A functionalized Mxenes-modified biomass-based polyurea and its preparation method and coating

Abstract

The embodiment of the present invention discloses a functionalized MXenes modified biomass-based polyurea, which includes, by weight: 25-45 parts of biomass material, 15-25 parts of isocyanate, 0.1-3 parts of catalyst, 0.1-15 parts of oxidant, 0.1-1 parts of neutralizer, 20-40 parts of amine ring-opener, 0.1-5 parts of amine chain extender, 0.5-10 parts of MXenes nanomaterial, 0.5-15 parts of organic silicon fluorine modifier, 0.1-3 parts of cross-linking agent, 5-15 parts of dispersant, 0.5-10 parts of surface modifier, and 1-5 parts of solvent. A highly cross-linked organic whole is formed by the bonding of isocyanate, biomass polyamine, amine chain extender, silicon fluorine modifier, and nano MXenes material, so that the formed coating has the advantages of heat resistance, tensile performance, bonding performance, anti-aging, acid and alkali resistance, and hydrolysis resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of functional polymers and protective coatings, and in particular to a functionalized Mxenes-modified biomass-based polyurea and a preparation method and coating thereof. Background Art

[0002] In recent years, with the acceleration of urbanization, the use of concrete and metal materials has long been popularized in various fields of the national economy. However, the corrosion, cracking, aging and wear problems of concrete and metal materials have also emerged in an endless stream, which not only causes huge losses to production and life, but also threatens people's life safety at all times. Therefore, while improving the quality of life, people have higher and higher requirements for the protection of concrete-metal structures. Polyurea has been widely used in engineering waterproofing, anti-corrosion, vehicle wear resistance, equipment protection and other fields due to its durability, corrosion resistance, wear resistance, impact resistance and other advantages. However, due to its low cross-linking density, it is easy to crack and fall off under conditions such as vibration and alternating stress environment, and its application is greatly limited. In addition, most of the polyurea coatings on the market are petroleum-based polyureas, and as the two major problems of environmental protection and oil resource depletion are increasingly concerned, the applicable fields of petroleum-based polyureas are also reduced. Therefore, finding and developing renewable, environmentally friendly green new materials has become an important topic for scientific researchers.

[0003] Traditional polyurea coatings have a short gel time, are not sufficiently wetted with the substrate, do not bond firmly enough, and are mostly derived from petrochemical raw materials. The polymers produced are relatively brittle, lack flexibility, and have poor stability and corrosion resistance.

[0004] Therefore, in order to solve the above technical problems, it is necessary to develop a new polyurea coating with excellent water resistance, mechanical properties and chemical durability. Summary of the invention

[0005] The present invention aims to provide a functionalized MXenes-modified biomass-based polyurea and a preparation method and coating thereof, wherein the raw materials are renewable, degradable, non-toxic, cheap and abundant in source. The coating formed by the coating has excellent water resistance, mechanical properties and chemical durability, and can effectively inhibit the penetration and corrosion of water on its surface.

[0006] In order to achieve the above object, the present invention provides a functionalized Mxenes-modified biomass-based polyurea, wherein the functionalized Mxenes-modified biomass-based polyurea comprises, by weight:

[0007] 25-45 parts of biomass materials, 15-25 parts of isocyanates, 0.1-3 parts of catalysts, 0.1-15 parts of oxidants, 0.1-1 parts of neutralizers, 20-40 parts of amine ring-openers, 0.1-5 parts of amine chain extenders, 0.5-10 parts of MXenes nanomaterials, 0.5-15 parts of organosilicon fluorine modifiers, 0.1-3 parts of cross-linking agents, 5-15 parts of dispersants, 0.5-10 parts of surface modifiers, and 1-5 parts of solvents.

[0008] Further, the biomass material is selected from one or more of glucose, guar gum, soybean oil, corn oil, peanut oil, sesame oil, castor oil, rapeseed oil and olive oil;

[0009] The isocyanate is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), HDI trimer, dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI) and lysine diisocyanate (LDI);

[0010] The amine chain extender is selected from one or more of 2,6-diaminopyridine, 1,6-hexanediamine, dopamine, MOCA, ethylenediamine, diethylenetriamine (DETA), diethyltoluenediamine, diethylenetriamine and N-aminoethylpiperazine;

[0011] The organosilicon fluorine modifier is selected from one or more of 1H, 1H, 2H, 2H perfluorododecyltriethoxysilane (HFDS), polytrifluoropropylmethylsiloxane (PTFPMS), 1H, 1H, 2H, 2H perfluorododecyltrichlorosilane (PFDTS), KH-550, KH-560, octadecyltrichlorosilane (ODTS), phenyltrimethoxysilane (PTMS), trimethylchlorosilane (TMCS), chlorotrimethylsilane (Me3SiCl), vulcanized silicone rubber, heptafluoro-1,1,2,2-tetrahydrodecyldimethylchlorosilane (HFTD), methyl silicone resin (Al), silicone, 1,1,1,3,3,3-hexamethyldisilazane (HMDS) and methyltriethoxysilane.

[0012] Furthermore, the catalyst is selected from one or more of formic acid (HCOOH), acetic acid (CH3COOH), concentrated sulfuric acid (H2SO4), tetrafluoroboric acid (HBF4), dibutyltin dilaurate (DBTDL), stannous octoate, bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth cyclopentanoate.

[0013] Furthermore, the oxidant is selected from one or more of H2O2, peroxybenzoic acid (PhCO3H), peracetic acid (CH3CO3H), trichloroacetic acid peroxide (CClCO3H), benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide and tert-butyl peroxide.

[0014] Further, the neutralizing agent is selected from one or more of triethylamine (TEA), triisopropanolamine, triethanolamine (TEOA), diethanolamine, dimethylethanolamine (DMEA), diethylethanolamine (DEEA) and 2-amino-2-methylpropanol.

[0015] Furthermore, the amine ring-opening agent is selected from one or more of isopropanolamine, methylamine, ethylenediamine, monoethanolamine (MEOA), ethylamine and 2-hydroxyethylamine.

[0016] Further, the cross-linking agent is selected from one or more of ferric chloride (FeCl3), ferrous chloride (FeCl2), manganese dichloride (MnCl2), zinc oxide, aluminum chloride, aluminum sulfate, boric acid, borax, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate;

[0017] The dispersant is selected from one or more of ethanol, deionized water, acetone, butanone, sodium dodecyl sulfate and methyl amyl alcohol;

[0018] The surface modifier is selected from one or more of ethylene glycol, sodium dodecyl sulfate, sodium hexadecylbenzene sulfonate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, dioctyl sodium sulfosuccinate, sodium stearate and polysorbate;

[0019] The defoaming agent is selected from one or more of higher alcohols, polydimethylsiloxane, ethanol, emulsified silicone oil, lauryl phenylacetate, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropanolamine ether, polyoxypropylene glycerol ether and polyoxypropylene;

[0020] The leveling agent is selected from one or more of butyl cellulose, polyacrylic acid, diacetone alcohol, polydimethylsiloxane, polymethylphenylsiloxane, Solvesso 150 and carboxymethyl cellulose;

[0021] The solvent is selected from one or more of N,N-dimethylformamide (DMF), acetone (AC), tetrahydrofuran (THF), 2-butanone, dimethyl sulfoxide (DMSO), isopropyl acetate, propylene glycol and pyridine.

[0022] The embodiment of the present invention also provides a method for preparing a functionalized Mxenes-modified biomass-based polyurea, the method comprising:

[0023] The biomass material and the catalyst are mixed, heated to 45-80°C, and then an oxidant is added to react for 3-6 hours, then washed with water until neutral and distilled under reduced pressure to obtain a light yellow transparent epoxidized bio-oil;

[0024] After the amine ring-opener and the epoxy bio-oil are mixed and heated to 50-65° C., a catalyst is added dropwise under stirring and condensation reflux conditions, and after the addition is completed, the temperature is continued to be raised to 80-100° C. and reacted at a constant temperature for 2-5 hours, washed to neutrality, filtered to obtain an upper layer of oily substance, and subjected to reduced pressure distillation to obtain a biomass-based polyamine;

[0025] The biomass-based polyamine, catalyst, solvent and isocyanate are mixed and heated in a water bath to 65-80° C., stirred and reacted for 1-2 hours, and then an amine chain extender is added. The isocyanate content of the system is detected. When the isocyanate content no longer changes, the temperature is lowered to 60-75° C., a cross-linking agent is added and reacted for 1-2 hours, and then the temperature is further lowered to 25-40° C., a neutralizer is added and a neutralization reaction is carried out for 1-1.5 hours, and then an organosilicon fluorine modifier is added and reacted for 1-2 hours, and then a functionalized Mxenes nanomaterial is added and reacted for 1-2 hours, and the solvent is removed by distillation under reduced pressure to obtain a functionalized Mxenes-modified biomass-based polyurea.

[0026] The embodiment of the present invention further provides a coating, wherein the coating is a membrane formed by coating and curing the functionalized Mxenes-modified biomass-based polyurea.

[0027] The functionalized Mxenes-modified biomass-based polyurea is mixed with a proper amount of solvent, defoamer and leveling agent, and then uniformly coated on a substrate and cured to form a film.

[0028] The components described in this step are as follows, by weight: 1 to 5 parts of solvent, 0.1 to 1.5 parts of defoaming agent and 0.1 to 1.5 parts of leveling agent.

[0029] One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0030] 1. A functionalized Mxenes-modified biomass-based polyurea and a preparation method thereof provided in an embodiment of the present invention form a highly cross-linked organic whole through the bonding action of components such as isocyanate, biomass polyamine, amine chain extender, silicon-fluorine modifier and nano-Mxenes material by chemical bonds, coordination bonds, hydrogen bonds and intermolecular interactions, so that the coating formed by the prepared coating has the advantages of excellent heat resistance, tensile properties, adhesion properties, anti-aging, acid and alkali resistance and hydrolysis resistance.

[0031] 2. The main raw material of the prepared product comes from renewable, degradable, non-toxic and cheap biomass oil. The raw material is abundant and the preparation process is simple. It not only saves energy consumption, but also is environmentally friendly during the synthesis process. It can replace petrochemical products to a certain extent and alleviate the energy crisis.

[0032] 3. After the coating is modified with functionalized Mxenes materials, it not only provides cross-linking points for the system to form dense cross-links, but also successfully introduces surface groups of Mxenes materials such as -OH, -F and O2- into the system. It also successfully transfers the ultra-high conductivity, high energy and power density of Mxenes materials into the coating, making it have potential characteristics in the fields of energy storage, electrochemistry, photocatalysis, electromagnetic shielding, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are some embodiments of the embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0034] Figure 1 The present invention provides a flow chart of a method for preparing a functionalized Mxenes-modified biomass-based polyurea. DETAILED DESCRIPTION

[0035] The following will be combined with specific implementation methods and examples to specifically describe the embodiments of the present invention, and the advantages and various effects of the embodiments of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementation methods and examples are used to illustrate the embodiments of the present invention, rather than to limit the embodiments of the present invention.

[0036] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood according to the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the embodiments of the present invention belong. In the event of a conflict, this specification takes precedence.

[0037] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the embodiments of the present invention can be purchased from the market or prepared by existing methods.

[0038] The technical solution provided by the embodiment of the present invention is to solve the above technical problems, and the overall idea is as follows:

[0039] According to another typical embodiment of the present invention, a method for preparing a functionalized Mxenes-modified biomass-based polyurea is provided, such as Figure 1 As shown, the method includes:

[0040] Step S1, mixing the biomass material and the catalyst, heating to 45-80°C, adding an oxidant and reacting for 3-6 hours, then washing with water until neutral and distilling under reduced pressure to obtain a light yellow transparent epoxidized bio-oil;

[0041] The reaction equation involved is: (taking H2O2 as a catalyst as an example)

[0042]

[0043] By weight, 25-45 parts of biomass material, 0.1-3 parts of catalyst, 0.1-15 parts of oxidant;

[0044] Step S2, after the amine ring-opener and the epoxy bio-oil are mixed and heated to 50-65° C., a catalyst is added dropwise under stirring and condensation reflux conditions, and after the addition is completed, the temperature is continued to be raised to 80-100° C. and reacted at a constant temperature for 2-5 hours, and the upper layer of oily substance is obtained by filtering after washing to neutrality, and the biomass-based polyamine is obtained by vacuum distillation;

[0045] The reaction equation involved is:

[0046]

[0047] By weight, 20-40 parts of amine ring-opener, 0.1-3% of catalyst,

[0048] Step S3, adding a dispersant and a surfactant to the MXenes nanomaterial to obtain a functionalized MXenes nanomaterial;

[0049] In the step S3, by weight, 0.5 to 10 parts of MXenes nanomaterial, 5 to 10 parts of dispersant and 0.5 to 10 parts of surfactant;

[0050] Step S4, the biomass-based polyamine, catalyst, solvent and isocyanate are mixed and heated in a water bath to 65-80° C., stirred and reacted for 1-2 hours, then an amine chain extender is added, the isocyanate content of the detection system is detected until the isocyanate content no longer changes, the temperature is lowered to 60-75° C., a cross-linking agent is added and reacted for 1-2 hours, then the temperature is further lowered to 25-40° C., a neutralizer is added and a neutralization reaction is carried out for 1-1.5 hours, then an organosilicon fluorine modifier is added and reacted for 1-2 hours, then a functionalized Mxenes nanomaterial is added and reacted for 1-2 hours, and the solvent is removed by distillation under reduced pressure to obtain a functionalized Mxenes modified biomass-based polyurea.

[0051] Since catalyst is added in step S1, S2 and S4, the total amount is 0.1 to 3 parts, and the three steps are added respectively: S1: 0.1 to 1.2 parts; S2: 0.1 to 0.8 parts; S4: 0.1 to 1.0 parts;

[0052] In parts by weight, isocyanate 15-25 parts, amine chain extender 0.1-5 parts, cross-linking agent 0.1-3 parts, neutralizer 0.1-1 parts, MXenes nanomaterial 0.5-10 parts, organosilicon fluorine modifier 0.5-15 parts, dispersant 5-15 parts, surface modifier 0.5-10 parts;

[0053] The method for preparing a functionalized Mxenes-modified biomass-based polyurea provided in an embodiment of the present invention forms a highly cross-linked organic whole through the bonding action of components such as isocyanate, biomass polyamine, amine chain extender, silicon-fluorine modifier and nano-Mxenes material by chemical bonds, coordination bonds, hydrogen bonds and intermolecular interactions, so that the coating formed by the prepared coating has the advantages of excellent heat resistance, tensile properties, adhesion properties, anti-aging, acid and alkali resistance and hydrolysis resistance.

[0054] The embodiment of the present invention also provides a coating, which is a film formed by coating and curing the functionalized Mxenes modified biomass-based polyurea. That is, the functionalized Mxenes modified biomass-based polyurea is mixed with an appropriate amount of solvent, defoamer and leveling agent and evenly coated on a substrate to form a film. The coating has potential characteristics in the fields of energy storage, electrochemistry, photocatalysis, electromagnetic shielding, etc.

[0055] The functionalized Mxenes-modified biomass-based polyurea and the preparation method thereof of the present application will be described in detail below in combination with examples, comparative examples and experimental data.

[0056] The MXenes nanomaterials of the embodiments of the present invention can be purchased directly or prepared by the following method:

[0057] A certain mass of LiF is dissolved in HCl to prepare an etching solution, and then the measured Ti3C2Tx is slowly added to the above solution under magnetic stirring at a certain temperature for a certain time. After the reaction is completed, the residue is washed several times by centrifugation with deionized water (DI) until a dark green supernatant with a pH>6 is obtained. Then, the obtained Ti3C2Tx and anhydrous ethanol are ultrasonically treated in an ice bath for a certain time, and then centrifuged to obtain a sediment. DI water is added to the sediment and ultrasonically treated to promote the exfoliation and stratification of Ti3C2Tx flakes. The supernatant obtained after centrifugation is a colloidal suspension of Ti3C2Tx nanosheets. The temperature is 45-50°C, the reaction time is 24-36h, and the ice bath ultrasonic time is 20-45min. The reaction principle is as follows:

[0058] LiF+HCl=HF+LiCl

[0059] Ti3AlC2+3HF=AlF3+1.5H2+Ti3C2

[0060] Ti3C2+H2O+HF=Ti3C2(OH,F)+H2.

[0061] Example 1

[0062] A functionalized Mxenes-modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of tetrafluoroboric acid (catalyst), 0.5 parts by weight of dibutyltin dilaurate (catalyst), 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine (neutralizer), 30 parts by weight of isopropanolamine (amine ring-opener), 1 part by weight of 2,6-diaminopyridine (amine chain extender), 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550 (organic silicon fluorine modifier), 0.5 parts by weight of FeCl3 (cross-linking agent), 5 parts by weight of acetone (dispersant), 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF (solvent).

[0063] Preparation method:

[0064] (1) Sesame oil and concentrated sulfuric acid are added to a 500 mL reactor equipped with a mechanical stirrer. After the temperature is raised to a certain temperature, peroxyformic acid is slowly added to the reaction system and reacted for a certain time. After the reaction is completed, the oil is washed with water until neutral, and the oil is distilled under reduced pressure to obtain a light yellow transparent epoxy bio-oil, and the epoxy value is measured.

[0065] (2) Weigh isopropanolamine and the epoxidized bio-oil of step 1) in a reactor, heat the reaction system to a certain temperature, add fluoroboric acid dropwise under stirring and condensation reflux conditions, control the addition to be completed within 1 hour, then continue to heat, and react at a constant temperature for a certain time. After the reaction is completed, wash it with sodium bicarbonate (NaCO3) and deionized water until it is neutral, filter out the lower clear liquid, and invert the upper oily substance in the reactor to distill under reduced pressure to obtain a biomass-based polyamine, and determine its amine value.

[0066] (3) The Ti3C2Tx suspension is vacuum dried to constant weight, a certain mass of Ti3C2Tx is weighed and dissolved in DMF, and then treated with ice bath ultrasound for a certain time. Then, a measured surfactant is gradually added, and the reaction is carried out for a certain time under magnetic stirring. Finally, the precipitate is collected by centrifugation and dried under vacuum to obtain functionalized Ti3C2Tx powder. The ice bath ultrasound time is 20-45 minutes, and the magnetic stirring reaction time is 3-5 hours. (The surfactant and Ti3C2Tx form a strong bond with non-covalent bonds)

[0067] (4) The dried biomass-based polyamine, dibutyltin dilaurate, DMF and the corresponding mass of isophorone diisocyanate were added to a nitrogen-filled reactor (with a stirrer and a reflux condenser), heated to a certain temperature in a water bath, reacted for a certain period of time under medium-speed stirring, and then 2,6-diaminopyridine was added. When the viscosity was too high during the reaction, acetone was added dropwise to adjust the viscosity. The isocyanate content of the system was detected every 30 minutes. When the isocyanate content no longer changed, the reaction system was cooled to a certain temperature, and FeCl3 crosslinking agent was added. After crosslinking for a certain period of time, the temperature was further cooled, triethylamine was added for neutralization, and KH-550 was added after sufficient neutralization. After a certain period of reaction, the functionalized Mxenes nanomaterials dispersed in acetone were added, stirred at a high speed for a certain period of time, and the solvent was removed by reduced pressure distillation to obtain the functionalized Mxenes modified biomass-based polyurea. Finally, it is evenly coated on a polytetrafluoroethylene plate, placed at room temperature for a certain period of time, and then placed in a high-temperature oven for curing to obtain a functionalized Mxenes-modified biomass-based polyurea coating.

[0068] Finally, the mixture is mixed with a solvent (1 part by weight), a defoamer (0.5 parts by weight) and a leveling agent (0.5 parts by weight), and the mixture is evenly coated on a substrate and cured to form a film.

[0069] Example 2

[0070] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 25 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of tetrafluoroboric acid (catalyst), 0.5 parts by weight of dibutyltin dilaurate (catalyst), 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine (neutralizer), 30 parts by weight of isopropanolamine (amine ring-opener), 1 part by weight of 2,6-diaminopyridine (amine chain extender), 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550 (organic silicon fluorine modifier), 0.5 parts by weight of FeCl3 (crosslinker), 5 parts by weight of acetone (dispersant), 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of defoamer, leveling agent, and 3 parts by weight of DMF (solvent). The preparation method is the same as that of Example 1.

[0071] Example 3

[0072] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 45 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of tetrafluoroboric acid (catalyst), 0.5 parts by weight of dibutyltin dilaurate (catalyst), 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine (neutralizer), 30 parts by weight of isopropanolamine (amine ring-opener), 1 part by weight of 2,6-diaminopyridine (amine chain extender), 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550 (organic silicon fluorine modifier), 0.5 parts by weight of FeCl3 (crosslinker), 5 parts by weight of acetone (dispersant), 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of defoamer, leveling agent, and 3 parts by weight of DMF (solvent). The preparation method is the same as that of Example 1.

[0073] Example 4

[0074] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 15 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of tetrafluoroboric acid (catalyst), 0.5 parts by weight of dibutyltin dilaurate (catalyst), 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine (neutralizer), 30 parts by weight of isopropanolamine (amine ring-opener), 1 part by weight of 2,6-diaminopyridine (amine chain extender), 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550 (organic silicon fluorine modifier), 0.5 parts by weight of FeCl3 (crosslinker), 5 parts by weight of acetone (dispersant), 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of defoamer, leveling agent, and 3 parts by weight of DMF (solvent). The preparation method is the same as that of Example 1.

[0075] Example 5

[0076] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 25 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of tetrafluoroboric acid (catalyst), 0.5 parts by weight of dibutyltin dilaurate (catalyst), 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine (neutralizer), 30 parts by weight of isopropanolamine (amine ring-opener), 1 part by weight of 2,6-diaminopyridine (amine chain extender), 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550 (organic silicon fluorine modifier), 0.5 parts by weight of FeCl3 (crosslinker), 5 parts by weight of acetone (dispersant), 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of defoamer, leveling agent, and 3 parts by weight of DMF (solvent). The preparation method is the same as that of Example 1.

[0077] Example 6

[0078] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 25 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 1 part by weight of 2,6-diaminopyridine, 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550, 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0079] Example 7

[0080] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of 2,6-diaminopyridine, 2 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550, 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0081] Example 8

[0082] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of dopamine, 5 parts by weight of functionalized Mxenes, 5 parts by weight of KH-550, 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0083] Example 9

[0084] A functionalized Mxenes modified biomass-based polyurea protective coating includes the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of dopamine, 5 parts by weight of functionalized Mxenes, 5 parts by weight of 1H, 1H, 2H, 2H perfluorododecyltriethoxysilane (HFDS), 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0085] Example 10

[0086] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of ethylenediamine, 2 parts by weight of dopamine, 5 parts by weight of functionalized Mxenes, 5 parts by weight of 1H, 1H, 2H, 2H perfluorododecyltriethoxysilane (HFDS), 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0087] Embodiment 11

[0088] A functionalized Mxenes modified biomass-based polyurea protective coating includes the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of 2,6-diaminopyridine, 5 parts by weight of functionalized Mxenes, 5 parts by weight of 1H,1H,2H,2H perfluorododecyltriethoxysilane (HFDS), 0.5 parts by weight of manganese dichloride (MnCl2), 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0089] Comparative Example 1

[0090] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of 2,6-diaminopyridine, 2 parts by weight of functionalized Mxenes, 5 parts by weight of acetone, 10 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0091] Comparative Example 2

[0092] A functionalized Mxenes modified biomass-based polyurea protective coating comprises the following components in parts by weight: 40 parts by weight of sesame oil, 20 parts by weight of isophorone diisocyanate, 0.5 parts by weight of concentrated sulfuric acid, 0.5 parts by weight of fluoroboric acid, 0.5 parts by weight of dibutyltin dilaurate, 10 parts by weight of peroxyformic acid, 0.5 parts by weight of triethylamine, 30 parts by weight of isopropanolamine, 2 parts by weight of 2,6-diaminopyridine, 5 parts by weight of KH-550, 0.5 parts by weight of FeCl3, 5 parts by weight of acetone, 0.5 parts by weight of a defoamer, a leveling agent, and 3 parts by weight of DMF. The preparation method is the same as that of Example 1.

[0093] Experimental Example 1

[0094] For the convenience of comparison, the formulations of the polyurea coatings prepared in Examples 1 to 8 above are summarized in Table 1.

[0095] Table 1

[0096]

[0097]

[0098] The functionalized Mxenes modified biomass-based polyurea coating prepared in the above example was coated, and the thickness of the two coatings was 1.5±0.2 mm. The physical properties tested are shown in Table 2 below:

[0099] Table 2 Physical properties of functionalized Mxenes modified biomass-based polyurea protective coating

[0100]

[0101] From Table 2, we can see that:

[0102] In Comparative Example 1, only nano-Mxenes material was added without adding isocyanate, biomass polyamine, amine chain extender, or silicon-fluorine modifier. The obtained functionalized Mxenes-modified biomass-based polyurea protective coating had low bonding strength and tensile strength, and the tensile strength retention rate was also low.

[0103] In Comparative Example 2, no nano-Mxenes material was added, and the obtained functionalized Mxenes-modified biomass-based polyurea protective coating had low bonding strength and tensile strength, and the tensile strength retention rate was also low.

[0104] The coating formed by the coating of the embodiment of the present invention has excellent water resistance, mechanical properties and chemical durability, and can effectively inhibit the penetration and corrosion of moisture to its surface.

[0105] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article, or apparatus.

[0106] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present invention.

[0107] Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the embodiments of the present invention. Thus, if these modifications and variations of the embodiments of the present invention fall within the scope of the claims of the embodiments of the present invention and their equivalents, the embodiments of the present invention are also intended to include these modifications and variations.

Claims

1. A functionalized Mxenes-modified biomass-based polyurea, characterized in that: The functionalized Mxenes modified biomass-based polyurea comprises, by weight: 25-45 parts of biomass material, 15-25 parts of isocyanate, 0.1-3 parts of catalyst, 0.1-15 parts of oxidant, 0.1-1 parts of neutralizer, 20-40 parts of amine ring opener, 0.1-5 parts of amine chain extender, 0.5-10 parts of MXenes nanomaterial, 0.5-15 parts of organosilicon fluorine modifier, 0.1-3 parts of cross-linking agent, 5-15 parts of dispersant, 0.5-10 parts of surfactant, 1-5 parts of solvent; The biomass material is selected from one or more of glucose, guar gum, soybean oil, corn oil, peanut oil, sesame oil, castor oil, rapeseed oil and olive oil; The isocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, HDI trimer, dicyclohexylmethane diisocyanate, toluene diisocyanate and lysine diisocyanate; The cross-linking agent is selected from one or more of ferric chloride, ferrous chloride, manganese dichloride, zinc oxide, aluminum chloride, aluminum sulfate, boric acid, borax, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate; The preparation method of the functionalized Mxenes-modified biomass-based polyurea comprises: The biomass material and the catalyst are mixed, heated to 45-80°C, and then an oxidant is added to react for 3-6 hours, then washed with water until neutral and distilled under reduced pressure to obtain a light yellow transparent epoxidized bio-oil; After the amine ring-opener and the epoxy bio-oil are mixed and heated to 50-65° C., a catalyst is added dropwise under stirring and condensation reflux conditions, and after the addition is completed, the temperature is continued to be raised to 80-100° C. and reacted at a constant temperature for 2-5 hours, washed to neutrality, filtered to obtain an upper layer of oily substance, and subjected to reduced pressure distillation to obtain a biomass-based polyamine; Adding MXenes nanomaterials to dispersants and surfactants to obtain functionalized MXenes nanomaterials; The biomass-based polyamine, catalyst, solvent and isocyanate are mixed and heated in a water bath to 65-80° C., stirred and reacted for 1-2 hours, then an amine chain extender is added, the isocyanate content of the system is detected, and when the isocyanate content no longer changes, the temperature is lowered to 60-75° C., a cross-linking agent is added and reacted for 1-2 hours, then the temperature is further lowered to 25-40° C., a neutralizer is added and a neutralization reaction is carried out for 1-1.5 hours, then an organosilicon fluorine modifier is added and reacted for 1-2 hours, then the functionalized Mxenes nanomaterial is added and reacted for 1-2 hours, and the solvent is removed by distillation under reduced pressure to obtain a functionalized Mxenes-modified biomass-based polyurea.

2. A functionalized Mxenes-modified biomass-based polyurea according to claim 1, characterized in that: The functionalized Mxenes modified biomass-based polyurea comprises, by weight: 34-42 parts of biomass materials, 18-24 parts of isocyanate, 0.1-3 parts of catalyst, 0.1-15 parts of oxidant, 0.1-1 part of neutralizer, 20-40 parts of amine ring-opener, 0.1-5 parts of amine chain extender, 0.5-10 parts of MXenes nanomaterials, 3-15 parts of organosilicon fluorine modifier, 0.1-3 parts of cross-linking agent, 5-15 parts of dispersant, 1-8 parts of surfactant, 0.1-1 part of defoamer, 0.1-1 part of leveling agent and 1-5 parts of solvent.

3. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The amine chain extender is selected from one or more of 2,6-diaminopyridine, 1,6-hexanediamine, dopamine, MOCA, ethylenediamine, diethylenetriamine, diethyltoluenediamine, diethylenetriamine and N-aminoethylpiperazine; The organosilicon fluorine modifier is selected from one or more of 1H, 1H, 2H, 2H perfluorododecyltriethoxysilane, polytrifluoropropylmethylsiloxane, 1H, 1H, 2H, 2H perfluorododecyltrichlorosilane, KH-550, KH-560, octadecyltrichlorosilane, phenyltrimethoxysilane, trimethylchlorosilane, chlorotrimethylsilane, vulcanized silicone rubber, heptafluoro-1,1,2,2-tetrahydrodecyldimethylchlorosilane, methyl silicone resin, silicone, 1,1,1,3,3,3-hexamethyldisilazane and methyltriethoxysilane.

4. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The catalyst is selected from one or more of formic acid, acetic acid, concentrated sulfuric acid, tetrafluoroboric acid, dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth cyclopentanoate.

5. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The oxidant is selected from one or more of H2O2, peroxybenzoic acid, peracetic acid, trichloroacetic acid peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide and tert-butyl peroxide.

6. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The neutralizing agent is selected from one or more of triethylamine, triisopropanolamine, triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and 2-amino-2-methylpropanol.

7. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The amine ring-opener is selected from one or more of isopropanolamine, methylamine, ethylenediamine, monoethanolamine, ethylamine and 2-hydroxyethylamine.

8. A functionalized Mxenes-modified biomass-based polyurea according to claim 1 or 2, characterized in that: The dispersant is selected from one or more of ethanol, deionized water, acetone, butanone, sodium dodecyl sulfate and methyl amyl alcohol; The surfactant is selected from one or more of sodium dodecyl sulfate, sodium hexadecylbenzene sulfonate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, dioctyl sodium sulfosuccinate, sodium stearate and polysorbate; The solvent is selected from one or more of N,N-dimethylformamide, acetone, tetrahydrofuran, 2-butanone, dimethyl sulfoxide, isopropyl acetate, propylene glycol and pyridine.

9. A method for preparing the functionalized Mxenes-modified biomass-based polyurea according to any one of claims 1 to 8, characterized in that: The method comprises: The biomass material and the catalyst are mixed, heated to 45-80°C, and then an oxidant is added to react for 3-6 hours, then washed with water until neutral and distilled under reduced pressure to obtain a light yellow transparent epoxidized bio-oil; After the amine ring-opener and the epoxy bio-oil are mixed and heated to 50-65° C., a catalyst is added dropwise under stirring and condensation reflux conditions, and after the addition is completed, the temperature is continued to be raised to 80-100° C. and reacted at a constant temperature for 2-5 hours, washed to neutrality, filtered to obtain an upper layer of oily substance, and subjected to reduced pressure distillation to obtain a biomass-based polyamine; Adding MXenes nanomaterials to dispersants and surfactants to obtain functionalized MXenes nanomaterials; The biomass-based polyamine, catalyst, solvent and isocyanate are mixed and heated in a water bath to 65-80° C., stirred and reacted for 1-2 hours, then an amine chain extender is added, the isocyanate content of the system is detected, and when the isocyanate content no longer changes, the temperature is lowered to 60-75° C., a cross-linking agent is added and reacted for 1-2 hours, then the temperature is further lowered to 25-40° C., a neutralizer is added and a neutralization reaction is carried out for 1-1.5 hours, then an organosilicon fluorine modifier is added and reacted for 1-2 hours, then the functionalized Mxenes nanomaterial is added and reacted for 1-2 hours, and the solvent is removed by distillation under reduced pressure to obtain a functionalized Mxenes-modified biomass-based polyurea.

10. A coating, characterized in that: The coating is a membrane formed by coating and curing the functionalized Mxenes-modified biomass-based polyurea described in any one of claims 1 to 8.

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