Plant-based weather-resistant waterborne polyurethane mortar with super-long operation period and preparation method thereof
Patent Information
- Application Number
- CN202610810973.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-05
- Publication Date
- 2026-10-27
AI Technical Summary
[0003]2.芳香族聚异氰酸酯的耐候性问题
（1）超长操作期与施工便利性
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of waterborne polyurethane mortar technology, specifically relating to a plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period, its preparation method and application. Background Technology
[0002] Traditional water-based polyurethane mortar flooring materials are mainly composed of water-based polyol emulsions, isocyanate curing agents, and reactive pigments and fillers, making them a three-component flooring material. This material combines almost all the advantages of polyurethane polymers and inorganic concrete, such as high strength, wear resistance, and chemical corrosion resistance. However, this material has some significant limitations in practical applications, mainly in the following aspects: 1. Short construction application period In traditional water-based polyurethane mortar flooring materials, multiple reactions occur simultaneously during construction, including the hydration reaction between water and cement, and the cross-linking reaction between the curing agent and the polyol emulsion. These reactions release a significant amount of heat during mixing, leading to a shortened reaction time. The pot life of the mixed material is typically between 20 and 30 minutes, necessitating rapid completion of construction operations, increasing construction difficulty and labor costs. Therefore, extending the pot life of the material while ensuring rapid hardening after construction is a major challenge currently facing water-based polyurethane mortar flooring.
[0003] 2. Weather resistance issues of aromatic polyisocyanates Traditional water-based polyurethane mortars are primarily used in indoor environments, and the curing agents they use are mostly aromatic polyisocyanates, such as mixtures of MDI (diphenylmethane diisocyanate) and polymethylene polyphenyl polyisocyanate. These aromatic polyisocyanates are prone to yellowing and chalking after exposure to light, resulting in a significantly shortened product lifespan. Therefore, the application of this material in outdoor environments is limited, making it difficult to meet the requirements for higher weather resistance.
[0004] 3. Shrinkage issues of organic and inorganic materials Waterborne polyurethane mortar is a flooring material that combines organic resins and inorganic materials. Due to the asynchronous hardness development of the organic and inorganic materials, strong shrinkage forces are generated, and they do not easily penetrate the substrate. After drying, this strong shrinkage force can cause natural cracking. To solve this problem, it is usually necessary to cut anchor joints to increase the tensile strength of the flooring, allowing it to adapt to the deformation of the substrate and thus preventing coating cracking. However, the treatment of these joints places high demands on the strength of the substrate and the application team. Improper treatment can prevent the substrate from achieving good stress dispersion, easily leading to paint peeling and cracking. Furthermore, the additional topcoat layer applied to achieve an easy-to-clean surface also has disadvantages such as easy wear and short-lasting protection.
[0005] In summary, traditional waterborne polyurethane mortar flooring materials have shortcomings in key performance aspects such as short application period, poor weather resistance, and susceptibility to shrinkage and cracking, which limit their application in wider and harsher environments (especially outdoors). Therefore, developing a new type of waterborne polyurethane mortar material that can simultaneously improve these defects has significant practical implications and broad application prospects. Summary of the Invention
[0006] This invention aims to overcome the shortcomings of existing technologies and provide a plant-based, weather-resistant waterborne polyurethane mortar with an ultra-long working period and its preparation method. The material prepared by this invention has comprehensive advantages such as an ultra-long working period, excellent weather resistance, low shrinkage, no need for cutting or topcoating, high density and easy cleaning, and environmental friendliness and odorlessness.
[0007] To solve the above problems, the present invention is achieved through the following technical solution: The first objective of this invention is: A plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period is provided, which is composed of component A, component B, component C and component D mixed in a weight ratio of 1~5:1~5:1~25:0.1~2; Component A is a polyol emulsion comprising modified vegetable oil polyol resin. The modified vegetable oil polyol resin is prepared by using castor oil and soybean oil in a weight ratio of 5-8:1-5 as raw materials, through a nano-microphase alcoholysis reaction, a formic acid / H2O2 in-situ epoxidation reaction, and a binary modified ring-opening grafting reaction catalyzed by an acidic ionic liquid, and its hydroxyl value is 150-240 mgKOH / g. Component B is a mixture of polyisocyanate and toughening agent, wherein the toughening agent is a compound that can coexist with isocyanate groups; The C component is a filler composition comprising white cement and aggregate; The D component is a color paste comprising the modified vegetable oil polyol resin.
[0008] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: The modified vegetable oil polyol resin comprises the following preparation steps: S1. Alcohololysis reaction: In the presence of an alkaline ionic liquid catalyst and a first surfactant, the mixture of castor oil and soybean oil is subjected to an alcoholic alcoholic reaction to obtain the alcoholic product; The first surfactant is castor oil polyoxyethylene ether; S2. Epoxidation reaction: The alcoholysis product is subjected to an epoxidation reaction with hydrogen peroxide and formic acid to obtain an epoxidized intermediate; S3. Ring-opening grafting reaction: In the presence of an acidic ionic liquid catalyst and a second surfactant, the epoxidized intermediate is subjected to a ring-opening grafting reaction with a hydrophobic modifier containing hydroxyl groups to obtain the modified vegetable oil polyol resin. The second surfactant is a mixture of aliphatic hydrocarbons and emulsifiers containing a binary hydrophobic system.
[0009] In this invention, the synergistic use of the alkaline ionic liquid catalyst and the acidic ionic liquid catalyst constructs a unique reaction microenvironment. The acidic sites efficiently activate the ester bonds of vegetable oils, promoting the alcoholysis reaction; while the alkaline sites activate the active groups in the hydrophobic modifier containing hydroxyl groups (such as dihydroxyl-terminated organosilicon), enhancing its reactivity. Within this microenvironment, a selective ring-opening grafting reaction occurs. Through precise control of the reaction conditions, a high grafting rate can be achieved while effectively retaining the necessary hydroxyl functional groups in the product molecule, thereby obtaining a modified vegetable oil polyol resin with a stable hydroxyl value in the range of 150–240 mgKOH / g and excellent hydrophobic properties.
[0010] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: In the alcoholysis reaction: The alkaline ionic liquid catalyst is choline hydroxide, with the structural formula [Choline][OH]. The acidic ionic liquid catalyst is 1-butyl-3-methylimidazolium hydrogen sulfate, with the structural formula [BMIM][HSO4]. The amount of the alkaline ionic liquid catalyst used is 1-3% of the total mass of the castor oil and soybean oil; The amount of the first surfactant added is 0.5–1.0 wt% of the total mass of the reaction system. The alcohol is a mixed solvent of glycerol and methanol, wherein the mass ratio of glycerol to methanol is 1:2 to 1:3, and the molar ratio of the mixed solvent to the mixed vegetable oil is 6:1 to 12:1. The alcoholysis reaction is carried out in the presence of a co-solvent, which is polyethylene glycol dimethyl ether with a molecular weight of 400-600, and the amount added is 15-20 wt% of the total mass of the reaction system. And / or, In the epoxidation reaction: The amount of formic acid used is 10-20% of the mass of the alcoholysis product; Hydrogen peroxide was added in the form of a 30% H2O2 aqueous solution, and the amount used was 1.1 to 1.3 times the molar amount of double bonds in the alcoholysis product; The epoxidation reaction is carried out in toluene solvent, and the amount of toluene used is 50-80% of the mass of the alcoholysis product; And / or, In the ring-opening grafting reaction: The amount of the acidic ionic liquid catalyst used is 1-5% of the mass of the epoxidation intermediate; The hydrophobic modifier containing hydroxyl groups includes a bihydroxyl-terminated organosilicon, which is premixed with the second surfactant in a molar ratio of 1:1.5 to 1:2 and dissolved in paraffin oil to form a modifier stock solution, wherein the amount of paraffin oil used is 30% to 40% of the total solid content; The mass ratio of the epoxidation intermediate to the modifier mother liquor is 10:3 to 10:4; The ring-opening grafting reaction is carried out in toluene solvent.
[0011] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: Component A comprises the following raw material components by weight percentage: The modified vegetable oil polyol resin comprises 20-70%, chain extender 0.1-2%, surfactant 0.01-2%, dispersant 0.5-2%, defoamer 0.1-2%, plasticizer 10-20%, paraffin oil 1-10%, and wetting and leveling agent 0.01-2%. The composition includes 0.01-2% bactericide, 0.01-2% catalyst, 10-40% deionized water, and the sum of all components is 100%. The chain extender is one or a combination of aliphatic diols, aromatic diols, and aromatic diamines; And / or, The surfactant is one or a combination of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether. And / or, The catalyst is a hydrolysis-resistant catalyst, and is one or a combination of organotin and organobismuth catalysts; And / or, The plasticizer is one or a combination of didecyl phthalate, di(2-propylheptyl) phthalate, bisphenol A bis(diphenyl phosphate), dioctyl phthalate, and dibutyl phthalate.
[0012] Preferably, The defoamer is one or a combination of BYK-019, BYK-1711, TEGO-901W, Foam Star ST2410AG, and BYK-024; The wetting and leveling agent is one or a combination of BYK-346, BYK-333, TEGO-4100, TEGOWET-270, and EFKA-3772; The bactericide is one or a combination of LPC5, LXE, BIOX520W, and BIOXABZ.
[0013] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: The polyisocyanate in component B is one or a combination of HDI biuret, isophorone diisocyanate (IPDI), tetramethyl isophthalamide diisocyanate (TMXDI), polyisocyanurate, dicyclohexylmethane diisocyanate (H12MDI), isophthalamide diisocyanate, and hexamethylene diisocyanate (HDI). Tetramethyl isophthalamide diisocyanate (TMXDI) is preferred.
[0014] In a preferred embodiment, the isocyanate group (-NCO) in the tetramethyl isophthalamide diisocyanate (TMXDI) molecule is linked to an aromatic ring via a methylene group. This unique structure combines the weather resistance of aliphatic isocyanates with the excellent adhesion to substrates of aromatic isocyanates. Simultaneously, the steric hindrance effect of the methyl group in the molecule helps regulate reactivity and delay the gelation time of the system, which plays a positive role in achieving the aforementioned "ultra-long operating period." Furthermore, this structural characteristic also helps improve the microphase separation structure of the polymer, giving the product better flexibility and rheological properties. Combining it with other curing agents such as polyisocyanurates can further synergistically optimize the final mechanical properties of the mortar.
[0015] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: The C component comprises the following raw material components in parts by weight: 1-40 parts white cement, 1-15 parts carbon dioxide absorbent, 10-70 parts aggregate, 0.01-0.5 parts powdered defoamer, 0.01-0.5 parts dihydroxyacetone, and 0.01-0.5 parts polycarboxylate superplasticizer; the aggregate is quartz sand.
[0016] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: The white cement is grade 52.5 white cement; And / or, The carbon dioxide absorbent is one or a combination of molecular sieve, calcium hydroxide, and zeolite; And / or, The mesh size of the quartz sand is one or a combination of 30-50 mesh, 50-100 mesh, and 80-120 mesh; And / or, The powdered defoamer is one or a combination of modified polyether defoamer, modified organosilicon defoamer, and mineral oil defoamer.
[0017] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: The D component comprises the following raw material components by weight percentage: The modified vegetable oil polyol resin is 10-40%, the dispersant is 0.5-5%, the defoamer is 0.1-2%, the plasticizer is 10-40%, the pigment is 1-40%, the filler is 1-40%, and the wetting and leveling agent is 0.01-2%, with the sum of all components being 100%.
[0018] A further optimization of the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period described in this invention is as follows: In component D: The pigment is one or a combination of titanium dioxide, carbon black, iron yellow, lemon yellow, iron red, phthalocyanine blue, phthalocyanine green, and royal blue pigments; And / or, The filler is one or a combination of silica powder and barium sulfate.
[0019] Preferably, The dispersant is one or a combination of BYK-181, BYK-190, DIS-188A, and SN-5027; The defoamer is one or a combination of BYK-019, BYK-1711, TEGO-901W, Foam Star ST2410AG, and BYK-024; The wetting and leveling agent is one or a combination of BYK-346, BYK-333, TEGO-4100, TEGOWET-270, and EFKA-3772.
[0020] The second objective of this invention is: A method for preparing the aforementioned plant-based weather-resistant waterborne polyurethane mortar with an ultra-long operating period is provided, comprising the following steps: Preparation of S1.A component: Modified vegetable oil polyol resin, chain extender, surfactant, dispersant, defoamer, plasticizer, paraffin oil, wetting and leveling agent, bactericide and catalyst are mixed in proportion, dispersed evenly at medium speed, deionized water is added, and then stirred at high speed for 30 to 40 minutes to obtain component A. Preparation of component S2.B: Polyisocyanate and toughening agent are mixed and stirred evenly to obtain component B; Preparation of S3.C component: The filler composition including white cement and aggregate is mixed evenly to obtain component C; Preparation of S4.D component: The modified vegetable oil polyol resin, dispersant, defoamer, plasticizer, pigment, filler and wetting leveling agent are mixed and dispersed at high speed for 10 to 40 minutes, and then ground to a fineness of less than 60 micrometers to obtain component D; the amount of each raw material in component D can be selected according to conventional or actual needs, or the aforementioned preferred range can be directly adopted.
[0021] S5. Mixing and construction: Mix components A, B, and D in proportion for 30-40 seconds, then add component C and mix for 2-3 minutes until homogeneous to prepare the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period.
[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) Long operating period and ease of construction This invention relates to a plant-based, weather-resistant waterborne polyurethane mortar with an ultra-long working time. Compared to conventional waterborne polyurethane mortars, the working time is significantly extended, reaching up to 50 minutes, ensuring construction even under high-temperature conditions. This greatly reduces construction difficulty and labor costs, and solves the problems of material waste and narrow construction window caused by the short working time and rapid curing of traditional materials.
[0023] (2) Excellent weather resistance and gloss and color retention This invention employs a specific plant-based polyol and aliphatic / alicyclic isocyanate curing agent system, combined with organosilicon modification technology, to give the product excellent UV aging resistance. It overcomes the defects of traditional aromatic curing agents, such as yellowing and chalking, making it suitable for various indoor and outdoor environments and extending its service life.
[0024] (3) Low shrinkage, high stability and no-cut construction The mortar of this invention effectively balances the properties (rigidity and flexibility) of inorganic mortar and polyurethane materials, exhibiting extremely low dimensional change rate and deformation, and maintaining stability without cracking for a long time. This characteristic eliminates the need for grooving during construction, enabling seamless, integrated construction, which not only enhances the overall aesthetics of the floor but also further simplifies the construction process.
[0025] (4) High-density coating, easy to clean and excellent stain and corrosion resistance The mortar of this invention can form a high-smoothness and dense coating through integrated construction, without the need for an additional protective topcoat. Stains on the coating surface are easy to clean without residue, and it has excellent stain resistance and chemical resistance.
[0026] (5) Optimized four-component system and wide construction adaptability The four-component system of this invention is optimized for moderate viscosity and convenient mixing and application. This system has a wide temperature adaptability range, effectively solving the problems of difficult application and poor curing associated with similar products in low-temperature environments.
[0027] (6) Excellent environmental protection, health and safety characteristics This invention incorporates renewable plant-based ingredients into the formula, making the product more environmentally friendly. The product is water-based, odor-free, and environmentally friendly, significantly reducing VOC content and possessing antibacterial and anti-mold properties, thus minimizing potential impacts on human health and the environment. It is suitable for various scenarios, including home and industrial applications.
[0028] (7) Energy and cost savings The grooving-free and cover-free characteristics of this invention save energy during production and construction. At the same time, the extended operating period reduces material waste, resulting in low overall operating costs. Detailed Implementation
[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention. Any simple improvements to the preparation method of this invention based on the inventive concept are within the scope of protection of this invention.
[0030] Example 1: Preparation of modified vegetable oil polyol resin The modified vegetable oil polyol resin is prepared by a method comprising the following steps: S1. Alcohololysis reaction: A basic ionic liquid [Choline][OH], comprising 1.5% of the mass of the mixed vegetable oil (castor oil: soybean oil = 5:2, total weight 100g), was dissolved in a mixed solvent of glycerol and methanol (glycerol: methanol = 1:2.2, molar ratio relative to the mixed oil 9:1); Add 15 wt% polyethylene glycol dimethyl ether (PEGDME, Mw=400) as a co-solvent, and add 0.55 wt% of the first surfactant (castor oil polyoxyethylene ether EL-40). The mixture was placed in a three-necked flask and activated by stirring at 60°C for 0.5 hours. Then, mixed vegetable oil was added, and the mixture was stirred and refluxed at 60°C for 2.5 hours. After the reaction, the mixture was allowed to stand and separate into layers. The upper crude product was washed three times with deionized water and once with saturated brine, dried over anhydrous sodium sulfate, and then evaporated by rotary evaporation to obtain product 1 (modified vegetable oleate). (The residual methanol, glycerol, and ionic liquid in the lower layer were recovered and reused by vacuum distillation.) S2. Epoxidation reaction: Add 100g of product 1, 13g of formic acid and 60g of toluene to a reaction flask and heat to 70°C; slowly add 30% H2O2 solution (the amount used is 1.25 times the molar amount of the double bond of product 1) dropwise, and control the temperature not to exceed 75°C; after the addition is complete, continue the reaction at 70°C for 4 hours; wash the reaction solution with warm water, wash with 10% sodium carbonate solution until neutral, wash with saturated brine, dry the organic phase and remove the solvent by rotary evaporation to obtain product 2 (epoxidized vegetable oil intermediate).
[0031] S3. Ring-opening grafting reaction: The second surfactant (Defoam NS801) containing a binary hydrophobic system was mixed with a double-terminated hydroxyl group organosilicon at a molar ratio of 1:1.7 and dissolved in paraffin oil (33% of the total solid content) to form a modifier mother liquor. Add 100g of product 2, 2.5g of acidic ionic liquid [BMIM][HSO4], an appropriate amount of toluene and 35g of the above-mentioned modifier mother liquor to the reaction flask, heat to 110°C under nitrogen protection, and stir and reflux for 6 hours. After the reaction was completed, the mixture was cooled, dissolved in ethyl acetate, washed with water until neutral, and the organic phase was dried and then rotary evaporated to obtain a light yellow transparent liquid with a hydroxyl value of 180 mgKOH / g, which is the modified vegetable oil polyol resin.
[0032] Example 2: A method for preparing a plant-based, weather-resistant waterborne polyurethane mortar with an ultra-long operating period. The mortar includes the following steps: Preparation of component S1.A: Modified vegetable oil polyol resin, chain extender, surfactant, dispersant, defoamer, plasticizer, paraffin oil, wetting and leveling agent, bactericide and catalyst are mixed in proportion, dispersed evenly at medium speed, deionized water is added, and then stirred at high speed for 35 minutes to obtain component A. Preparation of component S2.B: Polyisocyanate and toughening agent are mixed and stirred evenly to obtain component B; Preparation of S3.C component: The filler composition including white cement and aggregate is mixed evenly to obtain component C; Preparation of S4.D component: Modified vegetable oil polyol resin, dispersant, defoamer, plasticizer, pigment, filler, wetting and leveling agent are mixed and dispersed at high speed for 20 minutes, and then ground to a fineness of less than 60 micrometers to obtain component D; S5. Mixing and construction: Mix components A, B, and D in proportion for 40 seconds, then add component C and mix for 2 minutes until uniform to prepare the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period.
[0033] Examples 3-5 The preparation methods of Examples 3 to 5 are the same as those of Example 2, the main difference being that the composition and amount of some raw materials are different, as detailed in Table 1 below.
[0034] Comparative Examples 1-3 The preparation methods of Comparative Examples 1 and 2 are the same as those of Example 2, with the main difference being that the composition and amount of some raw materials are different, as detailed in Table 1 below.
[0035] Comparative Example 3 is a commercially available conventional water-based polyurethane mortar competitor. During the test, it was mixed and applied according to the mixing ratio provided in its product instructions (A:B:C:D = 5:5:21.6:1.6).
[0036] Table 1. Composition of raw materials for each specific component in the embodiments (by weight percentage, parts by weight)
[0037] Performance Testing and Result Analysis The products obtained in Examples 2-5 and Comparative Examples 1-3 were subjected to performance tests in accordance with relevant national standards. The specific test items, methods, and results are as follows: 1. Test Methods and Standards The following parameters were tested: container condition, coating appearance, working time, initial flowability, compressive strength, flexural strength, abrasion resistance, anti-slip properties, tensile bond strength, impact resistance, water resistance, chemical resistance, and salt water resistance: in accordance with the technical requirements of Table 5, Polymer Cement Composite Floor Coating Materials (JJ type), in GB / T 22374-2018 "Floor Coating Materials".
[0038] Dimensional change rate: Tested according to the method in Table 5 of GB / T 22374-2018 for polymer cement composite floor coating materials (FJ type).
[0039] Volatile organic compound (VOC) content and total volatile organic compound (TVOC) release: tested according to the method in Table 1 of GB / T 22374-2018 for solvent-based and water-based floor coating materials (Type J).
[0040] Artificial aging resistance: Tested according to Method 1 Cycle A in GB / T 1865-2009 "Artificial climate aging and artificial radiation exposure to filtered xenon arc radiation for paints and varnishes" for 400 hours.
[0041] Stain resistance: Tested according to the test method for interior wall coatings in GB / T 9780-2013 "Test method for stain resistance of architectural coatings".
[0042] Working time (high temperature 35℃): Refer to Table 5 of GB / T 22374-2018 "Floor Coating Materials" for polymer cement composite floor coating materials (JJ type) test.
[0043] The performance test results of the examples and comparative examples are shown in Table 2 below.
[0044]
[0045]
[0046] Results Analysis and Discussion
[0047] Based on the test data in the table above, the technical effects of the present invention are analyzed as follows: (1) Extremely long operating period
[0048] The operable time of Examples 2-5 reached 30-50 minutes, with Example 5 reaching as high as 50 minutes, far exceeding Comparative Example 1 (16 minutes) and Comparative Example 3 (18 minutes). This indicates that the present invention, by employing a specific modified vegetable oil polyol resin, a sterically hindered TMXDI curing agent, and a filler system containing dihydroxyacetone, effectively synergistically slows down the system reaction rate, achieving the core effect of "ultra-long operating time". The operating time of Comparative Example 2 (with the curing agent replaced by HT-600) (40 minutes) was still better than the traditional product, but shorter than Example 5, demonstrating the unique contribution of TMXDI in extending the operating time. Furthermore, at a high temperature of 35 degrees Celsius, Examples 2-5 still maintained excellent operating times, exhibiting good adaptability in Southeast Asia, tropical regions, and areas with consistently high temperatures, effectively solving the problem of difficult construction of conventional waterborne polyurethane mortar in high-temperature areas.
[0049] (2) Excellent weather resistance
[0050] In a 400-hour artificial aging test, all examples (2-5) maintained a "Grade 0" without any yellowing or chalking. In contrast, Comparative Example 1 (using a conventional polyol) and Comparative Example 3 (commercially available product) exhibited "severe discoloration and chalking." This result directly verifies the decisive role of the technical solution of this invention (aliphatic / alicyclic curing agent system and organosilicon-modified vegetable oil resin) in improving weather resistance. Comparative Example 2 also had a weather resistance grade of 0, indicating that the aliphatic curing agent is one of the key factors.
[0051] (3) Low shrinkage and high dimensional stability
[0052] Examples 2-5 exhibit extremely low dimensional change rates (0.01%-0.06%), with Example 5 reaching as low as 0.01%, achieving near-zero shrinkage. This allows for better "grooving-free" integrated construction of the product in terms of "constructability." In contrast, Comparative Examples 1 and 3 show dimensional change rates as high as 0.8%, necessitating "grooving" to release stress. This demonstrates that the optimized organic-inorganic composite system of this invention effectively balances shrinkage stress.
[0053] (4) Excellent mechanical and durability properties
[0054] The examples demonstrated superior performance compared to the comparative examples in terms of compressive / flexural strength, abrasion resistance, tensile bond strength, and impact resistance. For instance, Example 5 exhibited a 7-day compressive strength of 50 MPa and an abrasion loss of only 0.01 g, far exceeding national standards. This indicates that the high-functionality modified vegetable oil resin effectively improved crosslinking density and cohesive strength. Comparative Example 1 (using a conventional polyol) showed a significant decrease in all mechanical properties and durability, confirming the importance of this specific modified resin.
[0055] (5) Excellent stain resistance and easy cleaning
[0056] Examples 2-5 all achieved a perfect score of 10 in the stain resistance test, while Comparative Examples 1 and 3 only achieved 2. This clearly demonstrates that the double hydrophobic structure formed on the coating surface by organosilicon grafting modification in this invention endows the product with excellent daily stain resistance and easy cleaning ability.
[0057] (6) Environmental protection and health safety
[0058] The VOC and TVOC test results for all embodiments were "not detected," far below the national standard limits and comparative examples 1 and 3. This confirms the environmental advantages of the plant-based, water-based system of this invention.
[0059] Overall conclusion:
[0060] Test results show that the plant-based weather-resistant waterborne polyurethane mortars prepared in Examples 2-5 of this invention exhibit comprehensive and significant performance advantages in terms of workability, weather resistance, dimensional stability, mechanical properties, surface stain resistance, and environmental friendliness, with Example 4 showing the best overall performance. Comparative analysis with comparative examples fully verifies that the modified plant oil polyol resin, aliphatic / alicyclic curing agents such as TMXDI, and the optimized C component containing functional fillers are key to achieving these excellent properties. This invention successfully solves the problems of short workability, poor weather resistance, and easy shrinkage and cracking in traditional waterborne polyurethane mortars mentioned in the background art, providing an ideal material suitable for high-performance indoor and outdoor floor coatings.
[0061] In summary, the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any changes, modifications, and evolutions made by those skilled in the art without departing from the scope of the present invention using the disclosed technical content are considered equivalent embodiments of the present invention. Furthermore, any changes, modifications, and evolutions made to the above embodiments based on the essential technology of the present invention are within the protection scope of the present invention.
[0062] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0063] Experimental methods not specified in this invention are generally performed under conventional conditions or as recommended by the manufacturer.
[0064] Unless otherwise stated, the various optimized technical solutions in this invention can be combined with each other.
[0065] Unless otherwise stated, percentages and parts are weight percentages and weight parts.
[0066] Experimental methods not specified in the instructions and examples are generally performed under standard conditions or as recommended by the manufacturer.
[0067] The various raw materials, reagents and components used in this invention are all commonly used raw materials in the field unless otherwise stated.
[0068] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be used in the methods of this invention.
Claims
1. A plant-based, weather-resistant waterborne polyurethane mortar with an ultra-long working period, characterized in that: It is composed of components A, B, C and D mixed in a weight ratio of 1-5:1-5:1-25:0.1-2; Component A is a polyol emulsion comprising modified vegetable oil polyol resin. The modified vegetable oil polyol resin is prepared by using castor oil and soybean oil in a weight ratio of 5-8:1-5 as raw materials, through a nano-microphase alcoholysis reaction, a formic acid / H2O2 in-situ epoxidation reaction, and a binary modified ring-opening grafting reaction catalyzed by an acidic ionic liquid, and its hydroxyl value is 150-240 mgKOH / g. Component B is a mixture of polyisocyanate and toughening agent, wherein the toughening agent is a compound that can coexist with isocyanate groups; The C component is a filler composition comprising white cement and aggregate; The D component is a color paste comprising the modified vegetable oil polyol resin.
2. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 1, characterized in that: The modified vegetable oil polyol resin comprises the following preparation steps: S1. Alcohololysis reaction: In the presence of an alkaline ionic liquid catalyst and a first surfactant, the mixture of castor oil and soybean oil is subjected to an alcoholic alcoholic reaction to obtain the alcoholic product; The first surfactant is castor oil polyoxyethylene ether; S2. Epoxidation reaction: The alcoholysis product is subjected to an epoxidation reaction with hydrogen peroxide and formic acid to obtain an epoxidized intermediate; S3. Ring-opening grafting reaction: In the presence of an acidic ionic liquid catalyst and a second surfactant, the epoxidized intermediate is subjected to a ring-opening grafting reaction with a hydrophobic modifier containing hydroxyl groups to obtain the modified vegetable oil polyol resin. The second surfactant is a mixture of aliphatic hydrocarbons and emulsifiers containing a binary hydrophobic system.
3. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 2, characterized in that: In the alcoholysis reaction: The alkaline ionic liquid catalyst is choline hydroxide, with the structural formula [Choline][OH]. The acidic ionic liquid catalyst is 1-butyl-3-methylimidazolium hydrogen sulfate, with the structural formula [BMIM][HSO4]. The amount of the alkaline ionic liquid catalyst used is 1-3% of the total mass of the castor oil and soybean oil; The amount of the first surfactant added is 0.5–1.0 wt% of the total mass of the reaction system. The alcohol is a mixed solvent of glycerol and methanol, wherein the mass ratio of glycerol to methanol is 1:2 to 1:3, and the molar ratio of the mixed solvent to the mixed vegetable oil is 6:1 to 12:
1. The alcoholysis reaction is carried out in the presence of a co-solvent, which is polyethylene glycol dimethyl ether with a molecular weight of 400-600, and the amount added is 15-20 wt% of the total mass of the reaction system. And / or, In the epoxidation reaction: The amount of formic acid used is 10-20% of the mass of the alcoholysis product; Hydrogen peroxide was added in the form of a 30% H2O2 aqueous solution, and the amount used was 1.1 to 1.3 times the molar amount of double bonds in the alcoholysis product; The epoxidation reaction is carried out in toluene solvent, and the amount of toluene used is 50-80% of the mass of the alcoholysis product; And / or, In the ring-opening grafting reaction: The amount of the acidic ionic liquid catalyst used is 1-5% of the mass of the epoxidation intermediate; The hydrophobic modifier containing hydroxyl groups includes a bihydroxyl-terminated organosilicon, which is premixed with the second surfactant in a molar ratio of 1:1.5 to 1:2 and dissolved in paraffin oil to form a modifier stock solution, wherein the amount of paraffin oil used is 30% to 40% of the total solid content; The mass ratio of the epoxidation intermediate to the modifier mother liquor is 10:3 to 10:4; The ring-opening grafting reaction is carried out in toluene solvent.
4. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 1, characterized in that: Component A comprises the following raw material components by weight percentage: The modified vegetable oil polyol resin comprises 20-70%, chain extender 0.1-2%, surfactant 0.01-2%, dispersant 0.5-2%, defoamer 0.1-2%, plasticizer 10-20%, paraffin oil 1-10%, and wetting and leveling agent 0.01-2%. The composition includes 0.01-2% bactericide, 0.01-2% catalyst, 10-40% deionized water, and the sum of all components is 100%. The chain extender is one or a combination of aliphatic diols, aromatic diols, and aromatic diamines; And / or, The surfactant is one or a combination of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether. And / or, The catalyst is a hydrolysis-resistant catalyst, and is one or a combination of organotin and organobismuth catalysts; And / or, The plasticizer is one or a combination of didecyl phthalate, di(2-propylheptyl) phthalate, bisphenol A bis(diphenyl phosphate), dioctyl phthalate, and dibutyl phthalate.
5. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 1, characterized in that: The polyisocyanate in component B is one or a combination of HDI biuret, isophorone diisocyanate, tetramethyl isophthalimide diisocyanate, polyisocyanurate, dicyclohexylmethane diisocyanate, isophthalimide diisocyanate, and hexamethylene diisocyanate.
6. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 1, characterized in that: The C component comprises the following raw material components in parts by weight: 1-40 parts white cement, 1-15 parts carbon dioxide absorbent, 10-70 parts aggregate, 0.01-0.5 parts powdered defoamer, 0.01-0.5 parts dihydroxyacetone, and 0.01-0.5 parts polycarboxylate superplasticizer; The aggregate is quartz sand.
7. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 6, characterized in that: The white cement is grade 52.5 white cement; And / or, The carbon dioxide absorbent is one or a combination of molecular sieve, calcium hydroxide, and zeolite; And / or, The mesh size of the quartz sand is one or a combination of 30-50 mesh, 50-100 mesh, and 80-120 mesh; And / or, The powdered defoamer is one or a combination of modified polyether defoamer, modified organosilicon defoamer, and mineral oil defoamer.
8. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 1, characterized in that: The D component comprises the following raw material components by weight percentage: The modified vegetable oil polyol resin is 10-40%, the dispersant is 0.5-5%, the defoamer is 0.1-2%, the plasticizer is 10-40%, the pigment is 1-40%, the filler is 1-40%, and the wetting and leveling agent is 0.01-2%, with the sum of all components being 100%.
9. The plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period according to claim 8, characterized in that: The pigment is one or a combination of titanium dioxide, carbon black, iron yellow, lemon yellow, iron red, phthalocyanine blue, phthalocyanine green, and royal blue pigments; And / or, The filler is one or a combination of silica powder and barium sulfate.
10. A method for preparing a plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period as described in any one of claims 1 to 9, characterized in that: Includes the following steps: Preparation of S1.A component: Modified vegetable oil polyol resin, chain extender, surfactant, dispersant, defoamer, plasticizer, paraffin oil, wetting and leveling agent, bactericide and catalyst are mixed in proportion, dispersed evenly at medium speed, deionized water is added, and then stirred at high speed for 30 to 40 minutes to obtain component A. Preparation of component S2.B: Polyisocyanate and toughening agent are mixed and stirred evenly to obtain component B; Preparation of S3.C component: The filler composition including white cement and aggregate is mixed evenly to obtain component C; Preparation of S4.D component: Modified vegetable oil polyol resin, dispersant, defoamer, plasticizer, pigment, filler, wetting and leveling agent are mixed and dispersed at high speed for 10 to 40 minutes, and then ground to a fineness of less than 60 micrometers to obtain component D; S5. Mixing and construction: Mix components A, B, and D in proportion for 30-40 seconds, then add component C and mix for 2-3 minutes until homogeneous to prepare the plant-based weather-resistant waterborne polyurethane mortar with an ultra-long working period.