MMP-containing bio-based waterproof coating

Abstract

The invention discloses an MMP-containing bio-based waterproof coating, which belongs to the field of coatings and comprises a component A, a component B and a component C, the component A comprises the following components in parts by weight: 70 parts of a first composite solvent, 30-40 parts of nitrocellulose, 8-10 parts of a bio-based film-forming agent and an auxiliary agent; the component B comprises 60 parts of a second composite solvent and 40-45 parts of a composite nanofiller; the component C is a curing agent of the bio-based film-forming agent, and the mass ratio of the bio-based film-forming agent to the component C is (2.2-2.5): 1; the first composite solvent is prepared from 3-methyl-3-methoxy-1-butanol and a butyl butyryl lactate-ethanol solution, and the mass ratio of the 3-methyl-3-methoxy-1-butanol to the butyl butyryl lactate-ethanol solution is 3 to (2 to 2.5); the second composite solvent comprises methyl 3-methoxypropionate and isoparaffin, and the mass ratio of the methyl 3-methoxypropionate to the isoparaffin is 7: (3.3-3.5). Based on the nitrocellulose coating, the solid content of the coating is remarkably increased, so that the properties such as waterproofness and mechanical strength of the coating are enhanced.

Description

Technical Field

[0001] This invention belongs to the field of coatings and relates to a bio-based waterproof coating containing MMP. Background Technology

[0002] Nitrocellulose coatings, also known as nitrocellulose coatings, are a type of coating made by adding synthetic resins, toughening agents, and solvents to nitrocellulose as the main film-forming substance. Its biggest feature is that it dries quickly (surface dry in about 10 minutes), and the paint film is smooth and glossy and can be polished and repaired. However, it has a low solids content and poor mechanical strength, wear resistance, and water resistance of the coating. Summary of the Invention

[0003] The purpose of this invention is to provide a bio-based waterproof coating containing MMP, which solves the problems of low solid content and poor mechanical strength, wear resistance, and waterproof performance of existing nitrocellulose coatings.

[0004] The technical solution adopted in this invention is as follows:

[0005] A bio-based waterproof coating containing MMP, comprising component A, component B and component C;

[0006] Component A comprises the following components in parts by weight: 70 parts of the first composite solvent, 30-40 parts of nitrocellulose, 8-10 parts of bio-based film-forming agent, and additives;

[0007] Component B comprises 60 parts of a second composite solvent and 40-45 parts of composite nanofiller;

[0008] Component C is a curing agent for a bio-based film-forming agent, and the mass ratio of the bio-based film-forming agent to component C is 2.2-2.5:1;

[0009] The first composite solvent comprises 3-methyl-3-methoxy-1-butanol, butyryl lactate butyl ester-ethanol solution, wherein the mass ratio of 3-methyl-3-methoxy-1-butanol to butyryl lactate butyl ester-ethanol solution is 3:2-2.5;

[0010] The second composite solvent includes methyl 3-methoxypropionate and isoalkanes, with a mass ratio of methyl 3-methoxypropionate to isoalkanes of 7:3.3-3.5.

[0011] This application is based on nitrocellulose coatings. Taking advantage of its fast-drying properties, a high content of nanofillers is added to the coating to significantly increase the solid content of the coating, thereby enhancing the coating's waterproof and mechanical strength properties. During the research and development process, it was found that because the curing of nitrocellulose coatings mainly relies on the evaporation of solvents, when a large amount of nanofillers is added to the coating, the rapid evaporation of solvents causes intense physical compression between the nanoparticles due to the short-term escape of solvents. This can be regarded as an instantaneous escape, resulting in uneven distribution of internal stress in the coating, causing cracking and other problems, and making it impossible to form a continuous, dense, and smooth protective coating.

[0012] Based on the above problems, this application relates to a new solvent system, which is formed by combining a first composite solvent and a second composite solvent to replace the existing single fast-evaporating solvent. The use of solvents with different volatility produces a step-by-step evaporation effect, which makes the solvent evaporate gently. Compared with the evaporation of existing single solvents, the step-by-step evaporation of the solvent makes the stress change inside the coating more gradual, rather than concentrated. It can achieve uniform release and redistribution of stress inside the coating, effectively avoiding the problem of instantaneous escape of solvent in a short period of time, which prevents the formation of a continuous, dense and smooth protective coating.

[0013] Furthermore, the solid content in the coating affects its fluidity. The higher the solid content, the worse the fluidity and the more difficult it is to level. If the solvent evaporates rapidly during the leveling process of the coating, the fluidity of the coating will be even worse, which will seriously hinder the leveling of the coating and may even make the coating unusable and unable to form a uniform protective coating. Therefore, the step-evaporation solvent system of this invention provides sufficient time for the leveling of the coating and can effectively avoid the problem of leveling difficulties caused by the increase of solid content in the coating.

[0014] In the composite solvent system, MMP (methyl 3-methoxypropionate) is used as the core component of the composite nanofiller dispersion solvent. On the one hand, it achieves uniform distribution of the nanocomposite filler, and on the other hand, it does not leave a large amount of residue after volatilization during the curing process, thus reducing the content of volatile organic compounds during the use of the coating. In this invention, the nanofiller is first uniformly dispersed in the second composite solvent to form a slurry before being mixed with nitrocellulose and bio-based film-forming agent. This helps to improve the dispersion uniformity of the nanofiller and avoids the problem of uneven performance caused by excessively high local concentration due to local filler aggregation.

[0015] Furthermore, the composite nanofiller includes: stearic acid modified nano-calcium carbonate, polypropylene / maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, silane coupling agent modified nano-silica, and other functional nanofillers.

[0016] The mass ratio of stearic acid modified nano-calcium carbonate, maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, and silane coupling agent modified nano-silica is 2:3:5, and the total amount of other functional nanofillers is 2-3% of the total amount of composite nanofillers.

[0017] This invention primarily relates to a coating that can cure quickly and has high water resistance. Therefore, the nanofiller in this application includes hydrophobic stearic acid-modified nano-calcium carbonate, which, in addition to being used as a filler, enhances the hydrophobic effect of the coating. The polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material has good compatibility, which can improve the compatibility between the filler, polymer, and solvent. On the other hand, the plate-like structure of montmorillonite dispersed in the coating can effectively increase the diffusion path, making it difficult for water and corrosive ions to penetrate the coating. The silane coupling agent-modified nano-silica is mainly used to improve the strength, hardness, and wear resistance of the coating.

[0018] Furthermore, the other functional nanofillers include at least one of rare earth nanoparticles, nano titanium dioxide, nano graphene oxide, and nano zinc oxide.

[0019] Furthermore, the bio-based film-forming agent in component A is hydroxyl-terminated polylactic acid; and component C is a bio-based isocyanate oligomer.

[0020] To further achieve high water resistance, this invention also uses hydrophobic polylactic acid (PLA) as the film-forming agent. After cross-linking and curing of hydroxyl-terminated PLA with bio-based isocyanate oligomers, a PLA-polyurethane composite is formed. PLA has good hydrophobicity, and polyurethane has good elasticity. The combination of the two can improve the waterproof performance of the coating on the one hand, and the elasticity of polyurethane can buffer the physical compression between solids during solvent evaporation, further alleviating the problem of easy cracking of the coating caused by increased solid content.

[0021] Furthermore, component C is a 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer. The poly-2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate crosslinked polymer formed after crosslinking and curing of the 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer forms a hydrophobic layer upon contact with water in the air, further enhancing the waterproof performance of the entire coating.

[0022] Furthermore, the additive comprises the following components in parts by weight: 1-2 parts of non-silicone polymer defoamer, 1-2 parts of azobisisobutyronitrile initiator, and 2-3 parts of benzotriazole ultraviolet absorber.

[0023] Furthermore, the mass ratio of butyryl lactate to ethanol in the butyryl lactate-ethanol solution is 3:1.

[0024] Furthermore, the isoalkane is one or a mixture of two of isodecane and isododecane.

[0025] Furthermore, in the stearic acid-modified nano-calcium carbonate, stearic acid and nano-calcium carbonate are mixed and modified in a mass ratio of 2:1 to obtain stearic acid-modified nano-calcium carbonate.

[0026] Furthermore, the polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material is prepared by the following method: maleic anhydride-grafted polypropylene and organomontmorillonite are melted, extruded and granulated to obtain granules, which are then melt-extruded and granulated with polypropylene, and dried to obtain the polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material.

[0027] The amount of organomontmorillonite added is 3-4% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 5-6% of the mass of polypropylene.

[0028] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0029] 1. The present invention provides a bio-based waterproof coating containing MMP based on nitrocellulose coating. Taking advantage of its fast-drying properties, a high content of nanofillers is added to the coating to significantly increase the solid content of the coating, thereby enhancing the waterproof properties, mechanical strength and other properties of the coating.

[0030] 2. This invention uses a first composite solvent and a second composite solvent to form a new composite solvent system, replacing the existing single fast-evaporating solvent. The use of solvents with different volatility produces a step-by-step evaporation effect, which makes the solvent evaporate gently. Compared with the evaporation of existing single solvents, the step-by-step evaporation of the solvent makes the stress change inside the coating more gradual, rather than concentrated. It can achieve uniform release and redistribution of stress inside the coating, effectively avoiding the problem of instantaneous escape of solvent in a short period of time, which prevents the formation of a continuous, dense, and smooth protective coating.

[0031] 3. In order to further achieve high water resistance, the present invention also uses hydrophobic polylactic acid in the selection of film-forming agent. After cross-linking and curing of hydroxyl-terminated polylactic acid and bio-based isocyanate oligomer, a polylactic acid-polyurethane composite is formed. Polylactic acid has good hydrophobicity and polyurethane has good elasticity. The combination of the two can improve the waterproof performance of the coating on the one hand, and the elasticity of polyurethane can buffer the physical compression between solids during solvent evaporation, further alleviating the problem of easy cracking of the coating caused by the increase of solid content.

[0032] 4. The poly(2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate) cross-linked polymer formed by the cross-linking and curing of the 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer of the present invention will form a hydrophobic layer when it comes into contact with water in the air, which further improves the waterproof performance of the entire coating.

[0033] 5. The present invention combines stearic acid-modified nano-calcium carbonate, maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material, silane coupling agent-modified nano-silica, and other functional nanofillers to obtain a dense, waterproof, smooth, high-strength, and wear-resistant coating. Attached Figure Description

[0034] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort, wherein:

[0035] Figure 1 This is a flowchart illustrating the preparation process of a bio-based waterproof coating containing MMP.

[0036] Figure 2 This is a comparison chart of the waterproofing effects of the present invention. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0038] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0039] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0040] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0041] This invention provides a bio-based waterproof coating containing MMP, comprising component A, component B, and component C;

[0042] Component A comprises the following components in parts by weight: 70 parts of the first composite solvent, 30-40 parts of nitrocellulose, 8-10 parts of bio-based film-forming agent, and additives;

[0043] Component B comprises 60 parts of a second composite solvent and 40-45 parts of composite nanofiller;

[0044] Component C is a curing agent for a bio-based film-forming agent, and the mass ratio of the bio-based film-forming agent to component C is 2.2-2.5:1;

[0045] The first composite solvent comprises 3-methyl-3-methoxy-1-butanol, butyryl lactate butyl ester-ethanol solution, wherein the mass ratio of 3-methyl-3-methoxy-1-butanol to butyryl lactate butyl ester-ethanol solution is 3:2-2.5;

[0046] The second composite solvent includes methyl 3-methoxypropionate and isoalkanes, with a mass ratio of methyl 3-methoxypropionate to isoalkanes of 7:3.3-3.5.

[0047] The composite nanofiller includes: stearic acid modified nano-calcium carbonate, polypropylene / maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, silane coupling agent modified nano-silica, and other functional nanofillers; wherein the mass ratio of stearic acid modified nano-calcium carbonate, maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, and silane coupling agent modified nano-silica is 2:3:5, and the total amount of other functional nanofillers is 2-3% of the total amount of composite nanofiller.

[0048] The other functional nanofillers include at least one of rare earth nanoparticles, nano titanium dioxide, nano graphene oxide, and nano zinc oxide.

[0049] The bio-based film-forming agent in component A is hydroxyl-terminated polylactic acid; component C is a bio-based isocyanate oligomer.

[0050] Component C is a 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer. The preparation method is as follows: konjac polysaccharide and 2,5-furandicarboxylic acid undergo esterification under the catalysis of a catalyst to generate 2,5-furandicarboxylic acid konjac polysaccharide ester. The 2,5-furandicarboxylic acid konjac polysaccharide ester and isophorone diisocyanate are mixed in a mass ratio of 3:1 and heated to obtain the 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer.

[0051] The additives comprise the following components in parts by weight: 1-2 parts of non-silicone polymer defoamer, 1-2 parts of azobisisobutyronitrile initiator, and 2-3 parts of benzotriazole ultraviolet absorber.

[0052] The mass ratio of butyryl lactate to ethanol in the butyryl lactate-ethanol solution is 3:1. Butyryl lactate and ethanol are mixed at a mass ratio of 3:1 to obtain the butyryl lactate-ethanol solution.

[0053] The isoalkane is one or a mixture of two of isodecane and isododecane.

[0054] In the stearic acid-modified nano-calcium carbonate, stearic acid and nano-calcium carbonate are mixed and modified in a mass ratio of 2:1 to obtain stearic acid-modified nano-calcium carbonate.

[0055] The polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material is prepared by the following method: maleic anhydride-grafted polypropylene and organomontmorillonite are melted, extruded and granulated to obtain granules, which are then melt-extruded and granulated with polypropylene, and dried to obtain the polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material.

[0056] The amount of organomontmorillonite added is 3-4% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 5-6% of the mass of polypropylene.

[0057] The specific implementation method is as follows:

[0058] Example 1

[0059] Based on the above, such as Figure 1 As shown, a preferred embodiment of the present invention provides a bio-based waterproof coating containing MMP, which is prepared by the following method:

[0060] S1. First, butyryl lactate and ethanol are mixed at a mass ratio of 3:1 to obtain butyryl lactate-ethanol solution. Then, 3-methyl-3-methoxy-1-butanol and butyryl lactate-ethanol solution are mixed at a mass ratio of 3:2 to obtain the first composite solvent. 70 parts by weight of the first composite solvent are placed in a stirring tank, and 30 parts of nitrocellulose, 8 parts of hydroxyl-terminated polylactic acid, 1 part of non-silicone polymer defoamer, 1 part of azobisisobutyronitrile initiator, and 2 parts of benzotriazole ultraviolet absorber are added sequentially under stirring. After stirring evenly, component A is obtained.

[0061] S2. Stearic acid-modified nano-calcium carbonate, polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material (the amount of organic montmorillonite added is 3% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 6% of the mass of polypropylene) and silane coupling agent KH-560 modified nano-silica are pre-dry mixed according to a mass ratio of 2:3:5 to obtain a nano-mixture. 0.5% of cerium oxide nanoparticles and 2% of nano-titanium dioxide are added to the nano-mixture and mixed evenly to obtain a composite nanofiller.

[0062] The second composite solvent is obtained by uniformly mixing methyl 3-methoxypropionate and isodecane in a mass ratio of 7:3.3.

[0063] 60 parts by weight of the second composite solvent were added to a mixing tank. Under stirring, 40 parts of the composite nanofiller were slowly added to the second composite solvent and stirred until homogeneous to obtain component B. Under stirring, component B was slowly added to component A to obtain a mixed slurry.

[0064] S3. Mix the mixed slurry with 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer (component C), and stir evenly to obtain the target coating. The target coating is a bio-based waterproof coating containing MMP. The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer is 2.2:1.

[0065] Example 2

[0066] Based on the above, this embodiment, building upon Example 1, provides a preferred embodiment of the present invention of a bio-based waterproof coating containing MMP, which is prepared by the following method:

[0067] S1. First, butyryl lactate and ethanol are mixed at a mass ratio of 3:1 to obtain a butyryl lactate-ethanol solution. Then, 3-methyl-3-methoxy-1-butanol and the butyryl lactate-ethanol solution are mixed at a mass ratio of 3:2.3 to obtain the first composite solvent. 70 parts by weight of the first composite solvent are placed in a stirring tank, and under stirring, 35 parts of nitrocellulose, 9 parts of hydroxyl-terminated polylactic acid, 1.5 parts of non-silicone polymer defoamer, 1.5 parts of azobisisobutyronitrile initiator, and 2.5 parts of benzotriazole ultraviolet absorber are added sequentially. After stirring evenly, component A is obtained.

[0068] S2. Stearic acid-modified nano-calcium carbonate, polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material (the amount of organic montmorillonite added is 3% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 6% of the mass of polypropylene) and silane coupling agent KH-560 modified nano-silica are pre-dry mixed according to a mass ratio of 2:3:5 to obtain a nano-mixture. 0.5% of cerium oxide nanoparticles and 2% of nano-titanium dioxide are added to the nano-mixture and mixed evenly to obtain a composite nanofiller.

[0069] The second composite solvent is obtained by uniformly mixing methyl 3-methoxypropionate and isodecane in a mass ratio of 7:3.4.

[0070] 60 parts by weight of the second composite solvent were added to a mixing tank. Under stirring, 43 parts of composite nanofiller were slowly added to the second composite solvent and stirred until homogeneous to obtain component B. Under stirring, component B was slowly added to component A to obtain a mixed slurry.

[0071] S3. Mix the mixed slurry with 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer (component C), and stir evenly to obtain the target coating. The target coating is a bio-based waterproof coating containing MMP. The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer is 2.3:1.

[0072] A comparison of the waterproof coating prepared within the scope of this embodiment before and after waterproofing, such as... Figure 2 As shown, this application demonstrates a significant waterproofing effect.

[0073] Example 3

[0074] Based on the above, this embodiment, building upon Example 1, provides a preferred embodiment of the present invention of a bio-based waterproof coating containing MMP, which is prepared by the following method:

[0075] S1. First, butyryl lactate and ethanol are mixed at a mass ratio of 3:1 to obtain butyryl lactate-ethanol solution. Then, 3-methyl-3-methoxy-1-butanol and butyryl lactate-ethanol solution are mixed at a mass ratio of 3:2.5 to obtain the first composite solvent. 70 parts by weight of the first composite solvent are placed in a stirring tank. Under stirring, 40 parts of nitrocellulose, 10 parts of hydroxyl-terminated polylactic acid, 2 parts of non-silicone polymer defoamer, 2 parts of azobisisobutyronitrile initiator, and 3 parts of benzotriazole ultraviolet absorber are added in sequence. After stirring evenly, component A is obtained.

[0076] S2. Stearic acid-modified nano-calcium carbonate, polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material (the amount of organic montmorillonite added is 3% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 6% of the mass of polypropylene) and silane coupling agent KH-560 modified nano-silica are pre-mixed according to a mass ratio of 2:3:5 to obtain a nano-mixture. 0.5% of rare earth nanoparticles and 2% of nano-titanium dioxide by mass are added to the nano-mixture and mixed evenly to obtain a composite nanofiller.

[0077] The second composite solvent is obtained by uniformly mixing methyl 3-methoxypropionate and isodecane in a mass ratio of 7:3.5.

[0078] 60 parts by weight of the second composite solvent were added to a mixing tank. Under stirring, 45 parts of the composite nanofiller were slowly added to the second composite solvent and stirred until homogeneous to obtain component B. Under stirring, component B was slowly added to component A to obtain a mixed slurry.

[0079] S3. Mix the mixed slurry with 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer (component C), and stir evenly to obtain the target coating. The target coating is a bio-based waterproof coating containing MMP. The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer is 2.5:1.

[0080] Examples 4-5

[0081] Based on Example 2, Examples 4-5 differ from Example 2 in that the ratio of the first composite solvent is different, that is, the mass ratio of 3-methyl-3-methoxy-1-butanol, butyryl lactate-ethanol solution is different, and the specific ratio is shown in Table 1.

[0082] Table 1. Proportions of the first composite solvent

[0083] The ratio of the first composite solvent Example 2 The mass ratio of 3-methyl-3-methoxy-1-butanol, butyryl lactate, and ethanol solution is 3:2.3. Example 4 The mass ratio of 3-methyl-3-methoxy-1-butanol, butyryl lactate, and ethanol solution is 3:2. Example 5 The mass ratio of 3-methyl-3-methoxy-1-butanol, butyryl lactate, and ethanol solution is 3:2.5.

[0084] Examples 6-7

[0085] Based on Example 2, Examples 6-7 differ from Example 2 in that the ratio of the second composite solvent is different, that is, the ratio of methyl 3-methoxypropionate and isodecane is different, as shown in Table 2.

[0086] Table 2. Proportions of the second composite solvent

[0087] The ratio of the second composite solvent Example 2 Methyl 3-methoxypropionate and decadecane in a mass ratio of 7:3.4 Example 6 Methyl 3-methoxypropionate and decadecane in a mass ratio of 7:3.3 Example 7 methyl 3-methoxypropionate and isodecane in a mass ratio of 7:3.5

[0088] Example 8

[0089] Based on Example 2, the difference from Example 2 is that methyl 3-methoxypropionate and isododecane in a mass ratio of 7:3.4 are mixed evenly to obtain a second composite solvent.

[0090] Example 9

[0091] Based on Example 2, the difference from Example 2 is as follows: S2, stearic acid modified nano-calcium carbonate, polypropylene / maleic anhydride grafted polypropylene / montmorillonite nanocomposite material (the amount of organic montmorillonite added is 3% of the mass of polypropylene, and the amount of maleic anhydride grafted polypropylene added is 6% of the mass of polypropylene) and silane coupling agent KH-560 modified nano-silica are pre-dry mixed according to a mass ratio of 2:3:5 to obtain a nano-mixture. 0.5% of cerium oxide nanoparticles, 1% of nano-titanium dioxide, 1% of nano-zinc oxide and 0.5% of nano-graphene oxide are added to the nano-mixture and mixed evenly to obtain a composite nanofiller.

[0092] Examples 10-11

[0093] Based on Example 2, the difference from Example 2 is that the mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer is different, as detailed in Table 3;

[0094] Table 3. Curing agent dosage ratio

[0095] Increase in curing agent Example 2 The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer was 2.3:1. Example 10 The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer was 2.2:1. Example 11 The mass ratio of hydroxyl-terminated polylactic acid to 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer is 2.5:1.

[0096] Comparative Example 1

[0097] Based on Example 2, the difference from Example 2 is that the first composite solvent in this comparative example does not contain 3-methyl-3-methoxy-1-butanol, and the relevant steps in the preparation process have been adapted.

[0098] Comparative Example 2

[0099] Based on Example 2, the difference from Example 2 is that the first composite solvent in this comparative example does not contain butyryl lactate-ethanol solution, and the relevant steps in the preparation process have been adapted.

[0100] Comparative Example 3

[0101] Based on Example 2, the difference from Example 2 is that the first composite solvent in this comparative example does not contain ethanol, but is a mixture of 3-methyl-3-methoxy-1-butanol and butyryl lactate.

[0102] Comparative Example 4

[0103] Based on Example 2, the difference from Example 2 is that the second composite solvent in this comparative example does not contain methyl 3-methoxypropionate, and the relevant steps in the preparation process have been adapted.

[0104] Comparative Example 5

[0105] Based on Example 2, the difference from Example 2 is that the second composite solvent in this comparative example does not contain isodecane, and the relevant steps in the preparation process have been adapted.

[0106] Comparative Example 6

[0107] Based on Example 2, the difference from Example 2 is that this comparative example does not contain a second composite solvent, and the composite nanofiller is directly added to component A.

[0108] Comparative Example 7

[0109] Based on Example 2, but unlike Example 2, this comparative example does not contain 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer (component C).

[0110] Comparative Example 8

[0111] Based on Example 2, the difference from Example 2 is that this comparative example composite nanofiller does not contain stearic acid modified nano-calcium carbonate.

[0112] Comparative Example 9

[0113] Based on Example 2, the difference from Example 2 is that this comparative example composite nanofiller does not contain polypropylene / maleic anhydride grafted polypropylene / montmorillonite nanocomposite material.

[0114] Comparative Example 10

[0115] Based on Example 2, the difference from Example 2 is that this comparative example composite nanofiller does not contain silane coupling agent modified nano-silica.

[0116] Comparative Example 11

[0117] Based on Example 2, the difference from Example 2 is that this comparative example does not contain component B and does not perform step S2.

[0118] Comparative Example 12

[0119] Based on Example 2, the difference from Example 2 is that the bio-based film-forming agent in this comparative example is a plant oil-based polyol, and hydroxyl-terminated polylactic acid is not used.

[0120] Comparative Example 13

[0121] Based on Example 2, unlike Example 2, the solvent in this comparative example does not include the first composite solvent and the second composite solvent. Instead, a single acetone is used. Components A and B are added to the acetone solvent in sequence, and finally mixed with component C to obtain the coating.

[0122] Comparative Example 14

[0123] Based on Example 2, unlike Example 2, the solvent in this comparative example does not include the first composite solvent and the second composite solvent. Acetone and ethyl acetate with a mass ratio of 1:1 are used as composite solvents. Other components in component A and component B are directly added to the acetone and ethyl acetate composite solvent in sequence, and finally mixed with component C to obtain the coating.

[0124] Comparative Example 15

[0125] Based on Example 2, but unlike Example 2, this comparative example provides a nitrocellulose coating that uses acetone and ethyl acetate in a mass ratio of 1:1 as a composite solvent, without adding composite nanofillers. Other components in component A are added to the composite solvent in sequence, and finally mixed with component C to obtain the coating.

[0126] Comparative Example 16

[0127] Based on Example 2, but unlike Example 2, this comparative example provides a nitrocellulose coating that uses acetone and ethyl acetate in a mass ratio of 1:1 as a composite solvent, without adding composite nanofillers and component C, and the other components in component A are added to the composite solvent in sequence to obtain the coating.

[0128] Experimental Example 1

[0129] To test whether the coatings in Examples 1-11 and Comparative Examples 1-16 are workable, macroscopic inspection of the slurry before spraying and macroscopic inspection of the appearance of the coating after spraying are both required to meet the standards for workability.

[0130] Macroscopic inspection of the slurry before spraying: Inspect the uniformity of the slurry in the container before spraying, and check for abnormalities such as hard lumps or clumps.

[0131] Macroscopic inspection of the coating appearance after spraying: The coating was sprayed onto the sample substrate to a thickness of about 2 mm and placed in an environment of 25℃ and 50% humidity. The appearance of the coating was observed for 12 hours to check for abnormalities such as bubbles and cracks. The test results are shown in Table 4.

[0132] Table 4. Testing of Coating Workability

[0133] Macroscopic condition of the slurry before spraying Appearance of the coating after spraying Is it constructible? Examples 1-11 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 1 The slurry is uniform and free of lumps. The surface shows obvious cracks and roughness. Not constructible Comparative Example 2 The slurry is uneven and contains lumps. - Not constructible Comparative Example 3 The slurry is uniform and free of lumps. The coating has bumps, pits, and roughness. Not constructible Comparative Example 4 The slurry is uneven, contains hard lumps, and has sedimentation issues. - Not constructible Comparative Example 5 The slurry is uniform and free of lumps. Pinholes, rough, noticeably soft Not constructible Comparative Example 6 Unable to mix evenly - Not constructible Comparative Example 7 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 8 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 9 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 10 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 11 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 12 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 13 Uneven slurry, large amount of hard lumps - Not constructible Comparative Example 14 Uneven slurry, large amount of hard lumps - Not constructible Comparative Example 15 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable Comparative Example 16 The slurry is uniform and free of lumps. Normal, no abnormalities. Constructable

[0134] Experimental Example 2

[0135] According to the national standard GB / T 25271-2010, the solid content (determination of nonvolatile matter content (ISO 3251-2003)) and the surface drying time, water resistance, hardness (pencil hardness), adhesion (cross-cut test), and impact resistance of the coatings prepared in the constructible examples and comparative examples of Test Example 1 were tested. The results are shown in Table 5.

[0136] Surface drying time test: carried out in accordance with the provisions of GB / T1728—1979, and surface drying is carried out in accordance with the provisions of Method A;

[0137] Water resistance: The coating is sprayed onto the sample substrate to a thickness of about 2 mm and dried at 80±2℃ for 30 minutes. The immersion method is carried out according to GB / T9274—1988. The coated sample is immersed in Class III water that meets GB / T6682 standards. The duration of immersion when abnormalities occur is observed. Abnormal phenomena include wrinkles, blistering, cracking, and peeling.

[0138] Impact resistance: Tested according to GB / T 1732-1993 "Test Method for Impact Resistance of Coating Film".

[0139] Table 5 Performance test results of coatings and coating layers

[0140]

[0141] Based on the data in Tables 4 and 5, it can be seen that the first composite solvent in this application mainly maintains the uniformity of the overall base material, while the second composite solvent achieves the uniform dispersion of the composite nanofiller (high proportion). The first and second composite solvents work together to form a solvent evaporation gradient, preventing rapid solvent evaporation from causing cracks in the coating. The composite nanofiller in this application not only effectively increases the solid content of the coating but also enhances its mechanical strength and water resistance. The nitrocellulose coating prepared in this application has good water resistance and mechanical properties and can be used as a waterproof coating. The contact angle of the coatings in Examples 1-11 of this application is greater than 90°. After the coating of this application has cured, the VOC emissions in the area meet the standards after continuous ventilation for 24 hours.

[0142] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A bio-based waterproof coating containing MMP, characterized in that: Includes component A, component B, and component C; Component A comprises the following components in parts by weight: 70 parts of the first composite solvent, 30-40 parts of nitrocellulose, 8-10 parts of bio-based film-forming agent, and additives; Component B comprises 60 parts of a second composite solvent and 40-45 parts of composite nanofiller; Component C is a curing agent for a bio-based film-forming agent, and the mass ratio of the bio-based film-forming agent to component C is 2.2-2.5:1; The first composite solvent comprises 3-methyl-3-methoxy-1-butanol, butyryl lactate butyl ester-ethanol solution, wherein the mass ratio of 3-methyl-3-methoxy-1-butanol to butyryl lactate butyl ester-ethanol solution is 3:2-2.5; The second composite solvent includes methyl 3-methoxypropionate and isoalkanes, with a mass ratio of methyl 3-methoxypropionate to isoalkanes of 7:3.3-3.

5.

2. The bio-based waterproof coating containing MMP according to claim 1, characterized in that: The composite nanofillers include: stearic acid modified nano-calcium carbonate, polypropylene / maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, silane coupling agent modified nano-silica, and other functional nanofillers. The mass ratio of stearic acid modified nano-calcium carbonate, maleic anhydride grafted polypropylene / montmorillonite nanocomposite material, and silane coupling agent modified nano-silica is 2:3:5, and the total amount of other functional nanofillers is 2-3% of the total amount of composite nanofillers.

3. The bio-based waterproof coating containing MMP according to claim 2, characterized in that: The other functional nanofillers include at least one of rare earth nanoparticles, nano titanium dioxide, nano graphene oxide, and nano zinc oxide.

4. The bio-based waterproof coating containing MMP according to claim 1, characterized in that: The bio-based film-forming agent in component A is hydroxyl-terminated polylactic acid; component C is a bio-based isocyanate oligomer.

5. The bio-based waterproof coating containing MMP according to claim 2, characterized in that: Component C is a 2,5-furandicarboxylic acid konjac polysaccharide ester-isocyanate oligomer.

6. The bio-based waterproof coating containing MMP according to claim 5, characterized in that: The additives comprise the following components in parts by weight: 1-2 parts of non-silicone polymer defoamer, 1-2 parts of azobisisobutyronitrile initiator, and 2-3 parts of benzotriazole ultraviolet absorber.

7. The MMP-containing bio-based waterproof coating according to claim 1, characterized in that: The mass ratio of butyryl lactate to ethanol in the butyryl lactate-ethanol solution is 3:

1.

8. The MMP-containing bio-based waterproof coating according to claim 1, characterized in that: The isoalkane is one or a mixture of two of isodecane and isododecane.

9. The MMP-containing bio-based waterproof coating according to claim 2, characterized in that: In the stearic acid-modified nano-calcium carbonate, stearic acid and nano-calcium carbonate are mixed and modified in a mass ratio of 2:1 to obtain stearic acid-modified nano-calcium carbonate.

10. A bio-based waterproof coating containing MMP according to claim 2, characterized in that: The polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material is prepared by the following method: maleic anhydride-grafted polypropylene and organomontmorillonite are melted, extruded and granulated to obtain granules, which are then melt-extruded and granulated with polypropylene, and dried to obtain the polypropylene / maleic anhydride-grafted polypropylene / montmorillonite nanocomposite material. The amount of organomontmorillonite added is 3-4% of the mass of polypropylene, and the amount of maleic anhydride-grafted polypropylene added is 5-6% of the mass of polypropylene.

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