Waterborne polyurethane mortar terrace emulsion and application thereof

Abstract

The invention relates to a waterborne polyurethane mortar terrace emulsion and application thereof. The waterborne polyurethane mortar terrace emulsion comprises first polyester polyol, bio-based polyester polyol, a defoaming agent, a dispersing agent, an emulsifying agent, dihydric alcohol, a plasticizer, glycidyl ether and water. According to the invention, the star-structured polyol is introduced as a high-functionality core skeleton, a rigid network with high crosslinking density is constructed during curing, the terrace is directly endowed with excellent surface hardness and scratch resistance, and meanwhile, the three-dimensional spherical structure forms a stable conformation in latex particles, so that particle coalescence in the storage process is effectively inhibited, and the stability of the terrace is improved. Therefore, the long-term stability is guaranteed; alkyl glycidyl ether is introduced as a'bridge 'and'lubrication', so that the surface scratch resistance is improved, and the anchoring effect of an emulsion particle interface is enhanced. And finally, the storage stability (more than or equal to 15 days) of the emulsion and the surface hardness (Mohs hardness is more than 5) of the terrace are obviously improved.

Description

Technical Field

[0001] This invention relates to the field of floor coating technology, specifically to a water-based polyurethane mortar floor emulsion and its application. Background Technology

[0002] Waterborne polyurethane mortar flooring systems have been widely used in the industrial flooring sector due to their environmental friendliness and excellent physical properties. However, this technology still faces two key technical bottlenecks in practical applications: insufficient emulsion storage stability and poor scratch resistance of the floor surface.

[0003] Regarding scratch resistance, existing technologies often employ linear polyols (such as polyether polyols N210 and N220 or polyester polyols Sovermol series) as the soft segment matrix in waterborne polyurethane emulsions. The limited density of the three-dimensional cross-linked network formed during the curing process of these molecular structures results in surface hardness (pendulum hardness typically ≤120 seconds) and scratch resistance of the flooring material failing to meet the requirements of applications demanding high mechanical strength (such as logistics warehousing and heavy-duty workshops).

[0004] Regarding emulsion stability, in existing technologies, the molecular conformation of traditional linear polyols makes it difficult to form a stable interparticle interface film during emulsification. Especially under the conditions of high solids content and high filler addition unique to polyurethane mortar systems, latex particles are more prone to Ostwald curing and gravity sedimentation, resulting in a storage period of generally less than 1 week and insufficient freeze-thaw stability (demulsification occurs after 3 cycles).

[0005] However, there is an inherent technical contradiction between the scratch resistance of flooring surfaces and the stability of emulsions. Improving scratch resistance requires higher crosslinking density and rigid segments, which typically necessitates the use of polyols with high hydroxyl values, aromaticity, or rigid ring structures. However, such structures often compromise the storage stability and low-temperature film-forming properties of the emulsion. Therefore, developing a novel polyol structure and matching formulation system that can simultaneously overcome the limitations of emulsion stability and flooring scratch resistance has become a pressing technical challenge in this field. Summary of the Invention

[0006] Based on this, the purpose of this invention is to provide a technical solution that achieves synergistic optimization of the stability of waterborne polyurethane emulsion and the anti-slip properties of mortar flooring through innovation in the molecular structure of polyols, fundamentally overcoming the core defect in the prior art that the storage stability of emulsion and the wet anti-slip properties of the final floor surface cannot be improved simultaneously.

[0007] First aspect:

[0008] A water-based polyurethane mortar flooring emulsion, comprising the following components: The first group of raw materials consists of polyester polyol, bio-based polyester polyol, defoamer, dispersant, emulsifier, diol, plasticizer, glycidyl ether, and water, and the mass ratio of these nine raw materials is: (15-50):(0-20):(1.5-3):(0.1-0.6):(0-0.8):(3-12):(15-25):(5-15):(25-35); The first polyester polyol is prepared by the following method: The first small molecule polyol is mixed and reacted with a monoacid to obtain a polyester polyol intermediate; A crude dimer acid mixture is added to the polyester polyol intermediate and the mixture is reacted to obtain the first polyester polyol. The monoacids include at least one of octanoic acid, isooctanoic acid, lauric acid, palmitoleic acid, linoleic acid, stearic acid, and oleic acid; The first small molecule polyol includes at least one of trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol; The crude dimer acid mixture includes the monoacid, dimer acid and trimer acid, and the monoacid accounts for ≤30 wt.%, the dimer acid accounts for ≥55 wt.%, and the trimer acid accounts for ≤20 wt.%.

[0009] The specified content of mono-acid (≤30%), dimer acid (≥55%), and trimer acid (≤20%) is designed to precisely control the molecular structure and functionality of polyester polyols. Excessive mono-acid content will terminate the reaction, resulting in insufficient molecular weight and low crosslinking density of the polyol, severely impairing the surface hardness and abrasion resistance of the final flooring. Excessive trimer acid content can easily cause over-branching or even gelation, leading to uncontrolled synthesis and potentially compromising the storage stability of the emulsion. Sufficient dimer acid content, as the core flexible segment, is fundamental to ensuring both good mechanical strength and process applicability of the material.

[0010] The core technology of this invention lies in breaking through the contradiction and limitation of the traditional "hydrophilic stable emulsion - hydrophobic friction reduction". Through a precisely designed hydrophobic alkyl chain structure, it simultaneously achieves a significant improvement in emulsion storage stability (≥15 days) and floor surface hardness (Mohs hardness >5). Its core mechanism relies on the innovative application of the first polyester polyol and glycidyl ether.

[0011] This invention's formulation overcomes the traditional contradiction between storage stability and surface hardness by introducing a synergistic system of "star-shaped" polyols and alkyl glycidyl ethers, addressing the issue from the perspectives of molecular design and reaction mechanism. The "star-shaped" polyol, as a high-functionality (3.0-4.5) core framework, constructs a rigid network with high cross-linking density during curing, directly endowing the flooring with excellent surface hardness (Mohs hardness > 5) and scratch resistance. Simultaneously, its three-dimensional spherical structure forms a stable conformation within the latex particles, effectively inhibiting particle aggregation during storage, thus ensuring long-term stability.

[0012] Glycidyl ether plays a crucial synergistic role as a "bridge" and "lubricant": Firstly, its epoxy groups react with carboxyl groups and other groups on the polyurethane chain, acting as a reactive internal crosslinking agent to further strengthen the crosslinking network and improve bulk hardness; secondly, its long-chain alkyl groups migrate to the surface during film formation, forming a dense hydrophobic protective layer. This significantly improves surface scratch resistance and, due to its hydrophobic properties, enhances the anchoring effect at the latex particle interface, thereby synergistically improving the storage and mechanical stability of the emulsion. The "star-shaped" polyol provides a rigid framework, while glycidyl ether optimizes the interface and surface. Together, they achieve a balance between high crosslinking density (high hardness) and excellent colloidal stability (high storage stability), far exceeding the effects of single components or simple blends.

[0013] As a preferred embodiment, the hydroxyl value of the first polyester polyol is 100~240 mgKOH / g, and the average functionality is 2.2~3.5. Controlling the average functionality to be greater than 2.2 facilitates subsequent crosslinking and network formation, while controlling it to be less than 3.5 controls the crosslinking density.

[0014] As a preferred embodiment, the method for preparing the first polyester polyol further includes the following steps: The first small molecule polyol is mixed with the monoacid, a catalyst is added, and the mixture is evacuated and reacted at 180~240℃ for 3~16h. When the acid value of the reaction system is lower than 3mgKOH / g, the reaction ends and the polyester polyol intermediate is obtained. The crude dimer acid mixture is added to the polyester polyol intermediate, and the reaction is continued at a temperature of 180~240℃ for 3~16h. When the acid value of the reaction system is lower than 3mgKOH / g and the hydroxyl value of the reaction system reaches 100~240mgKOH / g, the reaction is terminated to obtain the first polyester polyol. The catalyst includes at least one of tetrabutyl titanate, tetraisopropyl titanate, tetraoctyl titanate, tetrabutyl zirconate, tetraisopropyl zirconate, dibutyltin dilaurate, and zinc antimony oxide.

[0015] When the acid value is higher than 3 mg KOH / g, the polyol contains too much unreacted organic acid, which ultimately affects the strength of the flooring. When the hydroxyl value in the reaction system reaches 100~240 mg KOH / g, it can ensure that the ratio of the number of hydroxyl groups in the polyol in the emulsion to the amount of isocyanate in the curing agent is appropriate.

[0016] As a preferred embodiment, the method for preparing the first polyester polyol further includes the following steps: The first small molecule polyol and the second small molecule polyol are mixed and reacted with a monoacid to obtain a polyester polyol intermediate. The second small molecule polyol is at least one of 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; The total amount of the first small molecule polyol and the second small molecule polyol is in a molar ratio of 1:1 to 4 to the monoacid. The polyester polyol intermediate contains at least two hydroxyl groups. The molar ratio of the carboxyl groups in the crude dimer acid mixture to the hydroxyl groups in the polyester polyol intermediate is (0.45 to 0.55):1.

[0017] Controlling the ratio of carboxyl groups in the crude dimer acid mixture to hydroxyl groups in the polyester polyol intermediate is to control the crosslinking density.

[0018] As a preferred embodiment, the waterborne polyurethane mortar flooring emulsion has a solid content of 65-75 wt.% and a hydroxyl content of 2-4 wt.%. When the solid content is too low, the emulsion exhibits poor film-forming properties and slow drying, resulting in substandard performance. When the hydroxyl content is too low, cross-linking is insufficient, leading to a soft and abrasion-insensitive paint film. When the hydroxyl content is too high, cross-linking is excessive, causing the paint film to become brittle. This content is fundamental for achieving the optimal NCO / OH ratio with the matching curing agent.

[0019] As a preferred embodiment, the bio-based polyester polyol is at least one of BASF Sovermol 750, Sovermol 1006 and Sovermol 908 or is primary refined castor oil.

[0020] The defoamer is a silicone-modified defoamer, and the silicone-modified defoamer is at least one of CDI4900 and TEGO-900 from Shenzhen Haiwei Additives New Material Technology Co., Ltd.

[0021] The dispersant is at least one of CDI104 and CDI101 from Shenzhen Haiwei Additives New Materials Technology Co., Ltd. The emulsifier is at least one of BASF Lutensol TO5, Lutensol TO7, Lutensol TO9 and REWOQUAT® CQ 100S; The diol is at least one selected from triethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol-600, polypropylene glycol-1000, and polypropylene glycol-2000; The plasticizer includes TXIB.

[0022] Among them, TXIB, as an environmentally friendly plasticizer, has the core advantage of combining excellent environmental safety with superior physical properties compared to traditional phthalate plasticizers. It is not only non-toxic, low in VOCs, and biodegradable, complying with stringent environmental regulations, but also significantly reduces system viscosity, improves processing leveling, and imparts a unique effect of dry, stain-resistant, and better-feeling surfaces to finished products. It is a highly efficient and multifunctional plasticizer upgrade option, and it does not migrate or leach out.

[0023] The second aspect: The application of a waterborne polyurethane mortar flooring emulsion as described in the first aspect includes the following steps: Mixed water-based polyurethane mortar floor emulsion: By weight, 15-50 parts of the first polyester polyol, 0-20 parts of the bio-based polyester polyol, 1.5-3 parts of the defoamer, 0.1-0.6 parts of the dispersant, 0-0.8 parts of the emulsifier, 3-12 parts of the diol, 5-15 parts of the glycidyl ether, and 15-25 parts of the plasticizer are placed in the first container. The temperature is <50℃, and the mixture is dispersed at a stirring speed of 1000-1200 rpm for 10-15 min. Then, 25-35 parts of water are added, and the mixture is dispersed at a stirring speed of 400-600 rpm for 5-10 min to obtain component A. Preparation of isocyanate curing agent: Place at least one of WANNATE PM-200, WANNATE IPDI, and WANNATE MDI-50 into a second container and disperse at a stirring speed of 400-600 rpm for 5-10 min to obtain component B; Preparation of mortar filler: By weight, 60-80 parts of 40-70 mesh or 70-140 mesh river sand, 16-25 parts of white cement, and 8-14 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at a stirring speed of 400-600 rpm for 10-15 minutes to obtain component C. Preparation of aqueous dispersible pigments: Place at least one of the following, Kedi waterborne polyurethane color paste and Yunze oil-in-water color paste, into a third container and disperse at a stirring speed of 400-600 rpm for 5-10 min to obtain component D. Mix components A, B, C, and D: The components A, B, and D are mixed and stirred evenly to obtain a mixed slurry. Then, component C is added to the mixed slurry, stirred and mixed evenly, and after curing, polyurethane mortar flooring can be prepared. The mass ratio of components A, B, C, and D is 1:(0.9-1.3):(1.5-6.2):(0-0.1).

[0024] As a preferred embodiment, when components A, B, and D are mixed, the stirring time is 20-30 s when the temperature is 20-35℃, and 30-50 s when the temperature is 10-20℃.

[0025] As a preferred embodiment, when component C is added to the mixed slurry, the stirring time is 1-1.5 min if the temperature is >30℃; 1.5-2 min if the temperature is 15-30℃; 2-3 min if the temperature is 10-15℃; and 3-5 min if the temperature is <10℃.

[0026] As a preferred embodiment, when components A, B, C, and D are mixed uniformly at 23°C, the viscosity is 20~1000 mPa•s.

[0027] Emulsification difficulties and deterioration of emulsion stability: After high-viscosity polyols react with isocyanates to form prepolymers, the viscosity of the system increases further, leading to a sharp increase in the dispersion energy barrier in water. During high-speed shear emulsification, it is difficult to form uniform and fine latex particles (particle size is easily >500 nm), and it is more likely to cause excessively wide particle size distribution, particle aggregation, or even demulsification, resulting in a significant decrease in storage stability (easy sedimentation and stratification) and freeze-thaw stability.

[0028] Construction and film-forming performance defects: When emulsions prepared with high-viscosity polyols are mixed with fillers and aggregates, the leveling properties, self-leveling ability, and workability of the mortar mixture will be severely degraded. This will lead to construction difficulties, scratches on the coating surface, and difficulty in removing air bubbles, ultimately affecting the surface smoothness, density, and overall mechanical properties of the floor.

[0029] Increased formulation and process costs: To reduce excessively high viscosity, it is often necessary to add additional solvents or large amounts of plasticizers for adjustment. This not only increases VOC emissions and may reduce the final hardness, but also increases the cost of raw materials and post-processing.

[0030] If the viscosity is too low (<20 mPa•s), it usually means that the molecular weight of the first polyester polyol is too low. Although it is easy to emulsify, it will lead to insufficient cohesion, compressive strength and abrasion resistance of the final coating. Attached Figure Description

[0031] Figure 1 The attenuated total reflectance infrared spectra of the polyester polyols prepared in Examples 1-3 and Comparative Examples 1-3 are shown. Detailed Implementation

[0032] The present invention will now be described more fully. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Experimental methods in the following examples or comparative examples, where specific conditions are not specified, are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials, reagents, etc., used, unless otherwise specified, are all commercially available from the conventional market.

[0033] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the embodiments of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any or all possible combinations of one or more of the associated listed items.

[0034] In the description of this application, it should be understood that the terms "first," "second," "third," etc., are used only to distinguish similar objects and are not necessarily used to describe a specific order or sequence, nor should they be construed as indicating or implying relative importance. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0035] A water-based polyurethane mortar flooring emulsion, having a solid content of 65-75 wt.% and a hydroxyl content of 2-4 wt.%, specifically comprises the following components: First, polyester polyol, bio-based polyester polyol, defoamer, dispersant, emulsifier, diol, plasticizer, glycidyl ether and water.

[0036] The mass ratio of the nine raw materials—first polyester polyol, bio-based polyester polyol, defoamer, dispersant, emulsifier, diol, plasticizer, glycidyl ether, and water—is (15-50):(0-20):(1.5-3):(0.1-0.6):(0-0.8):(3-12):(15-25):(5-15):(25-35).

[0037] The first polyester polyol has a hydroxyl value of 100~240mgKOH / g and an average functionality of 2.2~3.5.

[0038] The bio-based polyester polyol is at least one of BASF Sovermol 750, Sovermol 1006, Sovermol 908 and first-grade refined castor oil; In this embodiment of the invention, the defoamer is a silicone-modified defoamer, specifically, at least one of CDI4900 and TEGO-900 from Shenzhen Haiwei Additives New Materials Technology Co., Ltd.

[0039] The dispersant is at least one of CDI104 and CDI101 from Shenzhen Haiwei Additives New Materials Technology Co., Ltd.

[0040] The emulsifier is at least one of BASF Lutensol TO5, Lutensol TO7, Lutensol TO9 and REWOQUAT® CQ100S.

[0041] The diol is at least one of triethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol-600 (PEG-600), polypropylene glycol-1000 (PEG-1000), polypropylene glycol-2000 (PEG-2000), and polypropylene glycol-4000 (PEG-4000).

[0042] Glycidyl ethers are C10-C14 alkyl glycidyl ethers.

[0043] In this embodiment of the invention, the plasticizer is an environmentally friendly plasticizer. Specifically, the environmentally friendly plasticizer selected is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB).

[0044] The preparation method of the first polyester polyol includes the following steps: The first and second small molecule polyols are mixed with a single acid, a catalyst is added, and the mixture is evacuated and reacted at 180-240°C for 3-16 hours. The reaction ends when the acid value of the reaction system is lower than 3 mg KOH / g, yielding a polyester polyol intermediate.

[0045] The total molar ratio of the first and second small-molecule polyols to the monoacid is 1:1 to 4, and the polyester polyol intermediate contains at least two hydroxyl groups. The first small-molecule polyol includes at least one of trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol; the second small-molecule polyol is at least one of the following four diols: 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, or tripropylene glycol.

[0046] Monoacids include at least one of the following: octanoic acid, isooctanoic acid, lauric acid, palmitoleic acid, linoleic acid, stearic acid, and oleic acid.

[0047] A mixture of crude dimer acid was added to the polyester polyol intermediate, and the reaction was continued at 180-240℃ for 3-16 hours. The reaction was terminated when the acid value of the reaction system was below 3 mg KOH / g and the hydroxyl value of the reaction system reached 100-240 mg KOH / g, yielding the first polyester polyol. The molar ratio of carboxyl groups in the crude dimer acid mixture to hydroxyl groups in the polyester polyol intermediate was (0.45-0.55):1.

[0048] In this embodiment of the invention, the crude dimer acid mixture includes monoacid, dimer acid and trimer acid, with monoacid content ≤30wt.%, dimer acid content ≥55wt.%, and trimer acid content ≤20wt.%.

[0049] The catalyst includes at least one of tetrabutyl titanate, tetraisopropyl titanate, tetraoctyl titanate, tetrabutyl zirconate, tetraisopropyl zirconate, dibutyltin dilaurate, and zinc antimony oxide.

[0050] A method for preparing polyurethane mortar flooring includes the following steps: Mixed water-based polyurethane mortar floor emulsion: By weight, 15-50 parts of the first polyester polyol, 0-20 parts of the bio-based polyester polyol, 1.5-3 parts of the organosilicon-modified defoamer, 0.1-0.6 parts of the dispersant, 0-0.8 parts of the emulsifier, 3-12 parts of the diol, 5-15 parts of the glycidyl ether, and 15-25 parts of the plasticizer are placed in the first container. The temperature is <50℃, and the mixture is dispersed at a stirring speed of 1000-1200 rpm for 10-15 min. Then, 25-35 parts of deionized water are added, and the mixture is dispersed at a stirring speed of 400-600 rpm for 5-10 min to obtain component A.

[0051] Preparation of isocyanate curing agent: At least one of WANNATE PM-200, WANNATE IPDI, and WANNATE MDI-50 is placed in a second container and dispersed at a stirring speed of 400-600 rpm for 5-10 minutes to obtain component B. In this embodiment of the invention, WANNATE PM-200 is used as an example.

[0052] Preparation of mortar filler: By weight, 60-80 parts of 40-70 mesh or 70-140 mesh river sand, 16-25 parts of white cement, and 8-14 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at a speed of 400-600 rpm for 10-15 minutes to obtain component C.

[0053] Preparation of aqueous dispersible pigments: Place at least one of the following, Kedi waterborne polyurethane color paste and Yunze oil-in-water color paste, into a third container and disperse at a stirring speed of 400-600 rpm for 5-10 min to obtain component D.

[0054] Mix components A, B, C, and D: The mass ratio of components A, B, C, and D is 1:(0.9-1.3):(1.5-6.2):(0-0.1).

[0055] Mix components A, B, and D. If the temperature is 20-35℃, the stirring time is 20-30 s; if the temperature is 10-20℃, the stirring time is 20-50 s. After stirring evenly, a mixed slurry is obtained.

[0056] Then, component C is added to the mixed slurry. If the temperature is >30℃, the stirring time is 1-1.5 min; if the temperature is 15-30℃, the stirring time is 1.5-2 min; if the temperature is 10-15℃, the stirring time is 2-3 min; if the temperature is <10℃, the stirring time is 3-5 min. After mixing, the viscosity at 23℃ is 20~1000 mPa•s, preferably 20~200 mPa•s. After curing, polyurethane mortar flooring can be prepared.

[0057] In this embodiment of the invention, the methods for determining the working time, flowability, compressive strength, flexural strength, impact resistance, surface hardness, water resistance, alkali resistance, acid resistance, oil resistance and salt water resistance of the waterborne polyurethane mortar self-leveling floor emulsion refer to JC / T 2327-2015; wherein, the surface hardness is measured using a Mohs hardness tester.

[0058] Example 1 Preparation of the first polyester polyol: 440.5 g (1.56 mol) of oleic acid and 351.3 g (2.62 mol) of trimethylolpropane were mixed evenly, tetrabutyl titanate was added, and the mixture was evacuated and reacted at 180-240℃ for 6 h. The acid value was determined by acid titration to be below 3 mg KOH / g, indicating that the reaction had reached its endpoint. Then, 620.2 g of crude dimer acid mixture was added, and the mixture was evacuated again and reacted for 6 h. The acid value was determined by acid titration to be below 3 mg KOH / g, and the hydroxyl value was determined by hydroxyl titration to be 167 mg KOH / g, indicating that the reaction had reached its endpoint and the structure of the obtained product met expectations, thus obtaining the first polyester polyol-1.

[0059] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 15 parts of first polyester polyol-1, 17 parts of first-grade refined castor oil, 1.5 parts of TEGO900 defoamer, 0.1 parts of CDI101 dispersant, 0.2 parts of CQ100s emulsifier, 6 parts of PPG600 and dipropylene glycol, 5 parts of C12-C14 glycidyl ether, and 25.2 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0060] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0061] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0062] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0063] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0064] Example 2 Preparation of the first polyester polyol: 398.9 g (1.41 mol) of oleic acid, 125.2 g (0.95 mol) of trimethylolpropane and 85.8 g (0.63 mol) of pentaerythritol were mixed evenly, tetrabutyl titanate was added, and the mixture was vacuum-sealed and reacted at 180-240℃ for 6 h. The acid value was determined by acid value titration to be below 3 mg KOH / g, confirming that the reaction had reached the endpoint. Then, 251 g of crude dimer acid mixture was added, and the mixture was vacuum-sealed again and reacted for 6 h. The acid value was determined by acid value titration to be below 3 mg KOH / g, and the hydroxyl value was determined by hydroxyl value titration to be 200 mg KOH / g, confirming that the reaction had reached the endpoint and that the structure of the obtained product met expectations, thus obtaining the first polyester polyol-2.

[0065] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 15 parts of first polyester polyol-2, 15 parts of first-grade refined castor oil, 2 parts of TEGO900 defoamer, 0.4 parts of CDI101 dispersant, 0.6 parts of CQ100s emulsifier, 6 parts of PPG2000 and triethylene glycol, 10 parts of C12-C14 glycidyl ether, and 21 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0066] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0067] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0068] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0069] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0070] Example 3 Preparation of the first polyester polyol: 178.6 g (1.04 mol) of decanoic acid, 292.8 g (1.04 mol) of oleic acid, 140.5 g (1.05 mol) of trimethylolpropane and 133.8 g (0.98 mol) of pentaerythritol were mixed evenly, tetrabutyl titanate was added, and the mixture was vacuum-sealed and reacted at 180-240℃ for 6 h. When the acid value was measured to be below 3 mg KOH / g by acid value titration, the reaction was confirmed to have reached the endpoint. Then, 385.4 g of crude dimer acid mixture was added, and the mixture was vacuum-sealed again and reacted for 6 h. When the acid value was measured to be below 3 mg KOH / g by acid value titration and the hydroxyl value was measured to be 185 mg KOH / g by hydroxyl value titration, the reaction was confirmed to have reached the endpoint and the structure of the obtained product was as expected, thus obtaining the first polyester polyol-3.

[0071] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 17 parts of first polyester polyol-3, 20 parts of first-grade refined castor oil, 1.5 parts of TEGO900 defoamer, 0.1 parts of CDI101 dispersant, 0.1 parts of CQ100s emulsifier, 5 parts of PPG1000 and tetraethylene glycol, 5 parts of glycidyl ether tert-carbonate, and 21.3 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0072] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0073] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0074] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0075] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0076] Comparative Example 1 Preparation of polyester polyol: 780.6 g (2.76 mol) of oleic acid and 532.3 g (3.97 mol) of trimethylolpropane were mixed evenly, tetrabutyl titanate was added, and the mixture was evacuated and reacted at 180-240℃ for 6 h. The reaction endpoint was determined by acid value titration to be below 3 mg KOH / g. Then, 328.5 g of adipic acid was added, and the mixture was evacuated again and reacted for 6 h. The acid value was determined by acid value titration to be below 3 mg KOH / g, and the hydroxyl value was determined by hydroxyl value titration to be 167 mg KOH / g. The reaction endpoint was determined to be reached and the structure of the obtained product was as expected, thus obtaining polyester polyol-1.

[0077] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 20 parts of polyester polyol-1, 12 parts of first-grade refined castor oil, 1.5 parts of TEGO900 defoamer, 0.1 parts of CDI101 dispersant, 0.2 parts of CQ100s emulsifier, 6 parts of PPG600 and dipropylene glycol, 5 parts of C12-C14 glycidyl ether, and 25 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0078] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0079] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0080] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0081] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0082] Comparative Example 2 Preparation of polyester polyol: 1050.3g (3.72mol) oleic acid, 107.4g (0.80mol) trimethylolpropane and 408.5g (3.00mol) pentaerythritol were mixed evenly, tetrabutyl titanate was added, and the mixture was evacuated and reacted at 180-240℃ for 6h. The reaction endpoint was determined by acid value titration to be below 3mgKOH / g. Then, 171.1g adipic acid and 154.8g sebacic acid were added, and the mixture was evacuated and reacted for another 6h. The acid value was determined by acid value titration to be below 3mgKOH / g, and the hydroxyl value was determined by hydroxyl value titration to be 203mgKOH / g. The reaction endpoint was determined to be reached and the structure of the obtained product was as expected, thus obtaining polyester polyol-2.

[0083] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 20 parts of polyester polyol-2, 10 parts of first-grade refined castor oil, 2 parts of TEGO900 defoamer, 0.4 parts of CDI101 dispersant, 0.6 parts of CQ100s emulsifier, 6 parts of PPG2000 and triethylene glycol, 10 parts of C12-C14 glycidyl ether, and 21 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0084] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0085] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0086] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0087] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0088] Comparative Example 3 Preparation of polyester polyol: 301.3 g (1.75 mol) of decanoic acid, 549.6 g (1.95 mol) of oleic acid, 370.9 g (2.76 mol) of trimethylolpropane and 191.9 g (1.41 mol) of pentaerythritol were mixed evenly, tetrabutyl titanate was added, and the mixture was evacuated and reacted at 180-240℃ for 6 h. The reaction endpoint was determined by acid value titration to be below 3 mg KOH / g. Then, 160.8 g of adipic acid and 239.7 g of sebacic acid were added, and the mixture was evacuated and reacted for another 6 h. The acid value was determined by acid value titration to be below 3 mg KOH / g, and the hydroxyl value was determined by hydroxyl value titration to be 188 mg KOH / g. The reaction endpoint was determined to be reached and the structure of the obtained product was as expected, thus yielding polyester polyol-3.

[0089] Preparation of waterborne polyurethane mortar floor emulsion: By weight, 27 parts of polyester polyol-3, 10 parts of first-grade refined castor oil, 1.5 parts of TEGO900 defoamer, 0.1 parts of CDI101 dispersant, 0.1 parts of CQ100s emulsifier, 5 parts of PPG1000 and tetraethylene glycol, 5 parts of glycidyl ether tert-carbonate, and 21.3 parts of TXIB plasticizer were placed in a container and dispersed at 1000 rpm for 15 min at 25℃. Then, 30 parts of deionized water were slowly added and dispersed at 500 rpm for 10 min to obtain component A. The stability of component A emulsion was observed and recorded, and the results are shown in Table 2.

[0090] Preparation of isocyanate curing agent: Place WANNATE PM-200 in a container and disperse it at a stirring speed of 500 rpm for 5 min to obtain component B.

[0091] Preparation of mortar filler: By weight, 71 parts of 70-140 mesh river sand, 21 parts of white cement, and 8 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at 500 rpm for 15 min to obtain component C.

[0092] Preparation of water-based dispersion pigment: Cody water-based polyurethane pigment is placed in a container and dispersed at a stirring speed of 500 rpm for 10 min to obtain component D.

[0093] By weight, 2.5 parts of component A, 2.8 parts of component B, and 0.1 parts of component D were mixed and stirred at 25°C for 30 seconds to obtain a slurry. Then, 12.5 parts of component C were added to the slurry and stirred at 25°C for 1.5 minutes. The final mixture was poured into a mold for curing. The workability, flowability, impact resistance, compressive strength, flexural strength, surface hardness, and acid and alkali corrosion resistance of the final mortar flooring product were tested, and the results are shown in Table 2.

[0094] Table 1 Summary of components in Examples 1-3 and Comparative Examples 1-3

[0095] Table 2 Performance results of mortar flooring products in Examples 1-3 and Comparative Examples 1-3

[0096] By comparing the results of examples and comparative examples prepared with polyols of different viscosities, it is evident that only when the viscosity of the polyester polyol is controlled within the range of 20–1000 mPa·s can the prepared waterborne polyurethane emulsion possess both excellent storage stability and applicability for construction. Polyols within this range facilitate the formation of latex particles with uniform particle size and stable structure, ensuring the emulsion remains intact for over 15 days without stratification. Emulsions prepared with excessively high-viscosity polyester polyols, due to difficulties in emulsification and dispersion, are prone to sedimentation and flocculation during storage; the leveling properties and workability of the mortar prepared from them also deteriorate significantly, leading to a decrease in the smoothness of the floor surface. Ultimately, the flooring prepared using polyols of suitable viscosity exhibits significant advantages in compressive strength, surface hardness, and abrasion resistance.

[0097] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A water-based polyurethane mortar flooring emulsion, characterized in that, It includes the following components: The first group of raw materials consists of polyester polyol, bio-based polyester polyol, defoamer, dispersant, emulsifier, diol, plasticizer, glycidyl ether, and water, and the mass ratio of these nine raw materials is: (15-50):(0-20):(1.5-3):(0.1-0.6):(0-0.8):(3-12):(15-25):(5-15):(25-35); The first polyester polyol is prepared by the following method: The first small molecule polyol is mixed and reacted with a monoacid to obtain a polyester polyol intermediate; A crude dimer acid mixture is added to the polyester polyol intermediate and the mixture is reacted to obtain the first polyester polyol. The monoacids include at least one of octanoic acid, isooctanoic acid, lauric acid, palmitoleic acid, linoleic acid, stearic acid, and oleic acid; The first small molecule polyol includes at least one of trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol; The crude dimer acid mixture includes the monoacid, dimer acid and trimer acid, and the monoacid accounts for ≤30 wt.%, the dimer acid accounts for ≥55 wt.%, and the trimer acid accounts for ≤20 wt.%.

2. The water-based polyurethane mortar flooring emulsion according to claim 1, characterized in that, The first polyester polyol has a hydroxyl value of 100~240 mgKOH / g and an average functionality of 2.2~3.

5.

3. The water-based polyurethane mortar flooring emulsion according to claim 2, characterized in that, The method for preparing the first polyester polyol further includes the following steps: The first small molecule polyol is mixed with the monoacid, a catalyst is added, and the mixture is evacuated and reacted at 180~240℃ for 3~16h. When the acid value of the reaction system is lower than 3mgKOH / g, the reaction ends and the polyester polyol intermediate is obtained. The crude dimer acid mixture is added to the polyester polyol intermediate, and the reaction is continued at a temperature of 180~240℃ for 3~16h. When the acid value of the reaction system is lower than 3mgKOH / g and the hydroxyl value of the reaction system reaches 100~240mgKOH / g, the reaction is terminated to obtain the first polyester polyol. The catalyst includes at least one of tetrabutyl titanate, tetraisopropyl titanate, tetraoctyl titanate, tetrabutyl zirconate, tetraisopropyl zirconate, dibutyltin dilaurate, and zinc antimony oxide.

4. The water-based polyurethane mortar flooring emulsion according to claim 3, characterized in that, The method for preparing the first polyester polyol further includes the following steps: The first small molecule polyol and the second small molecule polyol are mixed and reacted with a monoacid to obtain a polyester polyol intermediate. The second small molecule polyol is at least one of 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; The total amount of the first small molecule polyol and the second small molecule polyol is in a molar ratio of 1:1 to 4 to the monoacid. The polyester polyol intermediate contains at least two hydroxyl groups. The molar ratio of the carboxyl groups in the crude dimer acid mixture to the hydroxyl groups in the polyester polyol intermediate is (0.45 to 0.55):

1.

5. The water-based polyurethane mortar flooring emulsion according to claim 1, characterized in that, The solid content of the waterborne polyurethane mortar floor emulsion is 65-75 wt.%, and the hydroxyl content is 2-4 wt.%.

6. The waterborne polyurethane mortar flooring emulsion according to claim 1, characterized in that, The bio-based polyester polyol is at least one of BASF Sovermol 750, Sovermol 1006 and Sovermol 908 or is first-grade refined castor oil. The defoamer is a silicone-modified defoamer, and the silicone-modified defoamer is at least one of CDI4900 and TEGO-900 from Shenzhen Haiwei Additives New Material Technology Co., Ltd. The dispersant is at least one of CDI104 and CDI101 from Shenzhen Haiwei Additives New Materials Technology Co., Ltd. The emulsifier is at least one of BASF Lutensol TO5, Lutensol TO7, Lutensol TO9 and REWOQUAT® CQ100S; The diol is at least one selected from triethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol-600, polypropylene glycol-1000, and polypropylene glycol-2000; The plasticizer includes TXIB.

7. An application of the waterborne polyurethane mortar flooring emulsion as described in any one of claims 1 to 6, comprising the following steps: Mixed water-based polyurethane mortar floor emulsion: By weight, 15-50 parts of the first polyester polyol, 0-20 parts of the bio-based polyester polyol, 1.5-3 parts of the defoamer, 0.1-0.6 parts of the dispersant, 0-0.8 parts of the emulsifier, 3-12 parts of the diol, 5-15 parts of the glycidyl ether, and 15-25 parts of the plasticizer are placed in the first container. The temperature is <50℃, and the mixture is dispersed at a stirring speed of 1000-1200 rpm for 10-15 min. Then, 25-35 parts of water are added, and the mixture is dispersed at a stirring speed of 400-600 rpm for 5-10 min to obtain component A. Preparation of isocyanate curing agent: Place at least one of WANNATE PM-200, WANNATE IPDI, and WANNATE MDI-50 into a second container and disperse at a stirring speed of 400-600 rpm for 5-10 min to obtain component B; Preparation of mortar filler: By weight, 60-80 parts of 40-70 mesh or 70-140 mesh river sand, 16-25 parts of white cement, and 8-14 parts of alkaline earth metal hydroxide are added to a dry mixing equipment and stirred at a stirring speed of 400-600 rpm for 10-15 minutes to obtain component C. Preparation of aqueous dispersible pigments: Place at least one of the following, Kedi waterborne polyurethane color paste and Yunze oil-in-water color paste, into a third container and disperse at a stirring speed of 400-600 rpm for 5-10 min to obtain component D. Mix components A, B, C, and D: The components A, B, and D are mixed and stirred evenly to obtain a mixed slurry. Then, component C is added to the mixed slurry, stirred and mixed evenly, and after curing, polyurethane mortar flooring can be prepared. The mass ratio of components A, B, C, and D is 1:(0.9-1.3):(1.5-6.2):(0-0.1).

8. The application of the waterborne polyurethane mortar flooring emulsion according to claim 7, characterized in that, When components A, B, and D are mixed, the stirring time is 20-30 s if the temperature is 20-35℃, and 30-50 s if the temperature is 10-20℃.

9. The application of the waterborne polyurethane mortar flooring emulsion according to claim 7, characterized in that, When component C is added to the mixed slurry, the stirring time is 1-1.5 min if the temperature is >30℃; 1.5-2 min if the temperature is 15-30℃; 2-3 min if the temperature is 10-15℃; and 3-5 min if the temperature is <10℃.

10. The application of the waterborne polyurethane mortar flooring emulsion according to claim 7, characterized in that, At 23°C, the viscosity of components A, B, C, and D after uniform mixing is 20~1000 mPa•s.

Images