for 1 hour to form lysozyme phase transition nano-film on the surface of the silicon wafer.

Example 8

1. At room temperature, adding 20mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, adjusting the pH to 8 by using 5mol/L sodium hydroxide aqueous solution, adding 200mg of whey protein into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; and soaking the silicon wafer in the mixed solution, and culturing at room temperature for 1h to form the whey protein phase transition nano film on the surface of the silicon wafer.

2. And (3) soaking the whey protein phase transition nano-film obtained in the step (1) in a cellulose nanocrystalline suspension with the mass fraction of 0.5% for 2 hours to obtain the cellulose nanocrystalline modified whey protein phase transition nano-film, namely the biomass-based antifouling coating.

Example 9

1. At room temperature, adding 50mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 50mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; soaking the silicon wafer in the mixed solution, and culturing at room temperature for 1h to form the lysozyme phase transition nano-film on the surface of the silicon wafer.

2. And (3) soaking the lysozyme phase-transition nano-film obtained in the step (1) in a cellulose nano-crystal suspension with the mass fraction of 1.0% for 2 hours to obtain the lysozyme phase-transition nano-film for modifying cellulose nano-crystals, namely the biomass-based antifouling coating.

Fig. 8 illustrates that the underwater contact angles of the different organic agents are all greater than 150 ° on the anti-fouling coating. Fig. 9 illustrates that the underwater contact angles of different petroleum products on the anti-fouling coating are all greater than 150 °. Fig. 10 illustrates that the underwater contact angles of different edible oils on the antifouling coating are all greater than 150 °. Figure 11 confocal laser graphs show that bovine serum albumin does not adhere on the anti-fouling coating (confocal laser graphs have no fluorescent signal). The scanning electron microscope figure of fig. 12 shows that escherichia coli did not adhere on the antifouling coating.

Example 10

1. At room temperature, adding 50mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L sodium hydroxide aqueous solution, adding 50mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; pouring the mixed solution into a rapeseed oil packaging bottle for soaking, culturing for 2 hours at room temperature, and forming a lysozyme phase transformation nano film on the inner wall of the rapeseed oil bottle.

2. And (2) dip-coating the lysozyme phase-transition nano-film obtained in the step (1) into a cellulose nano-crystal suspension with the mass fraction of 0.5%, and soaking for 2h to obtain the lysozyme phase-transition nano-film modified with the cellulose nano-crystal, namely a rapeseed oil packaging bottle modified by a bio-based antifouling coating.

Example 11

1. At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; pouring the mixed solution into a sesame oil packaging bottle for soaking, culturing for 2h at room temperature, and forming a lysozyme phase transformation nano-film on the inner wall of the sesame oil bottle.

2. And (3) dip-coating the cellulose nanocrystal suspension with the mass fraction of 0.5% on the lysozyme phase transition nano-film obtained in the step (1), and soaking for 2 hours to obtain the lysozyme phase transition nano-film modified with the cellulose nanocrystals, namely the sesame oil packaging bottle modified by the bio-based antifouling coating.

FIG. 13 illustrates that the sesame oil packaging bottle decorated with the antifouling coating can be washed clean of oil stains only by water.

Example 12

1. At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; and pouring the mixed solution into a ceramic bowl for soaking, culturing for 2 hours at room temperature, and forming the lysozyme phase transition nano-film on the inner wall of the ceramic bowl.

2. And (2) dip-coating the cellulose nanocrystal suspension with the mass fraction of 0.5% on the lysozyme phase transition nano-film obtained in the step (1), and soaking for 2 hours to obtain the lysozyme phase transition nano-film for modifying the cellulose nanocrystals, namely the ceramic bowl modified by the bio-based antifouling coating.

Fig. 14 illustrates that the contact angles of the antifouling coating after acid soup corrosion are still all larger than 150 °.

Example 13

1. At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then uniformly mixing the two solutions to obtain a mixed solution; and spraying the mixed solution on an underwater optical lens, culturing at room temperature, and forming a lysozyme phase transition nano-film on the surface of the underwater optical lens after the mixed solution is completely volatilized.

2. And (2) spraying cellulose nanocrystalline suspension with the mass fraction of 0.5% on the lysozyme phase transition nano-film obtained in the step (1), and volatilizing and drying the solution to obtain the lysozyme phase transition nano-film for modifying cellulose nanocrystals, namely the underwater optical lens modified by the bio-based antifouling coating.

Fig. 15 illustrates that the contact angle of the underwater oil on the underwater optical lens modified with the anti-fouling coating is greater than 150 °.

Example 14

1. At room temperature, 143mg of tris (2-carboxyethyl) phosphate hydrochloride is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, the pH value is adjusted to 8 by using 5mol/L of sodium hydroxide aqueous solution, 40mg of bovine serum albumin is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, and then the two solutions are uniformly mixed to obtain a mixed solution; spraying the mixed solution on clothes, culturing at room temperature, and forming bovine serum albumin phase transition nano-film on the surface of the clothes after the mixed solution is completely volatilized.

2. And (2) spraying a cellulose nanocrystal suspension with the mass fraction of 0.5% on the bovine serum albumin phase-transition nano film obtained in the step (1), and volatilizing and drying the solution to obtain the bovine serum albumin phase-transition nano film for modifying the cellulose nanocrystal, namely the garment modified by the bio-based antifouling coating.

Example 15

At room temperature, adding 40mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 40mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adding 10mL of cellulose nanocrystal suspension with the mass fraction of 0.1%, and uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution on a wooden table, culturing at room temperature, and obtaining the biomass-based antifouling coating on the wooden table after the mixed solution is completely volatilized.

Fig. 16 illustrates that the contact angle of the underwater oil on the antifouling coating modified wood was still greater than 150 °.

Example 16

At room temperature, 143mg of tris (2-carboxyethyl) phosphate hydrochloride is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, the pH value is adjusted to 7 by using 5mol/L of sodium hydroxide aqueous solution, 40mg of bovine serum albumin is added into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, 10mL of cellulose nanocrystal suspension with the mass fraction of 0.1% is added, and then the three solutions are uniformly mixed to obtain a mixed solution; and spraying the mixed solution on the surface of the shoe, culturing at room temperature, and after the mixed solution is completely volatilized, obtaining the biomass-based antifouling coating on the new shoe.

Example 17

At room temperature, adding 50mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 9 by using 5mol/L of sodium hydroxide aqueous solution, adding 50mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adding 10mL of bacterial nano-fiber suspension with the mass fraction of 0.5%, and uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution on a metal product, culturing at room temperature, and after the mixed solution is completely volatilized, obtaining the biomass-based antifouling corrosion inhibition coating on the metal product.

Example 18

At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, adjusting the pH to 9 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of whey protein into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, adding 10mL of cellulose nanocrystal suspension with mass fraction of 0.5%, and uniformly mixing the three solutions to obtain a mixed solution; and respectively soaking the glass bottle, the plastic bottle and the packaging box in the mixed solution, culturing at room temperature for 1h, pouring out the mixed solution, and washing the glass bottle, the plastic bottle and the packaging box with deionized water to obtain the biomass-based antifouling coating modified glass bottle, plastic bottle and packaging box.

Fig. 17 illustrates that the soil on the plastic packaging box decorated with the antifouling coating can be washed clean with water only without detergent.

Example 19

At room temperature, adding 30mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 9 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lactalbumin into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adding 10mL of cellulose nanocrystal suspension with the mass fraction of 0.1%, and then uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution on a stainless steel water tank, culturing at room temperature, and obtaining the biomass-based antifouling coating on the stainless steel water tank after the mixed solution is completely volatilized.

Fig. 18 illustrates that the contact angle of the underwater oil on the stainless steel modified by the antifouling coating is more than 150 °.

Example 20

At room temperature, adding 50mg of L-cysteine into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adding 10mL of cellulose nanocrystal suspension with the mass fraction of 0.1%, and uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution into an iron pan, culturing at room temperature, and obtaining the biomass-based antifouling coating in the iron pan after the mixed solution is completely volatilized.

Fig. 19 illustrates that the oil stain on the iron pan decorated by the antifouling coating can be cleaned by only using water without detergent.

Example 21

At room temperature, adding 50mg of ammonium persulfate into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adjusting the pH value to 7.5 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with the pH value of 7.4, adding 10mL of cellulose nanocrystal suspension with the mass fraction of 0.1%, and uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution into a rapeseed oil packaging bottle, culturing at room temperature, completely volatilizing the mixed solution to obtain a biomass-based antifouling coating in the rapeseed oil packaging bottle, and cleaning and fastening oil stains only by washing with water.

Example 22

At room temperature, adding 50mg of dithiothreitol into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, adjusting the pH to 8 by using 5mol/L of sodium hydroxide aqueous solution, adding 30mg of lysozyme into 10mL of 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution with pH of 7.4, adding 10mL of cellulose nanocrystal suspension with mass fraction of 0.1%, and uniformly mixing the three solutions to obtain a mixed solution; and spraying the mixed solution into a ceramic bowl, culturing at room temperature, completely volatilizing the mixed solution to obtain a biomass-based antifouling coating in the ceramic bowl, and cleaning and tightly driving oil stains only by washing with water.

Claims

1. A biomass-based antifouling material characterized by: the antifouling material is an antifouling coating formed by modifying a biomass nano material on a protein phase transition nano film obtained by protein under the action of a structure conversion agent, and the biomass nano material has a closely arranged structure;

the biomass nano material is selected from any one of cellulose nanocrystals, microfibrillated cellulose, bacterial nanocellulose, chitosan nanocrystals, chitin nanocrystals and xylan nanocrystals, or any one of the biomass nano materials subjected to surface modification;

the structure transforming agent is any one of cysteine, glutathione, mercaptoethanol, dithiothreitol, tris (2-carboxyethyl) phosphate, hydrogen peroxide, peroxyacetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, sodium percarbonate, sodium perborate, oxygen, chlorine, fluorine gas, ozone, trivalent cobalt salt, periodic acid, sodium ferrate and lead dioxide;

the antifouling material is prepared by any one of the following methods:

the method comprises the following steps: adjusting the pH of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-100 mg/mL structure transforming agent to 4-10 by using NaOH, and then uniformly mixing the buffer solution with a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-100 mg/mL protein according to a volume ratio of 1; modifying the obtained mixed solution on the surface of a substrate in a dip coating or spraying or dripping manner, culturing for 0.2-5 hours at room temperature, and obtaining a protein phase transition nano film with strong adhesion on the surface of the substrate; dispersing the biomass nano material in ultrapure water to form a biomass nano material dispersion liquid with the mass fraction of 0.01-5%; modifying the dispersion liquid on the protein phase transition nano film in a dip coating or spray coating or spin coating mode to obtain a protein phase transition nano film for modifying the biomass nano material, namely a biomass-based antifouling coating;

the second method comprises the following steps: adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-100 mg/mL structure transforming agent to 4-10 by using NaOH, then uniformly mixing the buffer solution with a 2-100 mg/mL protein 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution and a biomass nano-material dispersion solution with the mass fraction of 0.01-5% according to a volume ratio of 1.

2. The biomass-based antifouling material according to claim 1, wherein: the protein is selected from any one of lysozyme, lactalbumin, soy protein, serum albumin, lactoferrin, fibrinogen, collagen, keratin, casein, stomach protein, beta-lactoglobulin, myoglobin, lactalbumin, albumin, collagen, glycinin, zein, gliadin, barley protein, kidney bean protein, serum, chymotrypsin, hemoglobin, myosin, rice protein, fibroin, alpha-amylase, albumin and skim milk.

3. The biomass-based antifouling material according to claim 1, wherein: adjusting the pH of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-10 mg/mL structure transforming agent to 6-10 by using NaOH, and then uniformly mixing the buffer solution with a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of a 2-10 mg/mL protein according to a volume ratio of 1; in the biomass nano material dispersion liquid, the mass fraction of the biomass nano material is 0.06% -2%.

4. The biomass-based antifouling material according to claim 1, wherein: the base material comprises any one of common experimental materials, tableware materials and food packaging materials, and the materials are selected from any one of silicon, glass, quartz, mica, pottery, porcelain, polymethyl methacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyurethane, phenolic resin, rubber, polypropylene, polyethylene terephthalate, polycarbonate, various alloy materials and wood.

5. The biomass-based antifouling material according to claim 1, wherein: in the dip-coating mode of the first method, the protein phase transition nano film is soaked in the biomass nano material dispersion liquid for 5-300 min; in the dip coating mode of the second method, the time for soaking the substrate in the mixed solution is 5-120 min.

6. Use of the biomass-based antifouling material according to claim 1 in any one of the following productive lives:

(1) The application in preparing the oil stain resistant packaging material with the oil stain resistant adhesion performance;

(2) Use in the preparation of a medical hygiene material resistant to the adhesion of microorganisms and proteins;

(4) The application in the preparation of oil stain resistant articles for daily use;

(6) The application in preparing the self-cleaning greasy dirt fabric.