Vegetable oil based polyols, waterborne polyurethanes and methods of making and use in a mortar floor coating

Abstract

The present application relates to a kind of vegetable oil-based polyols, water-based polyurethane and preparation method and application in mortar floor paint.The present application obtains vegetable oil-based polyols by epoxy plant oil and natural chlorogenic acid carry out epoxy ring-opening reaction;In addition, by vegetable oil-based polyols and isocyanate proportion under room temperature condition stirring reaction solidification, obtain vegetable oil-based water-based polyurethane;In addition, the present application also relates to the application of vegetable oil-based polyols in water-based polyurethane antistatic mortar floor paint.The vegetable oil-based water-based polyurethane prepared by vegetable oil-based polyols and isocyanate in the present application has good antibacterial effect;Further, the present application prepares water-based polyurethane antistatic mortar floor paint, and its performance is superior to the performance of ordinary water-based polyurethane mortar, and also endows it with the ability of antibacterial, conductive and excluding accumulated static charge (surface resistance long-term maintains 1×10 4 ~1×10 9 Without appearing attenuation).

Description

Technical Field

[0001] The present invention relates to the field of coating raw material synthesis and coating preparation, and in particular to a vegetable oil-based polyol, a waterborne polyurethane, a preparation method and an application thereof in mortar floor coatings. Background Art

[0002] Polyurethane (PU), also known as polyurethanes, has the general structural formula (-R-NH-COOR-)n (the figure below is a schematic diagram of the polyurethane synthesis route). It is a type of block copolymer combining flexible and rigid segments formed through the polycondensation reaction of polyols and isocyanates. Due to its advantages such as simple processing and molding, flexible preparation formulas, and diverse product forms, it is widely used in many areas of the national economy. However, traditional solvent-based polyurethanes are prone to producing large amounts of volatile organic compounds (VOCs), such as toluene, dichloromethane, and N,N-dimethylformamide. The use of these petrochemical raw materials poses serious environmental problems and health threats to human life. With the improvement of public safety awareness and the introduction of various environmental laws and regulations, the development of safe, non-toxic, and high-performance bio-based waterborne polyurethane materials has become a key focus of the industry.

[0003]

[0004] Since its birth in the 1970s, polyurethane mortar coating has quickly become a rising star in today's industrial and commercial coatings with its excellent performance. Waterborne polyurethane mortar is an organic-inorganic hybrid polymer composite material. The curing of the coating includes both the cross-linking reaction of the organic resin and the hydration reaction of the inorganic powder. Among them, cement is used as an inorganic gelling material, which is in situ compounded with the organic resin to make the coating have both the toughness and high adhesion of organic materials and the rigidity and high and low temperature resistance of inorganic materials. In addition, in order to give waterborne polyurethane mortar more functionality (such as anti-corrosion; antistatic; antibacterial, etc.), it can also be improved in a targeted manner. Modification methods include: synthesis process, additive addition, optimized compounding, etc., which can be widely used in food processing plants, electronic and electrical manufacturing, chemical processing plants and other floors with functional requirements.

[0005] In recent years, with the widespread use of polymer materials, the phenomenon of static charging has brought serious harm to life and production; especially in situations where floor systems are often subject to friction and easily accumulate a large amount of static charge. In order to combat static disasters and give floor coatings excellent conductivity, the development of functional anti-static floor coatings has become an urgent problem to be solved. Its common conductive media are generally divided into: carbon series, metal series, metal oxide series, conductive powder, conductive additives and new conductive materials. For building floor coatings, for cost considerations, carbon series conductive materials are usually used to achieve conductive / anti-static effects. However, due to their own physical and chemical properties, these materials will affect their dispersion in the matrix to a certain extent, resulting in uneven resistance distribution and poor flow and leveling properties of the paint surface.

[0006] Table 1: Advantages and disadvantages of various conductive materials

[0007]

[0008] Summary of the Invention

[0009] In order to solve the above-mentioned technical problems, the present invention provides a plant oil-based polyol, a water-based polyurethane, a preparation method and an application in mortar floor coatings. The preparation method of the plant oil-based polyol can give the prepared coating excellent environmental protection and a certain antibacterial effect. In addition, the three-dimensional decorative floor coating obtained by optimizing the composite with a conductive medium not only has an artistic decorative effect, but also has good conductive / anti-static functions.

[0010] To solve the above problems, the present invention is implemented through the following technical solutions:

[0011] The first object of the present invention is:

[0012] Provided is a method for preparing a vegetable oil-based polyol:

[0013] The epoxidized vegetable oil and natural chlorogenic acid are subjected to an epoxidation ring-opening reaction to obtain a vegetable oil-based polyol.

[0014] The preparation method of the vegetable oil-based polyol of the present invention is further optimized as follows:

[0015] The preparation method of the vegetable oil-based polyol of the present invention comprises the following preparation steps:

[0016] S1: Epoxy ring-opening reaction of epoxidized vegetable oil and natural chlorogenic acid;

[0017] The epoxy ring-opening reaction temperature is 75-85°C, and the stirring time is 60-180 minutes;

[0018] S2: The reactant prepared in step S1 is cooled to room temperature, extracted with ethyl acetate and washed with a saturated NaCl solution; finally, the ethyl acetate is removed by rotary evaporation to obtain a vegetable oil-based polyol.

[0019] The preparation method of the vegetable oil-based polyol of the present invention is further optimized as follows:

[0020] The method for preparing the vegetable oil-based polyol of the present invention comprises one or a combination of the following features:

[0021] The epoxy vegetable oil and natural chlorogenic acid have an epoxy:carboxyl functional group ratio of 1:1.0-1.2;

[0022] The epoxidized vegetable oil is one or a combination of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, and epoxidized sunflower oil; preferably, epoxidized soybean oil and epoxidized linseed oil. Depending on the type of epoxidized vegetable oil, the resulting polyol has a relative molecular weight between 200 and 1000, and its molecular structure contains reactive functional groups such as carbon-carbon double bonds, hydroxyl groups, and amino groups. The hydroxyl value is between 100 and 160, and the acid value is between 15 and 25.

[0023] The second object of the present invention is:

[0024] Provided is a vegetable oil-based polyol, which is prepared according to the above-mentioned preparation method of the vegetable oil-based polyol.

[0025] The third object of the present invention is:

[0026] Provided is a method for preparing a vegetable oil-based waterborne polyurethane, comprising the steps of: reacting the vegetable oil-based polyol and the isocyanate in a certain proportion under stirring at room temperature to obtain the vegetable oil-based waterborne polyurethane;

[0027] The weight ratio of the vegetable oil-based polyol to isocyanate is 4.2-4.4:4.6-5.

[0028] The preparation method of the vegetable oil-based waterborne polyurethane of the present invention is further optimized as follows:

[0029] The isocyanate is one or a combination of SUPRASEC 5005, DESMODUR VL, WANNATE PM-200, WANNATE MDI-50, and DESMODUR 2460M.

[0030] The fourth object of the present invention is:

[0031] Provided is a vegetable oil-based waterborne polyurethane, which is prepared according to the above-mentioned preparation method of the vegetable oil-based waterborne polyurethane.

[0032] The vegetable oil-based waterborne polyurethane of the present invention is a vegetable oil-based waterborne polyurethane with good antibacterial effect.

[0033] The fifth object of the present invention is:

[0034] Provided is a method for preparing a waterborne polyurethane antistatic mortar floor coating, comprising the following preparation steps:

[0035] s1: The vegetable oil-based polyol, tetraethylene glycol, plasticizer, defoamer, paraffin oil, and pure water prepared above are mixed in a weight ratio of 28-32:4-8:14-18:1-5:4-8:37-41, and water is slowly added to emulsify the mixture while stirring with a homogenizer to obtain a milky white emulsion-like aqueous dispersion;

[0036] s2: mechanically stirring and uniformly mixing the milky white emulsion-like aqueous dispersion prepared in step s1 with isocyanate, inorganic active aggregate, color paste and conductive composite material in a weight ratio of 4.2-4.4:4.6-5:18-21:0.08-1:0.03-0.05, and then curing at room temperature to obtain a waterborne polyurethane antistatic mortar floor coating;

[0037] The conductive medium in the conductive composite material is a composite of carbon fibers and functionalized carbon nanotubes (PDA@MWCNTs), and the mass ratio of carbon fibers to functionalized carbon nanotubes (PDA@MWCNTs) is 2-4:1-3. The conductive composite material has excellent antistatic properties and a stable specific resistance value.

[0038] The functionalized carbon nanotubes (PDA@MWCNTs) are prepared by the following steps:

[0039] Carbon nanotubes (MWCNTs) and dopamine (PDA) were added to a 30-50 mmol / L tris(hydroxymethyl)aminomethane hydrochloride (Tris) solution in a mass ratio of 1:1.2-1.5, and hydrochloric acid solution was added dropwise to adjust the pH to between 8 and 10. After ultrasonication at room temperature for 1 hour, magnetic stirring was performed for 8-24 hours to ensure sufficient reaction. Finally, the product was washed with anhydrous ethanol and centrifuged at high speed, and the obtained product was collected and dried in a vacuum drying oven at 60°C to obtain functionalized carbon nanotubes (PDA@MWCNTs).

[0040] In the present invention, all carbon nanotubes (MWCNTs) and carbon nanotubes MWCNTs mentioned include single-walled carbon nanotubes and multi-walled carbon nanotubes. Although the carbon nanotubes (MWCNTs) and carbon nanotubes MWCNTs in the text use the abbreviation of multi-walled carbon nanotubes MWCNTs, their meanings include single-walled carbon nanotubes and multi-walled carbon nanotubes; accordingly, functionalized carbon nanotubes (PDA@MWCNTs) and functionalized carbon nanotubes PDA@MWCNTs also have the same meaning.

[0041] Inspection and characterization are carried out in accordance with GB / T22374-2008, JC / T985-2005 and GB21866-2008.

[0042] The preparation method of the waterborne polyurethane antistatic mortar floor coating of the present invention is further optimized as follows:

[0043] It includes one or a combination of the following features:

[0044] The isocyanate is one or a combination of SUPRASEC 5005, DESMODUR VL, WANNATE PM-200, WANNATE MDI-50, and DESMODUR 2460M;

[0045] The inorganic active aggregate is a reactive filler, which includes:

[0046] Alkaline earth metal hydroxide, sand, white cement, lime, crushed rubber, crushed plastic, quartz sand or a combination thereof; preferably alkaline earth metal hydroxide and quartz sand, wherein alkaline earth metal hydroxide acts as a CO2 absorbent to reduce the occurrence of pores and foaming.

[0047] The color paste is made of raw materials including conductive carbon black and vegetable oil-based polyol, which are fully ground into a slurry and fully stirred during construction to obtain a mixture color paste with uniform and stable color.

[0048] The sixth object of the present invention is:

[0049] Provided is a waterborne polyurethane antistatic mortar floor coating, which is prepared according to the preparation method of the waterborne polyurethane antistatic mortar floor coating described above.

[0050] The waterborne polyurethane antistatic mortar floor coating of the present invention is green and environmentally friendly, has extremely low VOCs, is heavy-duty, is resistant to high and low temperatures, has good leveling properties, is resistant to dry-wet alternation, has good antibacterial properties, and has excellent antistatic properties.

[0051] The main reactions of the waterborne polyurethane antistatic mortar floor coating of the present invention are as follows:

[0052] 1. Preparation of vegetable oil-based polyols

[0053]

[0054] 2. Organic reactions involved in the preparation of waterborne polyurethane antistatic mortar floor coatings

[0055]

[0056] 3. Inorganic reactions involved in the preparation of waterborne polyurethane anti-static mortar floor coatings

[0057]

[0058] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0059] The plant oil-based waterborne polyurethane developed in the present invention is based on naturally renewable epoxy plant oil and chlorogenic acid containing a benzene ring structure. The chlorogenic acid, which is rich in hydroxyl and amino groups, provides abundant hydrogen bonding sites for the waterborne polyurethane, giving the plant oil-based waterborne polyurethane good antibacterial properties and mechanical strength. Dopamine (PDA) is used to surface-modify carbon nanotubes (MWCNTs). On the one hand, the dopamine (PDA) layer polymerized on the surface of the functionalized carbon nanotubes (PDA@MWCNTs) introduces functional molecules to the substrate surface, promoting strong interactions between active sites (-COOH, -OH, -NH2) and the waterborne polyurethane polymer molecular chains, resulting in better dispersibility of the conductive medium. Stronger electrostatic and π-π bond interactions can effectively improve the mechanical and conductive properties of the coating. On the other hand, the dopamine (PDA) layer polymerized on the surface of the carbon nanotubes (MWCNTs) can effectively prevent them from connecting with each other in the polyurethane matrix, thereby avoiding short circuits to a certain extent, ensuring that the resulting antistatic floor coating has excellent compressive strength, flexural strength, and good antistatic effect.

[0060] Furthermore, by regulating the structure of the vegetable oil, the antibacterial waterborne polyurethane is produced. This ensures that the waterborne polyurethane mortar maintains its inherent properties (heavy load, high hardness, good leveling, good abrasion resistance, scratch resistance, and chemical resistance) while also imparting antibacterial properties. Furthermore, the floor coating product produced by this invention complies with the national standard "GB / T22374-2008" for floor coating materials, ensuring that emissions of toxic and hazardous substances such as volatile organic compounds (VOCs) are far below national standards.

[0061] The waterborne polyurethane antistatic mortar floor coating of the present invention is composed of a self-leveling, waterborne polyurethane-based mortar layer with cement and antistatic materials. The organic-inorganic double cross-linked composite hybrid ensures that the coating has both the excellent flow and leveling properties, adhesion, and toughness of organic materials; and the high strength, impact resistance, chemical resistance, and high and low temperature resistance of inorganic materials. The high-modulus functional conductive medium (conductive carbon black, conductive carbon fiber, functionalized carbon nanotubes (PDA@MWCNTs)) runs through the double cross-linked network as the third phase, achieving strong hydrogen bonding with the polyurethane molecular chains, effectively improving the mechanical properties and conductive properties of the coating, and ensuring that the surface / volume resistance of the composite material is maintained stably at 1×10 4 ~1×10 9 Ω, achieving the conversion between static dissipative and conductive types. To a certain extent, it overcomes the shortcomings of the concrete system, such as cracking, blistering, and poor mechanical toughness. It also makes up for the shortcomings of the epoxy resin system, such as easy discoloration, poor wear resistance, poor high and low temperature resistance, and chemical corrosion resistance, and has a stronger ability to adapt to application conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 These are the surface effect diagrams of the mortar floor coatings of Examples 5 and 8 to 9 of the present invention.

[0063] Figure 2 These are AFM renderings of the mortar floor coatings of Examples 5 and 8 to 9 of the present invention. DETAILED DESCRIPTION

[0064] In order to make the application, technical solutions and advantages of the present invention more clearly understood, the present invention is described in detail with reference to specific embodiments. It should be understood that the embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. Any simple improvement to the preparation method of the present invention based on the concept of the present invention falls within the scope of protection of the present invention.

[0065] Example 1

[0066] Preparation of a vegetable oil-based waterborne polyurethane:

[0067] (1) First, a hydroxyl-rich vegetable oil-based polyol was synthesized: Epoxidized soybean oil and chlorogenic acid were added to a 50 mL round-bottom flask at a ratio of 1:1.0 for epoxy:carboxyl functional groups. The mixture was stirred at 80°C for 60–180 min. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and washed with saturated NaCl solution. Finally, the ethyl acetate was removed by rotary evaporation to obtain the vegetable oil-based polyol.

[0068] (2) The resulting vegetable oil based polyol and isocyanate (DESMODUR VL: WANNATE MDI-50 = 4: 1) were stirred at room temperature in a ratio of 4.4:5 to react and cure.

[0069] Example 2:

[0070] Example 2 differs from Example 1 in that:

[0071] Only DESMODUR VL in the isocyanate of Example 1 step (2) was replaced with SUPRASEC 5005, and the other parameters and steps refer to Example 1.

[0072] Example 3:

[0073] Example 3 differs from Example 1 in that:

[0074] Only DESMODUR VL in the isocyanate of Example 1 step (2) was replaced with WANNATE PM-200, and the other parameters and steps refer to Example 1.

[0075] Example 4:

[0076] Example 4 differs from Example 1 in that:

[0077] Only WANNATE MDI-50 in the isocyanate of Example 1 step (2) was replaced with DESMODUR 2460M, and the other parameters and steps refer to Example 1.

[0078] Preparation of an aqueous polyurethane

[0079] Preparation of an aqueous polyurethane

[0080] Only chlorogenic acid in Example 1 step (1) was replaced with glutaric acid, and the other parameters and steps refer to Example 1.

[0081] Preparation of an aqueous polyurethane

[0082] Preparation of an aqueous polyurethane

[0083] Only chlorogenic acid in Example 1 step (1) was replaced with citric acid, and the other parameters and steps refer to Example 1.

[0084] Table 2: Mechanical properties and antibacterial properties of the aqueous polyurethanes of Examples 1-4 and Comparative Examples 1-2

[0085] Examples Tensile stress (MPa) Elongation at break (%) Antibacterial rate (%) Example 1 15.32 100.5 97.64 Example 2 16.72 96.5 96.21 Example 3 17.82 93.9 94.93 Example 4 16.92 97.3 98.13 Comparative Example 1 10.14 78.5 34.68 Comparative Example 2 6.57 59.7 59.37

[0086] The antibacterial rate of the plant oil-based waterborne polyurethane prepared by the present invention significantly decreased from 97.6% to 34.68% and 59.37% after the chlorogenic acid was replaced with glutaric acid and citric acid, respectively. However, the antibacterial rate remained unchanged when the isocyanate was adjusted to the aforementioned combinations. This suggests that isocyanates have no significant inhibitory effect on waterborne plant oil-based waterborne polyurethanes, while the tri-acid structure of chlorogenic acid exhibits a favorable antibacterial effect on plant oil-based waterborne polyurethanes.

[0087] Example 5: A waterborne polyurethane antistatic mortar floor coating

[0088] Preparation of the waterborne polyurethane antistatic mortar floor coating of the present invention:

[0089] (1) Preparation of component A (preparation of vegetable oil-based polyol aqueous dispersion):

[0090] The vegetable oil-based polyol prepared in step (1) of Example 1, tetraethylene glycol, plasticizer, defoamer, paraffin oil, and pure water were mixed in a weight ratio of 30:6:16:3:6:39, and water was slowly added under stirring with a homogenizer to emulsify the mixture to obtain a milky white emulsion-like aqueous dispersion;

[0091] (2) Preparation of component B (preparation of curing agent):

[0092] Component B is an isocyanate curing agent;

[0093] Use industrial-grade MDI: DESMODUR VL, WANNATE PM-200, SUPRASEC 5005, combined with WANNATEMDI-50 and DESMODUR 2460M in a ratio of 4:1;

[0094] (3) Preparation of component C (preparation of inorganic active aggregate):

[0095] Component C includes the following components in parts by weight:

[0096] 56 parts of 30-50 mesh fine white sand, 36 parts of 52.5 grade Portland white cement, 8 parts of calcium hydroxide (CO2 absorbent);

[0097] Mix and stir with a horizontal spiral mixer for 10 minutes until uniform, and seal and package to obtain component C;

[0098] (4) Preparation of component D (preparation of color paste):

[0099] The vegetable oil-based polyol prepared in step (1) of Example 1, the plasticizer, the defoamer, the dispersant, the acetylene black, and the titanium dioxide were mixed in a ratio of 20:40:2:2:6:30, put into a high-speed blender for mixing, ground to a fineness of less than 100 μm, filtered, and packaged to obtain component D;

[0100] (5) Preparation of component E:

[0101] Carbon nanotubes (MWCNTs) and dopamine (PDA) are added to a 30-50 mmol / L tris(hydroxymethyl)aminomethane hydrochloride (Tris) solution in a mass ratio of 1:1.2-1.5, and a hydrochloric acid solution is added dropwise to adjust the pH to between 8 and 10. After ultrasonication at room temperature for 1 hour, magnetic stirring is performed for 8-24 hours to ensure sufficient reaction. Finally, the product is washed with anhydrous ethanol and centrifuged at high speed, and the resulting product is collected and dried in a vacuum drying oven at 60°C to obtain functionalized carbon nanotubes (PDA@MWCNTs). Subsequently, the functionalized carbon nanotubes (PDA@MWCNTs) and conductive fibers are mixed in a mass ratio of 4:1 to obtain component E.

[0102] (6) Preparation of waterborne polyurethane antistatic mortar floor coating of the present invention:

[0103] 4.4 parts by weight of component A are added with 1 part by weight of component D and 0.05 parts by weight of component E, and stirred at high speed (1600-2000 r / min) for 30-40 seconds. Then, 5 parts by weight of component B and 18 parts by weight of the mixed component C are added, and high-speed stirring is continued for 2-5 minutes to obtain Example 5, which is the water-based polyurethane antistatic mortar floor coating of the present invention.

[0104] Example 6:

[0105] The difference between Example 6 and Example 5 is that:

[0106] Only 0.05 parts by weight of component E in step (6) of Example 5 was replaced with 0.04 parts by weight, and the remaining parameters and steps were the same as in Example 5.

[0107] Example 7:

[0108] The difference between Example 7 and Example 5 is that:

[0109] Only 0.05 parts by weight of component E in step (6) of Example 5 was replaced with 0.03 parts by weight, and the remaining parameters and steps were the same as those of Example 5.

[0110] Comparative Example 3:

[0111] The difference between Comparative Example 3 and Example 5 is:

[0112] Only 0.05 parts by weight of component E in step (6) of Example 5 was replaced with 0 parts by weight, and the remaining parameters and steps were the same as those of Example 5.

[0113] Example 8:

[0114] The difference between Example 8 and Example 5 is that:

[0115] Only the mass ratio of functionalized carbon nanotubes (PDA@MWCNTs) to conductive fibers in step (5) of Example 5 was adjusted from 4:1 to 3:2, and the remaining parameters and steps were the same as in Example 5.

[0116] Example 9:

[0117] The difference between Example 9 and Example 5 is that:

[0118] Only the mass ratio of functionalized carbon nanotubes (PDA@MWCNTs) to conductive fibers in step (5) of Example 5 was adjusted from 4:1 to 2:3, and the remaining parameters and steps were the same as in Example 5.

[0119] Comparative Example 4:

[0120] The difference between Comparative Example 4 and Example 5 is:

[0121] Only the mass ratio of functionalized carbon nanotubes (PDA@MWCNTs) to conductive fibers in step (5) of Example 5 was adjusted to 4:1 so that only conductive fibers were used. The remaining parameters and steps were the same as in Example 5.

[0122] The antistatic waterborne polyurethanes of Examples 5 to 7 and Comparative Example 3 were tested in accordance with GB / T22374-2008, JC / T985-2005 and GB21866-2008.

[0123] Table 3: Performance tests of Examples 5 to 7 and Comparative Example 3

[0124]

[0125]

[0126] In Comparative Example 3, in which component E is not added, compared with 0.05 parts by weight in Example 5, 0.04 parts by weight in Example 6, and 0.03 parts by weight in Example 7, the proportions of other components are guaranteed to remain unchanged, and the test is carried out in accordance with GB / T22374-2008, JC / T985-2005, and GB21866-2008: the chemical resistance does not change significantly, but the antistatic property decreases by a certain order of magnitude, realizing the transformation of the surface resistance from the electrostatic conductive type to the electrostatic dissipative type; at the same time, the compressive flexural strength also decreases to a certain extent, indicating that the addition of conductive medium functionalized carbon nanotubes (PDA@MWCNTs) and conductive carbon fibers has a significant promoting effect on the mechanical properties and antistatic properties; due to the aggregation of the conductive medium, the coating is slightly thickened, resulting in a higher addition amount and a shorter operating time, but there is no obvious change in the appearance of the coating.

[0127] Table 4 Surface resistance values ​​of Example 5, Examples 8-9, and Comparative Example 4

[0128]

[0129] In Comparative Example 4, no functionalized carbon nanotubes (PDA@MWCNTs) were added, and the simple conductive carbon fibers could not reach the anti-static order of magnitude. Compared with Examples 5, 8, and 9, the surface resistance of the composite conductive medium containing functionalized carbon nanotubes (PDA@MWCNTs) and conductive carbon fibers was significantly reduced. As the amount of functionalized carbon nanotubes (PDA@MWCNTs) added increased, the interaction between the composite conductive medium and the substrate increased, forming stronger π-π bonds and electrostatic interactions, thereby forming a more effective conductive network.

[0130] In summary, the present invention prepares vegetable oil-based polyols by regulating the structure of vegetable oils, and combines the modification and doping of functional particles to make the performance of the prepared waterborne polyurethane antistatic mortar floor coating better than that of ordinary waterborne polyurethane mortar (heavy load resistance, high and low temperature resistance (-40 to 110°C), chemical resistance, etc.), and also gives it antibacterial, conductive and static charge accumulation elimination (surface resistance is maintained at 1×10 4 ~1×10 9 The invention can effectively fill the gap of water-based polyurethane mortar type anti-static floor materials, solve the shortcomings of conventional anti-static epoxy resin self-leveling floor, anti-static cast terrazzo, anti-static metal wear-resistant floor (corundum), and anti-static long-lasting veneer PVC floor in the market, meet the demand of optoelectronics, electronics and other industries for heavy-load resistant, anti-static and non-ignitable floor, improve the technical level of floor surface coating materials, and have great commercial development prospects.

[0131] The waterborne polyurethane antistatic mortar floor coating of the present invention has the advantages of being green and environmentally friendly, extremely low in VOCs, heavy-duty, resistant to high and low temperatures, good leveling properties, resistance to dry-wet alternation, and excellent antistatic properties.

[0132] As used herein, "GB / T22374-2008" is the national standard for floor coating materials. It specifies the terms and definitions, product classifications, hazardous substance limits, physical property requirements, test methods, inspection rules, labeling, packaging, transportation, and storage for synthetic resin-based floor coating materials with environmentally friendly requirements. This standard applies to floor coating materials with special functional requirements (such as antistatic and anti-slip properties) applied to surfaces such as cement mortar and concrete.

[0133] As used herein, “JC / T 985-2005” is a standard for cement-based self-leveling mortar for floor (a standard of the building materials industry standard (JC)), which specifies the scope, terms and definitions, classification and marking, requirements, test methods, inspection rules, and product marking, packaging, transportation and storage of cement-based self-leveling mortar for floor. The flow performance of the waterborne polyurethane mortar product refers to the flow degree detection item in the standard.

[0134] In summary, the above-mentioned embodiments are only the preferred examples of the present application, and do not limit the present application in any form; any slight changes, modifications and equivalent changes made by those skilled in the art within the scope of the technical solutions of the present application, using the disclosed technical content, are all considered equivalent examples of the present application; at the same time, any equivalent changes, modifications and evolution of the above-mentioned embodiments according to the essential technology of the present application are still within the protection scope of the technical solutions of the present application.

[0135] The technical features of the above-mentioned embodiments can be combined arbitrarily, and in order to make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described, however, as long as the combinations of the technical features do not exist contradictory, they should be considered as the scope of the present application.

[0136] The experimental methods not marked with specific conditions in the present application are usually according to the conventional conditions or according to the conditions suggested by the manufacturers.

[0137] The various optimized technical solutions in the present application can be combined with each other, unless otherwise specified.

[0138] Unless otherwise specified, the percentages and parts are weight percentages and weight parts.

[0139] The experimental methods not marked with specific conditions in the present application are usually according to the conventional conditions or according to the conditions suggested by the manufacturers.

[0140] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as familiar to those skilled in the art. In addition, any method and material similar or equivalent to the described content can be applied in the present application.

Claims

1. A method for preparing a vegetable oil-based polyol, characterized in that: The epoxy vegetable oil and natural chlorogenic acid are subjected to an epoxy ring-opening reaction to obtain a vegetable oil-based polyol; the epoxy vegetable oil and natural chlorogenic acid have an epoxy:carboxyl functional group ratio of 1:1.0-1.

2.

2. The method for preparing the vegetable oil-based polyol according to claim 1, wherein: It includes the following preparation steps: S1: Epoxy ring-opening reaction of epoxidized vegetable oil and natural chlorogenic acid; The epoxy ring-opening reaction temperature is 75-85°C, and the stirring time is 60-180 minutes; S2: The reactant prepared in step S1 is cooled to room temperature, extracted with ethyl acetate and washed with a saturated NaCl solution; finally, the ethyl acetate is removed by rotary evaporation to obtain a vegetable oil-based polyol.

3. The method for preparing the vegetable oil-based polyol according to claim 1, wherein: The epoxidized vegetable oil is one or a combination of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil and epoxidized sunflower seed oil.

4. A vegetable oil-based polyol, characterized in that: The polyol is prepared according to the method for preparing the vegetable oil-based polyol according to any one of claims 1 to 3.

5. A method for preparing a vegetable oil-based waterborne polyurethane, characterized in that: The method comprises the vegetable oil-based polyol and isocyanate according to claim 1, wherein the vegetable oil-based polyol and isocyanate are stirred and reacted in proportion at room temperature to obtain a vegetable oil-based waterborne polyurethane; The weight ratio of the vegetable oil-based polyol to the isocyanate is 4.2-4.4:4.6-5; The isocyanate is one or a combination of SUPRASEC 5005, DESMODUR VL, WANNATE PM-200, WANNATE MDI-50, and DESMODUR 2460M.

6. A vegetable oil-based waterborne polyurethane, characterized in that: The polyurethane is prepared according to the method for preparing the vegetable oil-based waterborne polyurethane according to claim 5.

7. A method for preparing a waterborne polyurethane antistatic mortar floor coating, characterized in that: It includes the following preparation steps: s1: The vegetable oil-based polyol prepared according to claim 1, tetraethylene glycol, plasticizer, defoamer, paraffin oil, and pure water are mixed in a weight ratio of 28-32:4-8:14-18:1-5:4-8:37-41, and water is slowly added thereto under stirring with a homogenizer to emulsify the mixture to obtain a milky white emulsion-like aqueous dispersion; s2: mechanically stirring and uniformly mixing the milky white emulsion-like aqueous dispersion prepared in step s1 with isocyanate, inorganic active aggregate, color paste and conductive composite material in a weight ratio of 4.2-4.4:4.6-5:18-21:0.08-1:0.03-0.05, and then curing at room temperature to obtain a waterborne polyurethane antistatic mortar floor coating; The conductive medium in the conductive composite material is a composite of carbon fiber and functionalized carbon nanotubes PDA@MWCNTs, and the mass ratio of carbon fiber to functionalized carbon nanotubes PDA@MWCNTs is 2-4:1-3; The functionalized carbon nanotubes PDA@MWCNTs are prepared by the following steps: Add carbon nanotubes (MWCNTs) and dopamine (PDA) in a mass ratio of 1:1.2-1.5 to a 30-50 mmol / L tris(hydroxymethyl)aminomethane hydrochloride (Tris) solution. Add hydrochloric acid solution to adjust the pH to 8-10. Ultrasonicate at room temperature for 1 hour, then magnetically stir for 8-24 hours to ensure sufficient reaction. Finally, the product was washed with anhydrous ethanol and centrifuged at high speed, and then dried in a vacuum oven at 60°C to obtain functionalized carbon nanotubes PDA@MWCNTs. The isocyanate is one or a combination of SUPRASEC 5005, DESMODUR VL, WANNATE PM-200, WANNATE MDI-50, and DESMODUR 2460M.

8. The method for preparing the waterborne polyurethane antistatic mortar floor coating according to claim 7, characterized in that: It includes one or a combination of the following features: The inorganic active aggregate is a reactive filler, which includes: Alkaline earth metal hydroxide, sand, white cement, lime, crushed rubber, crushed plastic, quartz sand or a combination thereof; The color paste is made of raw materials including conductive carbon black and vegetable oil-based polyol, which are fully ground into a slurry and fully stirred during construction to obtain a mixture color paste with uniform and stable color.

9. A waterborne polyurethane antistatic mortar floor coating, characterized by: The antistatic mortar floor coating is prepared according to the preparation method of the waterborne polyurethane antistatic mortar floor coating according to any one of claims 7 to 8.

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