A bio-based polyurethane high-wear coating and method of making the same

Abstract

The application belongs to the technical field of bio-based materials and wear-resistant coatings, and relates to a bio-based polyurethane high wear-resistant coating and a preparation method thereof. The bio-based polyurethane high wear-resistant coating comprises a component A and a component B. The component A comprises the following components: a bio-based polyol, a pigment and filler, a first composite plasticizer, a bio-based catalyst, a dispersing agent, a leveling agent and a first mixed solvent. The component B comprises the following components: a polyether polyol, a diisocyanate, a second composite plasticizer and a second mixed solvent. The application provides a bio-based polyurethane high wear-resistant coating and a preparation method thereof, which are prepared by using bio-based polyether polyol as a main raw material, using chitosan loaded nano-zinc oxide as a bio-based catalyst and containing three innovative composite plasticizing systems. The bio-based polyurethane high wear-resistant coating is suitable for the surface protection of components with high wear-resistant requirements, such as mechanical parts, transmission parts and sliding guide rails, and has environmental protection and excellent wear-resistant durability.

Description

Technical Field

[0001] This invention belongs to the field of bio-based materials and wear-resistant coatings, and relates to a bio-based polyurethane high wear-resistant coating and its preparation method. Background Technology

[0002] Polyurethane coatings, due to their excellent mechanical, adhesive, and processability properties, are widely used in the surface protection of various mechanical components, especially in applications requiring wear resistance. However, traditional polyurethane coatings rely on petroleum-based raw materials, which not only consume non-renewable resources but also generate large amounts of volatile organic compound (VOC) emissions, contradicting the "dual-carbon" strategy and green development concept. Furthermore, existing bio-based polyurethane coatings generally have insufficient wear resistance, with high coefficients of friction (typically >0.20) and limited wear cycles, making them unsuitable for extreme operating conditions such as mechanical transmission and sliding, thus limiting their application in high-end wear-resistant fields. Summary of the Invention

[0003] To address the technical bottlenecks in existing bio-based polyurethane coatings, such as insufficient wear resistance, high coefficient of friction, poor wear resistance and durability, and limited wear-enhancing effect of plasticizers, this invention provides a bio-based polyurethane high wear-resistant coating and its preparation method. By screening specific bio-based raw materials, designing an innovative composite plasticizing system, and developing bio-based catalysts, an efficient, environmentally friendly, and stable preparation system is constructed, achieving a significant improvement in the wear resistance of bio-based polyurethane coatings and promoting the industrial application of bio-based wear-resistant coatings in high-end machinery fields.

[0004] This invention provides a bio-based polyurethane high wear-resistant coating and its preparation method, which uses bio-based polyether polyol as the main raw material, chitosan-supported nano zinc oxide (CS-ZnO) as a bio-based catalyst, and contains three innovative composite plasticizing systems. It is suitable for surface protection of mechanical parts, transmission components, sliding guides and other components with high wear resistance requirements. It is environmentally friendly and has excellent wear resistance and durability, and can realize the resource utilization of waste biological resources.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0006] This invention discloses a bio-based polyurethane high wear-resistant coating, which comprises component A and component B;

[0007] Component A comprises the following components in parts by weight:

[0008] Bio-based polyols, 45.0~55.0 parts;

[0009] Pigments and fillers, 25.0~35.0 parts;

[0010] First composite plasticizer, 3.0~5.0 parts;

[0011] Bio-based catalyst, 0.5~1.5 parts;

[0012] Dispersant, 1.0~2.0 parts;

[0013] Leveling agent, 0.5~1.0 parts;

[0014] First mixed solvent, 20.0~30.0 parts;

[0015] Component B comprises the following components in parts by weight:

[0016] Polyether polyol, 30.0~40.0 parts;

[0017] Diisocyanate, 8.0~12.0 parts;

[0018] Second composite plasticizer, 2.0~4.0 parts;

[0019] Second mixed solvent, 15.0~25.0 parts;

[0020] The mass ratio of component A to component B is (1.0~1.2):(1.0~1.2):(1.0~1.2).

[0021] In some embodiments, the bio-based polyurethane high abrasion-resistant coating comprises component A and component B;

[0022] Component A comprises the following components in parts by weight:

[0023] Bio-based polyols, 48.0~52.0 parts;

[0024] Pigments and fillers, 28.0~32.0 parts;

[0025] First composite plasticizer, 4.0~5.0 parts;

[0026] Bio-based catalyst, 0.5~1.2 parts;

[0027] Dispersant, 1.0~1.8 parts;

[0028] Leveling agent, 0.8~1.0 parts;

[0029] First mixed solvent, 23.0~28.0 parts;

[0030] Component B comprises the following components in parts by weight:

[0031] Polyether polyol, 33.0~38.0 parts;

[0032] Diisocyanate, 8.0~12.0 parts;

[0033] Second composite plasticizer, 3.0~4.0 parts;

[0034] Second mixed solvent, 18.0~22.0 parts;

[0035] The mass ratio of component A to component B is (1.0~1.2):(1.0~1.2).

[0036] In some embodiments, the bio-based polyurethane high abrasion-resistant coating comprises component A and component B;

[0037] Component A comprises the following components in parts by weight:

[0038] Bio-based polyols, 50.0 parts;

[0039] Pigments and fillers, 30.0 parts;

[0040] First composite plasticizer, 4.0~5.0 parts;

[0041] Bio-based catalyst, 0.5~1.0 parts;

[0042] Dispersant, 1.5 parts;

[0043] Leveling agent, 0.8 parts;

[0044] First mixed solvent, 25.0 parts;

[0045] Component B comprises the following components in parts by weight:

[0046] Polyether polyol, 35.0 parts;

[0047] Diisocyanate, 10.0 parts;

[0048] Second composite plasticizer, 3.0~4.0 parts;

[0049] Second mixed solvent, 20.0 parts;

[0050] The mass ratio of component A to component B is 1.0:1.0.

[0051] The pigments and fillers can synergistically improve the coating's hardness, lubricity, and wear resistance and durability.

[0052] The bio-based catalyst can improve polymerization efficiency, enhance coating density, and thus improve wear resistance.

[0053] In some embodiments, component A of the bio-based polyurethane high abrasion-resistant coating further includes the following components in parts by weight: a second catalyst, 0.1 to 0.6 parts; wherein the second catalyst is BYK-190, DISPERBYK-194, or SURFADIOLS 190.

[0054] In some embodiments, the bio-based polyurethane high abrasion-resistant coating component A further includes the following components in parts by weight: a second catalyst, 0.1 to 0.3 parts; wherein the second catalyst is BYK-190, DISPERBYK-194, or SURFADIOLS 190.

[0055] In some embodiments, component A of the bio-based polyurethane high abrasion-resistant coating further includes the following component in parts by weight: a second catalyst, 0.2 parts; wherein the second catalyst is BYK-190.

[0056] In some embodiments, the bio-based polyol is bio-based polyol FH-2010; the pigments and fillers are composed of fumed silica, talc, and polytetrafluoroethylene; the mass ratio of fumed silica, talc, and polytetrafluoroethylene is (0.5~1.5):(1.0~3.0):(0.5~1.5); the first composite plasticizer is composed of diisononyl phthalate and bio-based wear-resistant reinforcing material, the mass ratio of diisononyl phthalate and bio-based wear-resistant reinforcing material is (1.2~2.8):1 0.0, wherein the bio-based wear-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomers; the dispersant is a wetting and dispersing agent DISPERBYK-110, a polyetheramine-modified polysiloxane superdispersant SD-600, or a polymeric superdispersant GS-9211 containing an acidic group polyester structure; the leveling agent is a polyether-modified organosilicon BYK-333, an organosilicon-modified acrylate leveling agent LA-900, or a polyether-modified polydimethylsiloxane copolymer MOK. 2620; the first mixed solvent is a mixture of xylene and n-butyl acetate in any volume ratio, optionally a mixture of xylene and n-butyl acetate in a volume ratio of 3:2; the polyether polyol is polypropylene glycol ether, polytetrahydrofuran ether glycol, or polyethylene glycol; the diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate; the second composite plasticizer is composed of diisononyl phthalate and bio-based wear-resistant reinforcing material, wherein the mass ratio of diisononyl phthalate to bio-based wear-resistant reinforcing material is (1.2~2.8):1.0, and the bio-based wear-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomer; the second mixed solvent is a mixture of xylene and n-butyl acetate in any volume ratio, optionally a mixture of xylene and n-butyl acetate in a volume ratio of 3:2.

[0057] In some embodiments, the pigments and fillers are composed of fumed silica, talc, and polytetrafluoroethylene; the mass ratio of fumed silica, talc, and polytetrafluoroethylene is 1.0:2.0:1.0.

[0058] In some embodiments, the first composite plasticizer is composed of diisononyl phthalate and a bio-based abrasion-resistant reinforcing material, wherein the mass ratio of diisononyl phthalate to the bio-based abrasion-resistant reinforcing material is 2.0:1.0, and the bio-based abrasion-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomer.

[0059] In some embodiments, the dispersant is a wetting and dispersing agent DISPERBYK-110 or a polymeric superdispersant GS-9211 containing an acidic group polyester structure.

[0060] In some embodiments, the leveling agent is polyether-modified silicone BYK-333 or polyether-modified polydimethylsiloxane copolymer MOK 2620.

[0061] In some embodiments, the polyether polyol is a polypropylene glycol ether.

[0062] In some embodiments, the diisocyanate is diphenylmethane diisocyanate.

[0063] In some embodiments, the second composite plasticizer is composed of diisononyl phthalate and a bio-based abrasion-resistant reinforcing material, wherein the mass ratio of diisononyl phthalate to the bio-based abrasion-resistant reinforcing material is 2.0:1.0, and the bio-based abrasion-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomer.

[0064] In some embodiments, the bio-based catalyst is chitosan-supported zinc oxide nanoparticles; the chitosan-supported zinc oxide nanoparticles are prepared by cross-linking chitosan and zinc oxide nanoparticles with glutaraldehyde using a glutaraldehyde cross-linking method.

[0065] In some embodiments, the chitosan-supported nano-zinc oxide may optionally be prepared by the following method:

[0066] Chitosan was dissolved in a first solvent and mixed to obtain a chitosan solution; the nano-zinc oxide was dispersed in a second solvent and mixed to obtain a nano-zinc oxide suspension; the chitosan solution and the nano-zinc oxide suspension were mixed, and then glutaraldehyde was added to the system to carry out a cross-linking reaction. After the reaction was completed, the solid and liquid were separated, the solid was washed, and dried to obtain chitosan-supported nano-zinc oxide.

[0067] In some embodiments, the chitosan has a degree of deacetylation ≥90%.

[0068] In some embodiments, the first solvent is a 0.5 vt% to 2.0 vt% aqueous solution of acetic acid.

[0069] In some embodiments, the first solvent is a 1.0 vt% aqueous solution of acetic acid.

[0070] In some embodiments, the concentration of chitosan in the chitosan solution is 10 mg / mL to 30 mg / mL.

[0071] In some embodiments, the concentration of chitosan in the chitosan solution is 20 mg / mL.

[0072] In some embodiments, the nano-zinc oxide has a particle size of 30-80 nm.

[0073] In some embodiments, the second solvent is deionized water.

[0074] In some embodiments, the concentration of nano zinc oxide in the nano zinc oxide suspension is 10 mg / mL to 30 mg / mL.

[0075] In some embodiments, the concentration of nano zinc oxide in the nano zinc oxide suspension is 20 mg / mL.

[0076] In some embodiments, the mass ratio of chitosan in the chitosan solution to zinc oxide in the zinc oxide nano-suspension is (1.5~2.5):(0.2~0.6).

[0077] In some embodiments, the mass ratio of chitosan in the chitosan solution to zinc oxide in the zinc oxide nano-suspension is 2.0:0.4.

[0078] In some embodiments, the glutaraldehyde exists in the form of an aqueous solution, wherein the concentration of glutaraldehyde in the solution is 20 wt% to 30 wt%.

[0079] In some embodiments, the glutaraldehyde is present in the form of an aqueous solution with a concentration of 25 wt%.

[0080] In some embodiments, the amount of glutaraldehyde used is based on the mass of the nano zinc oxide in the nano zinc oxide suspension, and the mass ratio of the nano zinc oxide to the glutaraldehyde is (0.3~0.6):(0.4~0.7).

[0081] In some embodiments, the amount of glutaraldehyde used is based on the mass of the nano zinc oxide in the nano zinc oxide suspension, and the mass ratio of the nano zinc oxide to the glutaraldehyde is 0.4:0.5.

[0082] In some embodiments, the crosslinking reaction is carried out at a temperature of 50°C to 70°C.

[0083] In some embodiments, the crosslinking reaction is carried out at a temperature of 60°C.

[0084] In some embodiments, the crosslinking reaction takes 1 h to 3 h.

[0085] In some embodiments, the crosslinking reaction takes 2 hours.

[0086] In some embodiments, the washing solid is washed sequentially with deionized water and ethanol.

[0087] In some embodiments, the drying is vacuum drying at 50°C to 70°C for 20 h to 28 h.

[0088] In some embodiments, the drying is performed by vacuum drying at 60°C for 24 h.

[0089] Furthermore, this invention discloses a method for preparing the above-mentioned bio-based polyurethane high-wear-resistant coating, comprising the following steps:

[0090] (1) Mix the above-mentioned parts by weight of bio-based polyol, dispersant, leveling agent and first mixed solvent; then add the above-mentioned parts by weight of pigments and fillers and mix well; finally add the above-mentioned parts by weight of bio-based catalyst and first composite plasticizer and mix well to form homogeneous component A;

[0091] (2) The polyether polyol in the above weight parts is dehydrated under reduced pressure. After the dehydration is completed, the temperature is lowered. Then, the diisocyanate and the second composite plasticizer in the above weight parts are added to the system to carry out the polymerization reaction and obtain the polymerization product. Finally, the second mixed solvent in the above weight parts is added to the polymerization product for dilution and filtered to obtain the homogeneous component B.

[0092] (3) Mix the components A and B, let stand to defoam, and you will get a bio-based polyurethane high wear-resistant coating.

[0093] In some embodiments, when the component A further includes a second catalyst, the component A is prepared by the following method: mixing the above-mentioned parts by weight of bio-based polyol, dispersant, leveling agent and first mixed solvent; then adding the above-mentioned parts by weight of pigments and fillers and mixing; finally adding the above-mentioned parts by weight of bio-based catalyst, second catalyst and first composite plasticizer and mixing to form homogeneous component A.

[0094] In some embodiments, in step (2), the dehydration under reduced pressure is carried out at 128°C to 135°C; the pressure for the dehydration under reduced pressure is -0.100 MPa to -0.090 MPa; the dehydration under reduced pressure continues until the water content is less than or equal to 0.05%; the cooling is carried out at 70°C to 85°C; the polymerization reaction is carried out at 75°C to 90°C; the polymerization reaction is carried out for 1.5 h to 3 h; and the polymerization reaction is carried out under inert gas protection.

[0095] In some embodiments, in step (2), the dehydration under reduced pressure is carried out at 128°C; the dehydration under reduced pressure is carried out at a pressure of -0.098 MPa; the dehydration under reduced pressure continues until the water content is less than or equal to 0.05%; the cooling is carried out at 78°C; the polymerization reaction is carried out at a reaction temperature of 80°C; the polymerization reaction is carried out for 2 hours; and the polymerization reaction is carried out under inert gas protection.

[0096] In some embodiments, in step (3), the mass ratio of component A to component B is (1.0~1.2):(1.0~1.2).

[0097] In some embodiments, in step (3), the mass ratio of component A to component B is 1.0:1.0.

[0098] The application of the aforementioned bio-based polyurethane high abrasion-resistant coating in the preparation of abrasion-resistant coatings and / or in the preparation of abrasion-resistant materials is also within the scope of protection of this invention.

[0099] Specifically, in the above applications, the above-mentioned bio-based polyurethane high wear-resistant coating can be applied to the surface of the substrate after being allowed to stand and defoam, and then cured at 25~35℃ for 24~48 h.

[0100] Beneficial effects:

[0101] Compared with the prior art, the advantages of the present invention are as follows:

[0102] (1) This invention is the first to compound the petroleum-based plasticizer diisononyl phthalate (DINP) with three bio-based wear-resistant reinforcing materials (PCL-diol, CGE, PLA-oligomer) in a specific ratio (mass ratio of 2:1) to construct three innovative composite plasticizing systems. DINP ensures the flexibility and processing performance of the coating, while the unique structure of the three bio-based wear-resistant reinforcing materials can undergo cross-linking reaction with the polyurethane molecular chain to form wear-resistant groups, significantly reducing the coefficient of friction of the coating (≤0.12) and increasing the number of wear cycles (≥4800 times). The synergistic effect of the two makes the coating have both excellent anti-corrosion and wear-resistant properties, solving the technical bottleneck that existing plasticizers cannot simultaneously achieve both anti-corrosion and wear-resistant properties.

[0103] (2) This invention uses chitosan-supported nano-zinc oxide (CS-ZnO) as a bio-based catalyst to replace traditional precious metal catalysts, reducing costs by more than 30%, and exhibiting good biocompatibility and recyclability. The nano-zinc oxide in CS-ZnO can exert antibacterial and anti-corrosion effects, and the amino groups of chitosan can form hydrogen bonds with the hydroxyl groups on the substrate surface, improving the adhesion between the coating and the substrate (≥8.0 MPa). It has high catalytic efficiency and no agglomeration or deactivation problems.

[0104] (3) The present invention uses bio-based polyether polyol (bio-based polyol FH-2010) as the main raw material. The aliphatic flexible segments in its molecular chain can improve the flexibility and deformation resistance of the coating. Combined with bio-based catalyst CS-ZnO and bio-based wear-resistant reinforcing material, the bio-based content (bio-carbon content ≥30%) is greatly increased, the use of petroleum-based raw materials is reduced, and VOCs emissions are reduced (≤185 g / L), which is in line with the concept of green chemistry development.

[0105] (4) The present invention uses a pigment and filler system composed of fumed silica, ultrafine talc powder and polytetrafluoroethylene micro powder in a mass ratio of 1:2:1. Fumed silica enhances the hardness of the coating, ultrafine talc powder improves lubricity, and polytetrafluoroethylene micro powder further reduces the coefficient of friction. The three work together to improve the wear resistance and durability of the coating.

[0106] (5) The preparation process of this invention is simple, the reaction conditions are mild (room temperature curing), no complicated equipment is required, continuous production can be realized, it is easy to scale up industrial applications, it is suitable for various substrates such as carbon steel and aluminum alloy, and has broad market prospects.

[0107] (6) The three bio-based wear-resistant reinforcing materials (PCL-diol, CGE, PLA-oligomer) provided by this invention are all renewable bio-based materials with good biocompatibility, biodegradability, and excellent lubrication performance. They are respectively compounded with DINP to form three composite plasticizing systems, which can specifically improve the wear resistance of the coating. Chitosan-supported nano zinc oxide (CS-ZnO) serves as a bio-based catalyst, which not only has high catalytic efficiency but also enhances the density of the coating, further improving wear resistance and durability. Combined with specific pigment and filler systems, dispersants, and leveling agents, a significant breakthrough in wear resistance can be achieved. Therefore, the bio-based polyurethane high wear-resistant coating developed by this invention, which uses bio-based polyether polyol (FH-2010) as raw material, CS-ZnO as catalyst, and contains three innovative composite plasticizing systems as its core, has important theoretical significance and practical application value.

[0108] (7) This invention employs a stepwise polymerization and composite curing process, using bio-based polyols as the core raw material. It utilizes a CS-ZnO bio-based catalyst to promote efficient polymerization of polyurethane molecular chains, thereby enhancing the coating's density. Simultaneously, it employs a composite plasticizing system composed of diisononyl phthalate (DINP) and bio-based wear-resistant reinforcing materials (polycaprolactone diol, cashew phenol glycidyl ether, or polylactic acid oligomer) at a mass ratio of 2:1. This, combined with a composite pigment and filler system composed of fumed silica, talc, and polytetrafluoroethylene, and the synergistic effect of dispersants and leveling agents, achieves a significant breakthrough in wear resistance. The wear-resistant coating prepared by this invention exhibits excellent adhesion (≥8.0 MPa), a low coefficient of friction (≤0.12), high wear resistance (≥4800 cycles), high bio-based content (≥29%), low VOC emissions (≤185 g / L), and is environmentally friendly. It is suitable for surface protection of mechanical parts, transmission components, sliding guides, and other components requiring high wear resistance, and has broad prospects for industrial application. Detailed Implementation

[0109] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0110] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0111] The bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.) used in the examples is a pale yellow transparent liquid with a hydroxyl value of 110±20 mgKOH / g, an acid value ≤1.0 mgKOH / g, and a viscosity of 1500±300 cps@25℃. It was found to contain aliphatic flexible segments with a molecular weight range of 3000 Da~5000 Da. It can improve the flexibility and deformation resistance of the coating, and help enhance its wear resistance.

[0112] The pigments and fillers used in the examples—fumed silica (particle size 10 nm~20 nm)—were purchased from Aladdin Reagent (Shanghai) Co., Ltd.; ultrafine talc powder (particle size 5 μm~10 μm)—were purchased from Aladdin Reagent (Shanghai) Co., Ltd.; and polytetrafluoroethylene micro powder (particle size 1 μm~5 μm)—were purchased from Aladdin Reagent (Shanghai) Co., Ltd.

[0113] The plasticizers used in the examples—diisononyl phthalate (DINP)—were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; polycaprolactone diol (PCL-diol), with a number-average molecular weight of 1000 Da~2000 Da, a hydroxyl value of 108~112 mgKOH / g, and a purity of ≥99%, were purchased from Shandong Yuanfeng Biotechnology Co., Ltd.; cashew phenol glycidyl ether (CGE), with an epoxy value of 0.10~0.12 mol / 100g and a viscosity of 400~500 cps@25℃, were purchased from Shandong Yuanfeng Biotechnology Co., Ltd.; and polylactic acid oligomer (PLA-oligomer), with a molecular weight of 800 Da~1200 Da and an acid value of ≤2.0 mgKOH / g, were purchased from Shandong Yuanfeng Biotechnology Co., Ltd.

[0114] The dispersant used in the examples, DISPERBYK-110, was purchased from BYK Additives (Shanghai) Co., Ltd.

[0115] The leveling agent used in the examples, BYK-333, was purchased from BYK Additives (Shanghai) Co., Ltd.

[0116] The polypropylene glycol ether (number average molecular weight 2000) used in the examples was purchased from Haian Petrochemical Plant in Jiangsu Province.

[0117] The diphenylmethane diisocyanate (MDI) used in the examples was purchased from Wanhua Chemical Group Co., Ltd.

[0118] The chitosan-supported nano-zinc oxide (CS-ZnO) used in the examples was prepared by cross-linking chitosan (degree of deacetylation ≥90%, purchased from Shanghai Yuanye Biotechnology Co., Ltd.) and nano-zinc oxide (particle size 30~80 nm, purchased from Aladdin Reagent (Shanghai) Co., Ltd.) with glutaraldehyde. The theoretical loading of nano-zinc oxide is 15%~25% (mass percentage, i.e., the percentage of the mass of nano-zinc oxide to the total mass of CS-ZnO), and its appearance is a light yellow powder.

[0119] The specific preparation method of chitosan-supported nano-zinc oxide used in the examples is as follows: 2.0 g of chitosan was weighed and dissolved in 100 mL of 1 wt% acetic acid aqueous solution, and stirred at room temperature until completely dissolved to obtain a chitosan solution. 0.4 g of nano-zinc oxide was weighed and ultrasonically dispersed in 20 mL of deionized water for 30 min (power 200-300 W) to obtain a nano-zinc oxide suspension. The nano-zinc oxide suspension was slowly added dropwise to the chitosan solution, and stirring was continued at room temperature for 30 min. Subsequently, 2.0 mL of 25 wt% glutaraldehyde aqueous solution was added to the system as a crosslinking agent, and the crosslinking reaction was carried out in a water bath at 60℃ for 2 h. After the reaction, the solid was centrifuged (8000 rpm, 10 min) and washed three times with deionized water and anhydrous ethanol. The solid was dried in a vacuum drying oven at 60℃ for 24 h and ground into a uniform powder to obtain chitosan-supported nano-zinc oxide, denoted as CS-ZnO. The theoretical loading of nano-zinc oxide in chitosan-supported nano-zinc oxide is approximately 16.7%.

[0120] The catalyst BYK-190 used in the examples was purchased from BYK Additives (Shanghai) Co., Ltd.

[0121] The relevant indicators and their detection methods or standards in the examples are as follows: adhesion, GB / T 5210-2006; salt spray resistance time, GB / T 10125-2021; coefficient of friction, GB / T 3960-2016; abrasion resistance cycles, GB / T 1768-2006; biochar content, GB / T 39715.2-2021; VOCs content, GB / T 23986-2009.

[0122] Example 1:

[0123] (1) Preparation of component A

[0124] Component A (kg level) comprises the following components in parts by weight:

[0125] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0126] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0127] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0128] Bio-based catalyst: CS-ZnO, 1.0 part;

[0129] Dispersant: DISPERBYK-110, 1.5 parts;

[0130] Leveling agent: BYK-333, 0.8 parts;

[0131] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0132] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0133] (2) Preparation of component B

[0134] Component B (kg level) comprises the following components in parts by weight:

[0135] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0136] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0137] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0138] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0139] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0140] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0141] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0142] Performance tests: adhesion 8.7 MPa, salt spray resistance time 3200 h, coefficient of friction 0.09, abrasion resistance 5800 cycles (10 N load, 100 r / min, the same for the following examples), biochar content 32%, VOCs content 172 g / L.

[0143] Example 2:

[0144] (1) Preparation of component A

[0145] Component A (kg level) comprises the following components in parts by weight:

[0146] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 45.0 parts;

[0147] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 25.0 parts;

[0148] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0149] Bio-based catalyst: CS-ZnO, 1.0 part;

[0150] Dispersant: DISPERBYK-110, 1.5 parts;

[0151] Leveling agent: BYK-333, 0.8 parts;

[0152] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0153] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0154] (2) Preparation of component B

[0155] Component B (kg level) comprises the following components in parts by weight:

[0156] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0157] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0158] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0159] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0160] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0161] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0162] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0163] Performance tests: Adhesion 8.2 MPa, salt spray resistance time 2950 h, coefficient of friction 0.11, abrasion resistance 4800 cycles (10 N load, 100 r / min), biochar content 29%, VOCs content 178 g / L.

[0164] Example 3:

[0165] (1) Preparation of component A

[0166] Component A (kg level) comprises the following components in parts by weight:

[0167] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 55.0 parts;

[0168] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 35.0 parts;

[0169] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0170] Bio-based catalyst: CS-ZnO, 1.0 part;

[0171] Dispersant: DISPERBYK-110, 1.5 parts;

[0172] Leveling agent: BYK-333, 0.8 parts;

[0173] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 30.0 parts.

[0174] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0175] (2) Preparation of component B

[0176] Component B (kg level) comprises the following components in parts by weight:

[0177] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0178] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0179] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0180] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0181] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0182] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0183] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0184] Performance tests: Adhesion 8.6 MPa, salt spray resistance time 3250 h, coefficient of friction 0.10, abrasion resistance 5300 cycles, biochar content 34%, VOCs content 182 g / L.

[0185] Example 4:

[0186] (1) Preparation of component A

[0187] Component A (kg level) comprises the following components in parts by weight:

[0188] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0189] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0190] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0191] Bio-based catalyst: CS-ZnO, 0.5 parts;

[0192] Dispersant: DISPERBYK-110, 1.0 part;

[0193] Leveling agent: BYK-333, 0.5 parts;

[0194] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0195] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0196] (2) Preparation of component B

[0197] Component B (kg level) comprises the following components in parts by weight:

[0198] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0199] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0200] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0201] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0202] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0203] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0204] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0205] Performance tests: Adhesion 8.1 MPa, salt spray resistance time 2900 h, coefficient of friction 0.12, abrasion resistance 4900 cycles (10 N load, 100 r / min), biochar content 31%, VOCs content 174 g / L.

[0206] Example 5:

[0207] (1) Preparation of component A

[0208] Component A (kg level) comprises the following components in parts by weight:

[0209] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0210] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0211] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0212] Bio-based catalyst: CS-ZnO, 1.0 part;

[0213] Dispersant: GS-9211 (a polymeric superdispersant containing acidic groups and polyester structure, purchased from Shanghai Zhicheng), 1.5 parts;

[0214] Leveling agent: MOK 2620 (polyether modified polydimethylsiloxane copolymer, purchased from Merck, Germany), 0.8 parts;

[0215] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0216] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0217] (2) Preparation of component B

[0218] Component B (kg level) comprises the following components in parts by weight:

[0219] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0220] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0221] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0222] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0223] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0224] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0225] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0226] Performance tests: Adhesion 8.8 MPa, salt spray resistance time 3300 h, coefficient of friction 0.09, abrasion resistance 5900 cycles, biochar content 32%, VOCs content 171 g / L.

[0227] Example 6:

[0228] (1) Preparation of component A

[0229] Component A (kg level) comprises the following components in parts by weight:

[0230] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0231] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0232] First composite plasticizer: (composed of diisononyl phthalate (DINP) and cashew phenol glycidyl ether (CGE), with a mass ratio of DINP:CGE=2:1), 5.0 parts;

[0233] Bio-based catalyst: CS-ZnO, 1.0 part;

[0234] Dispersant: DISPERBYK-110, 1.5 parts;

[0235] Leveling agent: BYK-333, 0.8 parts;

[0236] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0237] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0238] (2) Preparation of component B

[0239] Component B (kg level) comprises the following components in parts by weight:

[0240] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0241] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0242] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and cashew phenol glycidyl ether (CGE), with a mass ratio of DINP:CGE=2:1, 4.0 parts;

[0243] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0244] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0245] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0246] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0247] Performance tests: Adhesion 9.0 MPa, salt spray resistance time 3400 h, coefficient of friction 0.08, abrasion resistance 6200 cycles, biochar content 31%, VOCs content 175 g / L.

[0248] Example 7:

[0249] (1) Preparation of component A

[0250] Component A (kg level) comprises the following components in parts by weight:

[0251] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0252] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0253] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polylactic acid oligomer (PLA-oligomer) in a mass ratio of DINP:PLA-oligomer = 2:1), 4.0 parts;

[0254] Bio-based catalyst: CS-ZnO, 1.0 part;

[0255] Dispersant: DISPERBYK-110, 1.5 parts;

[0256] Leveling agent: BYK-333, 0.8 parts;

[0257] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0258] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0259] (2) Preparation of component B

[0260] Component B (kg level) comprises the following components in parts by weight:

[0261] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0262] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0263] The second composite plasticizer (composed of diisononyl phthalate (DINP) and polylactic acid oligomer (PLA-oligomer) in a mass ratio of DINP:PLA-oligomer = 2:1), 3.0 parts;

[0264] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0265] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0266] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0267] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of an aluminum alloy substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0268] Performance tests: Adhesion 8.5 MPa, salt spray resistance time 3100 h, coefficient of friction 0.09, abrasion resistance 5500 cycles, biochar content 32%, VOCs content 172 g / L.

[0269] Example 8:

[0270] (1) Preparation of component A

[0271] Component A (kg level) comprises the following components in parts by weight:

[0272] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0273] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0274] First composite plasticizer: (composed of diisononyl phthalate (DINP) and cashew phenol glycidyl ether (CGE), with a mass ratio of DINP:CGE=2:1), 4.0 parts;

[0275] Bio-based catalyst: CS-ZnO, 0.8 parts;

[0276] Second catalyst BYK-190, 0.2 parts;

[0277] Dispersant: DISPERBYK-110, 1.5 parts;

[0278] Leveling agent: BYK-333, 0.8 parts;

[0279] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0280] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst, second catalyst, and first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0281] (2) Preparation of component B

[0282] Component B (kg level) comprises the following components in parts by weight:

[0283] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0284] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0285] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and cashew phenol glycidyl ether (CGE), with a mass ratio of DINP:CGE=2:1), 3.0 parts;

[0286] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0287] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0288] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0289] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0290] Performance tests: Adhesion 9.2 MPa, salt spray resistance time 3500 h, coefficient of friction 0.07, abrasion resistance 6800 cycles, biochar content 32%, VOCs content 170 g / L.

[0291] Example 9: Catalyst Recycling Experiment

[0292] (1) Preparation of component A

[0293] Bio-based polyols: Bio-based polyol FH-2010 (Zhangjiagang Feihang Technology Co., Ltd.), 50.0 parts;

[0294] Pigments and fillers: (composed of fumed silica, ultrafine talc powder, and polytetrafluoroethylene micro powder, wherein the mass ratio of the three is: fumed silica: ultrafine talc powder: polytetrafluoroethylene micro powder = 1:2:1), 30.0 parts;

[0295] First composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 4.0 parts;

[0296] Bio-based catalyst: CS-ZnO, 1.0 part;

[0297] Dispersant: DISPERBYK-110, 1.5 parts;

[0298] Leveling agent: BYK-333, 0.8 parts;

[0299] First mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 25.0 parts.

[0300] Preparation of Component A: At room temperature, the above-mentioned parts by weight of bio-based polyol, dispersant, and leveling agent were added to a reactor, and the above-mentioned parts by weight of the first mixed solvent were added. Stirring was started (500 rpm) until completely dissolved. Then, the above-mentioned parts by weight of pigments and fillers were added, and the stirring speed was increased to 1300 rpm for dispersion for 45 min. Finally, the above-mentioned parts by weight of bio-based catalyst and the first composite plasticizer were added, and stirring was continued for 25 min to form homogeneous Component A.

[0301] (2) Preparation of component B

[0302] Polyether polyol: Polypropylene glycol ether (number average molecular weight 2000, purchased from Haian Petrochemical Plant, Jiangsu Province), 35.0 parts;

[0303] Diisocyanate: Diphenylmethane diisocyanate (MDI), 10.0 parts;

[0304] Second composite plasticizer: (composed of diisononyl phthalate (DINP) and polycaprolactone diol (PCL-diol), with a mass ratio of DINP:PCL-diol = 2:1), 3.0 parts;

[0305] Second mixed solvent: (composed of xylene and n-butyl acetate in a volume ratio of 3:2), 20.0 parts.

[0306] Preparation of component B: The above-mentioned parts by weight of polyether polyol were added to a reactor, heated to 128°C, and dehydrated for 35 min under a vacuum of -0.098 MPa until the water content was ≤0.05%; then cooled to 78°C, and the above-mentioned parts by weight of diisocyanate and the second composite plasticizer were added. The reaction was carried out at 80°C for 2 h under nitrogen protection (flow rate 80 mL / min) to obtain the polymerization product; the above-mentioned parts by weight of the second mixed solvent were added for dilution, and the mixture was filtered through a 5 μm filter to obtain the homogeneous component B.

[0307] (3) Preparation of bio-based polyurethane high wear-resistant coating

[0308] The components A and B prepared in this embodiment were mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until homogeneous. After standing at room temperature for 12 minutes to defoam, the mixture was uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 hours to obtain a bio-based polyurethane high wear-resistant coating.

[0309] After the first reaction was completed, the unreacted CS-ZnO catalyst in component A was separated by column chromatography, dried under vacuum, and reused in the next reaction. This cycle was repeated three times, with the reaction conditions remaining unchanged each time. This example aimed to investigate the recyclability of the catalyst. The results showed that the first coating had a salt spray resistance time of 3200 h and a friction coefficient of 0.09; the second coating had a resistance time of 3100 h and a friction coefficient of 0.10; and the third coating had a resistance time of 3000 h and a friction coefficient of 0.11. No significant decrease in catalytic activity was observed, demonstrating that the CS-ZnO catalyst has good recyclability.

[0310] Example 10: Scale-up Experiment

[0311] This embodiment is a scale-up experiment. According to the formula ratio of Example 1, the dosage of component A and component B is simultaneously increased by 1000 times (for example, the original 1 g corresponds to 1 kg).

[0312] Preparation of bio-based polyurethane high wear-resistant coating: The components A and B prepared in this example are mixed online in a static mixer at a mass ratio of 1:1 for 18 minutes until uniform. After standing at room temperature for 12 minutes to defoam, the mixture is uniformly coated on the surface of a carbon steel substrate (coating thickness 70 μm) and cured at 28°C for 36 h to obtain the bio-based polyurethane high wear-resistant coating.

[0313] Performance tests: Adhesion 8.8 MPa, salt spray resistance time 3250 h, coefficient of friction 0.09, abrasion resistance 5700 cycles, biochar content 32%, VOCs content 173 g / L.

[0314] Comparative Example 1: No catalyst

[0315] The experimental methods, the amount of each material, and the experimental scale were the same as in Example 1. The difference was that no bio-based catalyst CS-ZnO was added to component A, and a bio-based polyurethane high wear-resistant coating was finally prepared.

[0316] Performance tests: Adhesion 4.5 MPa, salt spray resistance time 1200 h, coefficient of friction 0.32, abrasion resistance 2200 cycles, biochar content 32%, VOCs content 172 g / L.

[0317] Comparative Example 2: Single Plasticizer

[0318] The experimental methods, the amount of each material, and the experimental scale were the same as in Example 1. The difference was that the first plasticizer used in component A was only diisononyl phthalate (4.0 parts by weight); the second plasticizer used in component B was only diisononyl phthalate (4.0 parts by weight). Finally, a bio-based polyurethane high wear-resistant coating was prepared.

[0319] Performance tests: Adhesion 7.2 MPa, salt spray resistance time 2000 h, coefficient of friction 0.26, abrasion resistance 2000 cycles, biochar content 28%, VOCs content 195 g / L.

[0320] Table 1 Comparison of reaction parameters and performance of each embodiment and comparative example

[0321]

[0322] As shown in Table 1, the composite plasticizing system of DINP, PCL-diol, CGE, and PLA-oligomer used in this invention, which is compounded with PCL-diol, CGE, and PLA-oligomer in a mass ratio of 2:1, combined with CS-ZnO bio-based catalyst and specific compound pigments and fillers, can effectively improve the overall performance of the coating. The coefficient of friction of the coating is controlled at ≤0.12, the wear resistance is ≥4800 times, the adhesion is ≥8.0MPa, and the VOCs content is ≤185g / L, which combines environmental protection and practicality.

[0323] In Example 8, a mixed catalytic system of CS-ZnO and BYK-190 was used to optimize the coating performance, with a friction coefficient as low as 0.07 and a wear resistance of up to 6800 cycles.

[0324] The large-scale experimental data of Example 10 are basically consistent with the laboratory data (Example 1), proving that the preparation process of the present invention is stable and reliable and can be scaled up for industrial production.

[0325] In Example 7, after the substrate was replaced with aluminum alloy, the coating performance fluctuated slightly but still remained at an excellent level, indicating that the coating is suitable for a variety of substrates and has a wide range of applications.

[0326] Comparative Examples 1 and 2 further verified the necessity of the core design of this invention: Comparative Example 1 did not add CS-ZnO catalyst, the coating adhesion dropped to 4.5 MPa, the salt spray resistance time was only 1200 h, the friction coefficient increased to 0.32, and the number of wear cycles dropped significantly to 2200; Comparative Example 2 used a single DINP plasticizer without adding bio-based wear-resistant reinforcing materials, the coating friction coefficient increased to 0.26, the number of wear cycles was only 2000, and the VOCs content increased to 195 g / L. The performance of both examples dropped significantly, highlighting the core role of CS-ZnO catalyst and composite plasticizing system.

[0327] This invention provides a concept and method for preparing a bio-based polyurethane high-wear-resistant coating. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

Claims

1. A bio-based polyurethane high-wear-resistant coating, characterized in that, The bio-based polyurethane high abrasion-resistant coating comprises component A and component B; Component A comprises the following components in parts by weight: Bio-based polyols, 45.0~55.0 parts; Pigments and fillers, 25.0~35.0 parts; First composite plasticizer, 3.0~5.0 parts; Bio-based catalyst, 0.5~1.5 parts; Dispersant, 1.0~2.0 parts; Leveling agent, 0.5~1.0 parts; First mixed solvent, 20.0~30.0 parts; Component B comprises the following components in parts by weight: Polyether polyol, 30.0~40.0 parts; Diisocyanate, 8.0~12.0 parts; Second composite plasticizer, 2.0~4.0 parts; Second mixed solvent, 15.0~25.0 parts; The mass ratio of component A to component B is (1.0~1.2):(1.0~1.2).

2. The bio-based polyurethane high-wear-resistant coating according to claim 1, characterized in that, The bio-based polyurethane high abrasion-resistant coating comprises component A and component B; Component A comprises the following components in parts by weight: Bio-based polyols, 48.0~52.0 parts; Pigments and fillers, 28.0~32.0 parts; First composite plasticizer, 4.0~5.0 parts; Bio-based catalyst, 0.5~1.2 parts; Dispersant, 1.0~1.8 parts; Leveling agent, 0.8~1.0 parts; First mixed solvent, 23.0~28.0 parts; Component B comprises the following components in parts by weight: Polyether polyol, 33.0~38.0 parts; Diisocyanate, 8.0~12.0 parts; Second composite plasticizer, 3.0~4.0 parts; Second mixed solvent, 18.0~22.0 parts; The mass ratio of component A to component B is (1.0~1.2):(1.0~1.2).

3. The bio-based polyurethane high-wear-resistant coating according to claim 1, characterized in that, The bio-based polyurethane high abrasion-resistant coating component A also includes the following components in parts by weight: The second catalyst is 0.1 to 0.6 parts; wherein the second catalyst is BYK-190, DISPERBYK-194 or SURFADIOLS 190.

4. The bio-based polyurethane high-wear-resistant coating according to claim 1 or 2, characterized in that, The bio-based polyol is bio-based polyol FH-2010; the pigments and fillers are composed of fumed silica, talc, and polytetrafluoroethylene; the mass ratio of fumed silica, talc, and polytetrafluoroethylene is (0.5~1.5):(1.0~3.0):(0.5~1.5); the first composite plasticizer is composed of diisononyl phthalate and bio-based wear-resistant reinforcing material, the mass ratio of diisononyl phthalate and bio-based wear-resistant reinforcing material is (1.2~2.8):1.

0. The bio-based wear-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomers; the dispersant is a wetting and dispersing agent DISPERBYK-110, a polyetheramine-modified polysiloxane superdispersant SD-600, or a polymeric superdispersant GS-9211 containing an acidic group polyester structure; the leveling agent is a polyether-modified organosilicon BYK-333, an organosilicon-modified acrylate leveling agent LA-900, or a polyether-modified polydimethylsiloxane copolymer MOK. 2620; the first mixed solvent is a mixture of xylene and n-butyl acetate in any volume ratio, optionally a mixture of xylene and n-butyl acetate in a volume ratio of 3:2; the polyether polyol is polypropylene glycol ether, polytetrahydrofuran ether glycol, or polyethylene glycol; the diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate; the second composite plasticizer is composed of diisononyl phthalate and bio-based wear-resistant reinforcing material, wherein the mass ratio of diisononyl phthalate to bio-based wear-resistant reinforcing material is (1.2~2.8):1.0, and the bio-based wear-resistant reinforcing material is any one or a combination of several of polycaprolactone diol, cashew phenol glycidyl ether, and polylactic acid oligomer; the second mixed solvent is a mixture of xylene and n-butyl acetate in any volume ratio, optionally a mixture of xylene and n-butyl acetate in a volume ratio of 3:

2.

5. The bio-based polyurethane high-wear-resistant coating according to claim 1 or 2, characterized in that, The bio-based catalyst is chitosan-supported nano-zinc oxide; the chitosan-supported nano-zinc oxide is prepared by cross-linking chitosan and nano-zinc oxide with glutaraldehyde according to the glutaraldehyde cross-linking method.

6. The method for preparing the bio-based polyurethane high-wear-resistant coating according to any one of claims 1 to 5, characterized in that, Includes the following steps: (1) Mix the bio-based polyol, dispersant, leveling agent and first mixed solvent in any weight proportions of any one of claims 1 to 5; then add the pigments and fillers in the weight proportions and mix well; finally add the bio-based catalyst and first composite plasticizer in the weight proportions and mix well to form homogeneous component A; (2) The polyether polyol of any one of claims 1 to 5 is subjected to dehydration under reduced pressure. After the dehydration is completed, the temperature is lowered. Then, the diisocyanate and the second composite plasticizer of the same weight are added to the system to carry out the polymerization reaction to obtain the polymerization product. Finally, the second mixed solvent of the same weight is added to the polymerization product for dilution and filtration to obtain the homogeneous component B. (3) Mix the components A and B, let stand to defoam, and you will get a bio-based polyurethane high wear-resistant coating.

7. The preparation method according to claim 6, characterized in that, When the component A further includes a second catalyst, the component A is prepared by the following method: mixing the bio-based polyol, dispersant, leveling agent and first mixed solvent in any weight proportions of any one of claims 1 to 5; then adding the pigments and fillers in the weight proportions and mixing; finally adding the bio-based catalyst, second catalyst and first composite plasticizer in the weight proportions and mixing to form a homogeneous component A.

8. The preparation method according to claim 6, characterized in that, In step (2), the dehydration under reduced pressure is carried out at 128℃~135℃; the dehydration under reduced pressure is carried out at a pressure of -0.100 MPa~-0.090 MPa; the dehydration under reduced pressure continues until the water content is less than or equal to 0.05%; the cooling is carried out at 70℃~85℃; the polymerization reaction is carried out at a reaction temperature of 75℃~90℃; the polymerization reaction is carried out for a reaction time of 1.5 h~3 h; the polymerization reaction is carried out under inert gas protection.

9. The preparation method according to claim 6, characterized in that, In step (3), the mass ratio of component A to component B is (1.0~1.2):(1.0~1.2).

10. The use of the bio-based polyurethane high abrasion-resistant coating according to any one of claims 1 to 5 in the preparation of abrasion-resistant coatings and / or in the preparation of abrasion-resistant materials.

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