Ultraviolet-proof and low-emissivity polymer stone-like finishing material and preparation method thereof

Abstract

The present application relates to the technical field of building materials, in particular to a kind of anti-ultraviolet, low-emissivity polymer stone-like finish material, it is characterized in that, by weight parts, including the following raw materials: including the following raw materials: cement 40-50 parts, binder 4-10 parts, filler 15-25 parts, water retaining agent 0.1-0.3 parts, water reducing agent 0.3-0.8 parts, expanding agent 2-5 parts, hydroxypropyl cellulose ether 0.2-0.5 parts, water 10-20 parts.The polymer stone-like finish material prepared by the present application has good compressive strength and anti-ultraviolet performance.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a UV-resistant, low-radiation polymer imitation stone finishing material and its preparation method. Background Technology

[0002] In the field of architectural decoration, natural stone has long dominated the high-end decoration market due to its natural texture and excellent physical properties. However, natural stone is non-renewable, and over-exploitation can easily lead to ecological damage. Furthermore, its heavy weight and high transportation costs, coupled with the need for specialized dry-hanging techniques during construction, not only extend the construction period but also pose safety hazards such as detachment. At the same time, the high price of natural stone makes it difficult to meet the economic demands of large-scale architectural decoration. Against this backdrop, stone-like veneer materials have emerged as a core alternative to natural stone.

[0003] Early stone-like materials used a mixture of cement, gypsum, and glass fiber as their main raw materials. While achieving a basic stone-like effect, they suffered from defects such as a stiff texture, poor weather resistance, and insufficient flexibility, making them susceptible to cracking and fading due to environmental factors. From the 1980s onwards, with the development of polymer material technology, solvent-based stone-like coatings were gradually promoted. However, due to their high VOC content and poor environmental performance, they contradicted the global trend of green building development, limiting their application scenarios.

[0004] Since the beginning of the 21st century, increasingly stringent environmental policies and the upgrading of building decoration demands have driven the transformation of imitation stone materials towards polymer-based materials. Polymer emulsions (such as acrylic acid, silicone-modified acrylic acid, and fluorocarbon resins), with their lightweight, flexibility, and environmentally friendly properties, have become the core substrate for imitation stone veneer materials, forming a new category of decorative materials: polymer imitation stone veneer materials. These materials, through the combination of polymer emulsions with fillers such as natural stone powder and colored sand, and advanced molding and spraying processes, can accurately replicate the texture of natural stone. They also possess advantages such as a weight only one-quarter that of natural stone, convenient construction, and controllable costs, effectively solving the pain points of natural stone applications. They are widely used in high-rise building exterior walls, interior decoration, and old wall renovation.

[0005] Patent CN115572498B discloses a stone-like cement art decorative material and a method for decorating with it. The stone-like cement art decorative material includes the following raw materials: epoxy resin; curing agent; cement; sand; color paste; adhesive; organo-bentonite; isomeric tridecyl alcohol polyoxyethylene ether; and N-methylpyrrolidone solution of modified polyurea. The method for decorating with it includes the following steps: S1, mixing epoxy resin and cement, then adding sand and silver powder, and stirring evenly; S2, adding color paste; S3, adding adhesive, organo-bentonite, isomeric tridecyl alcohol polyoxyethylene ether, and N-methylpyrrolidone solution of modified polyurea, and stirring evenly to obtain a mixture; S4, mixing the mixture from step S3 with the curing agent and then applying it to the decorative surface. The stone-like material prepared by this application has excellent construction performance.

[0006] Patent CN113666672B discloses a lightweight photocatalytic stone-like composite material. The raw materials of the stone-like composite material, by weight, include: stone-like powder, silicone-acrylic emulsion, stone powder, compatibilizer, processing aid, water, and dispersant. The stone-like powder comprises inorganic powder materials and acrylate monomers. The compatibilizer comprises: acrylate grafts and a photocatalyst. The preparation method of this lightweight photocatalytic stone-like composite material involves mixing the aforementioned materials, then molding and curing under preset conditions to obtain the stone-like composite material. The lightweight stone-like composite material prepared by the above method possesses both flexibility and strength, and can degrade environmental pollutants on the surface of the stone-like composite material.

[0007] As described in the aforementioned patent, traditional polymer-based stone-like materials are prone to photo-oxidative degradation of their polymer chains under long-term outdoor ultraviolet radiation, leading to surface powdering, cracking, decreased gloss, color fading, or yellowing, severely affecting the durability of their decorative effect. Therefore, there is an urgent need in the market for a polymer-based stone-like surface material with high ultraviolet shielding efficiency and excellent aging resistance. Summary of the Invention

[0008] In view of the problems existing in the prior art, the purpose of this invention is to obtain a polymer imitation stone surface material that has the advantages of UV protection and radiation reduction, without compromising the strength of concrete and with a long service life.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a UV-resistant, low-radiation polymer-based stone-like decorative material, comprising the following raw materials by weight: 40-50 parts cement, 4-10 parts binder, 15-25 parts filler, 0.1-0.3 parts water-retaining agent, 0.3-0.8 parts water-reducing agent, 2-5 parts expanding agent, 0.2-0.5 parts hydroxypropyl cellulose ether, and 10-20 parts water.

[0010] In some embodiments, the cement is silicate cement.

[0011] In some embodiments, the binder, by weight, comprises the following raw materials: 40-60 parts of polyol, 30-45 parts of isocyanate, 1-3 parts of crosslinking agent, 0.1-1 parts of catalyst, and 50-100 parts of solvent.

[0012] In some embodiments, the polyol is any one or more of polypropylene oxide polyol, polytetrahydrofuran polyol, or polyethylene oxide polyol.

[0013] Preferably, the polyol is a polytetrahydrofuran polyol.

[0014] In some embodiments, the isocyanate is any one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, or isophorone diisocyanate.

[0015] Preferably, the isocyanate is isophorone diisocyanate.

[0016] In some embodiments, the catalyst is any one or more of dibutyltin dilaurate, lead octanoate, or stannous octanoate. In some embodiments, the solvent is a mixture of dipropylene glycol methyl ether, dimethyl carbonate, and water.

[0017] Preferably, the mass ratio of dipropylene glycol methyl ether, dimethyl carbonate and water is (2-3):1:(0.5-1).

[0018] In some embodiments, the method for preparing the crosslinking agent includes the following steps: (1) Add p-hydroxybenzaldehyde to NMP and stir for 5-10 min, then add 2-amino-1,3-propanediol and glacial acetic acid, heat to 130-140℃, react for 20-24 h, and then perform post-treatment to obtain the compound; (2) The compound obtained in step (1) is added to thionyl chloride, cyanuric chloride and triethylamine, and the mixture is heated to 50-60℃ and reacted for 11-13h to obtain a crosslinking agent.

[0019] In some embodiments, the molar ratio of p-hydroxybenzaldehyde to 2-amino-1,3-propanediol is 1:(1-1.2).

[0020] In some embodiments, the mass ratio of the compound in step (2) to cyanuric chloride is (3.2-3.5):1.

[0021] The preparation method of the adhesive includes the following steps: adding polyol and part of solvent into a reaction vessel, stirring at 300-400 rpm for 1-2 hours, and then adding isocyanate, crosslinking agent, catalyst and remaining solvent under nitrogen protection, stirring at room temperature for 1-2 hours to obtain the adhesive.

[0022] Traditional polyurethane stone-like veneer materials are prone to fading, chalking, and cracking when exposed to outdoor ultraviolet rays for extended periods. Furthermore, their limited mechanical properties make them susceptible to dents and damage from impacts, leading to difficult repairs and color discrepancies between the repaired areas and the original finish, affecting overall aesthetics. This invention first utilizes a Schiff base reaction between the aldehyde group of p-hydroxybenzaldehyde and the amino group of 2-amino-1,3-propanediol to obtain a compound. Then, the three chlorine atoms of cyanuric chloride undergo a substitution reaction with the hydroxyl groups of the compound, forming multifunctional crosslinking sites. During curing, this allows for a more efficient and stable formation of a highly crosslinked network, increasing the mechanical properties of the stone-like veneer material. Additionally, the UV-absorbing structure is permanently anchored to the polymer backbone network nodes via chemical bonds, achieving both "integration" and long-lasting UV protection. Furthermore, the triazine ring effectively scatters and reflects ultraviolet rays and some thermal radiation, working synergistically with the filler to further enhance radiation protection performance.

[0023] In some embodiments, the filler is a mixture of barium sulfate and quartz sand.

[0024] Preferably, the mass ratio of barium sulfate to quartz sand is 1:(3-4).

[0025] This invention uses barium sulfate as its core function, which can effectively shield and attenuate various types of radiation. It also significantly increases the material's density, providing a substantial texture similar to natural stone, and improves the material's rheological properties during construction. Quartz sand serves as the structural framework, increasing the material's hardness and wear resistance, improving its mechanical strength and durability, and supporting the surface texture of the simulated stone. Together, they form a "rigid yet flexible" system, with complementary functions and synergistic effects. This ensures the material possesses excellent simulated stone appearance and physical properties while fundamentally endowing it with active radiation protection capabilities.

[0026] In some embodiments, the water-reducing agent is a polycarboxylate water-reducing agent.

[0027] A second aspect of this invention provides a method for preparing a UV-resistant, low-radiation polymer-based stone-like decorative material, comprising the following steps: The cement, binder, filler, water-retaining agent, water-reducing agent, expanding agent, hydroxypropyl cellulose ether, and water are stirred together for 1-2 hours to obtain the final product.

[0028] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention has prepared a polymer imitation stone surface material through formulation design. It has good UV resistance, does not damage the strength of concrete after construction, and adds specific fillers to give the material good radiation shielding effect.

[0029] (2) The present invention prepares a multifunctional crosslinking agent binder, which can form a highly crosslinked network more efficiently and stably during curing, thereby increasing the mechanical properties of the stone-like decorative material; in addition, the ultraviolet absorption structure is permanently anchored on the polymer main chain network nodes through chemical bonds, realizing the "integration" and long-term effectiveness of the ultraviolet protection function; furthermore, the triazine ring can effectively scatter and reflect ultraviolet rays and some thermal radiation, and work synergistically with the filler to further increase the radiation protection performance.

[0030] (3) This invention uses barium sulfate as the functional core and quartz sand as the structural skeleton. While ensuring that the material has excellent stone-like appearance and physical properties, it fundamentally endows it with active radiation protection capabilities. Detailed Implementation

[0031] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0032] In the following examples and comparative examples, all compounds and related reagents used were commercially available. Specifically, the polytetrahydrofuran diol had a Mn value of 2000; the cement was silicate cement 42.5; the average particle size of barium sulfate was 250 mesh; the average particle size of the quartz sand was 300 mesh; the water-reducing agent was polycarboxylate superplasticizer, model SP409, manufactured by Liaoning Kelong; the expanding agent was model EP-1000, manufactured by Xingna Technology; the water-retaining agent was hydroxyethyl cellulose, model DJ-30W, manufactured by Guangzhou Daojun Biotechnology Co., Ltd.; and the hydroxypropyl cellulose ether was model MPC 10M(S), manufactured by Shanghai Zhixi.

[0033] Unless otherwise specified, the post-processing steps such as "washing", "drying", and "extraction" used below are routine operations for those skilled in the art, and can be selected according to actual operations.

[0034] Preparation Example 1 The preparation method of crosslinking agent-1 includes the following steps: (1) Add 0.1 mol of p-hydroxybenzaldehyde to 100 ml of NMP and stir for 8 min. Then add 0.11 mol of 2-amino-1,3-propanediol and 30 ml of 6 mol / L glacial acetic acid. Heat to 135 °C and react for 22 h. Wash with acetone and anhydrous methanol and dry to obtain the compound. (2) Add 33g of the compound obtained in step (1) with 10g of cyanuric chloride and 6g of triethylamine to 200ml of thionyl chloride, heat to 55℃ and react for 12h, pour into 5wt% sodium carbonate aqueous solution at 5℃, then extract, collect the organic phase and dry to obtain crosslinking agent-1.

[0035] Preparation Example 2 The preparation method of crosslinking agent-2 is the same as that of preparation example 1, except that the amount of compound added in step (2) is 36g.

[0036] Preparation Example 3 The preparation method of crosslinking agent-3 is the same as that of preparation example 1, except that 2-amino-1,3-propanediol is replaced with 3-aminophenol in equal amounts.

[0037] Preparation Example 4 The preparation method of crosslinking agent-4 is the same as that of preparation example 1, except that cyanuric chloride is replaced with 1,3,5-trichlorobenzene in equal amounts.

[0038] Preparation Example 5 The preparation method of adhesive-1 includes the following steps: by weight, 50 parts of polytetrahydrofuran diol and 40 parts of solvent are added to a reaction vessel and stirred at 350 rpm for 1.5 h. Then, under nitrogen protection, 38 parts of isophorone diisocyanate, 2 parts of crosslinking agent-1, 0.5 parts of dibutyltin dilaurate and 35 parts of solvent are added and stirred at room temperature for 1.5 h to obtain adhesive-1. The solvent is a mixture of dipropylene glycol methyl ether, dimethyl carbonate and water, with a mass ratio of 2.5:1:0.8.

[0039] Preparation Example 6 The preparation method of binder-2 is the same as that of preparation example 1, except that crosslinking agent-1 is replaced with crosslinking agent-2 in equal amounts.

[0040] Preparation Example 7 The preparation method of binder-3 is the same as that of preparation example 1, except that crosslinking agent-1 is replaced with crosslinking agent-3 in equal amounts.

[0041] Preparation Example 8 The preparation method of binder-4 is the same as that of preparation example 1, except that crosslinking agent-1 is replaced with crosslinking agent-4 in equal amounts.

[0042] Preparation Example 9 The preparation method of binder-5 is the same as that of preparation example 1, except that crosslinking agent-1 is replaced with an equal amount of 1,4-butanediol.

[0043] Example 1 A UV-resistant, low-radiation polymer-based stone-like finishing material, comprising the following raw materials by weight: 45 parts cement, 7 parts binder-1, 20 parts filler, 0.2 parts water-retaining agent, 0.5 parts water-reducing agent, 4 parts expanding agent, 0.4 parts hydroxypropyl cellulose ether, and 15 parts water.

[0044] The filler is a mixture of barium sulfate and quartz sand in a mass ratio of 1:3.5.

[0045] The method for preparing the UV-resistant, low-radiation polymer imitation stone finishing material in this embodiment includes the following steps: The cement, binder-1, filler, water-retaining agent, water-reducing agent, expanding agent, hydroxypropyl cellulose ether and water are stirred for 1.5 hours to obtain the final product.

[0046] Example 2 A UV-resistant, low-radiation polymer-based stone-like finishing material, comprising the following raw materials by weight: 40 parts cement, 4 parts binder-1, 15 parts filler, 0.1 parts water-retaining agent, 0.3 parts water-reducing agent, 2 parts expansion agent, 0.2 parts hydroxypropyl cellulose ether, and 10 parts water.

[0047] The filler is a mixture of barium sulfate and quartz sand in a mass ratio of 1:3.

[0048] The method for preparing the UV-resistant, low-radiation polymer imitation stone finishing material in this embodiment includes the following steps: The cement, binder-1, filler, water-retaining agent, water-reducing agent, expanding agent, hydroxypropyl cellulose ether and water are stirred for 1 hour to obtain the final product.

[0049] Example 3 A UV-resistant, low-radiation polymer-based stone-like finishing material, comprising the following raw materials by weight: 50 parts cement, 10 parts binder-1, 25 parts filler, 0.3 parts water-retaining agent, 0.8 parts water-reducing agent, 5 parts expanding agent, 0.5 parts hydroxypropyl cellulose ether, and 20 parts water.

[0050] The filler is a mixture of barium sulfate and quartz sand in a mass ratio of 1:4.

[0051] The method for preparing the UV-resistant, low-radiation polymer imitation stone finishing material in this embodiment includes the following steps: The cement, binder-1, filler, water-retaining agent, water-reducing agent, expanding agent, hydroxypropyl cellulose ether and water are stirred for 1-2 hours to obtain the final product.

[0052] Example 4 A UV-resistant, low-radiation polymer imitation stone finishing material and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that adhesive-1 is replaced with adhesive-2 in equal amounts.

[0053] Example 5 A UV-resistant, low-radiation polymer imitation stone finishing material and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that binder-1 is replaced with binder-3 in equal amounts.

[0054] Example 6 A UV-resistant, low-radiation polymer imitation stone finishing material and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that adhesive-1 is replaced with adhesive-4 in equal amounts.

[0055] Example 7 A UV-resistant, low-radiation polymer imitation stone finishing material and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that adhesive-1 is replaced with adhesive-5 in equal amounts.

[0056] Performance testing 1. The adhesives prepared in Examples 5-9 are processed according to HG / T3689. The yellowing resistance level is determined according to the 2014 standard.

[0057] The test results are shown in Table 1: Table 1

[0058] 2. The polymer imitation stone veneer material prepared in each embodiment was added into a cube mold with a side length of 150 mm and vibrated to compact it using an electric vibration table. After 24 hours, the mold was removed and cured for 28 days at a temperature of 25±5℃ and a relative humidity of 95% to obtain test blocks. The compressive strength was tested according to the "Standard for Test Methods of Mechanical Properties of Ordinary Concrete" GB / T50081-2019. The test results are shown in Table 2: Table 2

[0059] As shown in Table 1, the polymer-based stone-like finishing materials of Examples 1-3 give concrete good compressive strength and good UV resistance. A comparison of the data from Example 4 and Example 1 shows that changing the ratio of the compound to cyanuric chloride may lead to changes in the degree of crosslinking and a decrease in compressive strength. A comparison of the data from Example 5 and Example 1 shows that replacing 2-amino-1,3-propanediol with an equal amount of 3-aminophenol may result in excessive rigidity and steric hindrance of the benzene ring, affecting subsequent reactions and causing a decrease in compressive strength. A comparison of the data from Comparative Example 1 and Example 1 in Example 6 shows that replacing cyanuric chloride with an equal amount of 1,3,5-trichlorobenzene reduces UV resistance. A comparison of the data from Example 1 and Example 7 shows that using a conventional crosslinking agent reduces both compressive strength and UV resistance.

[0060] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A UV-resistant, low-radiation polymer-based stone-like finishing material, characterized in that, By weight, it includes the following ingredients: 40-50 parts cement, 4-10 parts binder, 15-25 parts filler, 0.1-0.3 parts water-retaining agent, 0.3-0.8 parts water-reducing agent, 0.1-0.4 parts expanding agent, 0.2-0.5 parts hydroxypropyl cellulose ether, and 10-20 parts water.

2. The UV-resistant, low-radiation polymer-based stone-like finishing material according to claim 1, characterized in that, The cement is silicate cement.

3. The UV-resistant, low-radiation polymer-based stone-like finishing material according to claim 1, characterized in that, The binder, by weight, comprises the following raw materials: 40-60 parts of polyol, 30-45 parts of isocyanate, 1-3 parts of crosslinking agent, 0.1-1 parts of catalyst, and 50-100 parts of solvent.

4. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 3, characterized in that, The method for preparing the crosslinking agent includes the following steps: (1) Add p-hydroxybenzaldehyde to NMP and stir for 5-10 min, then add 2-amino-1,3-propanediol and glacial acetic acid, heat to 130-140℃, react for 20-24 h, and then perform post-treatment to obtain the compound; (2) The compound obtained in step (1) is added to thionyl chloride, cyanuric chloride and triethylamine, and the mixture is heated to 50-60℃ and reacted for 11-13h to obtain a crosslinking agent.

5. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 4, characterized in that, The molar ratio of p-hydroxybenzaldehyde to 2-amino-1,3-propanediol is 1:(1-1.2).

6. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 4, characterized in that, The mass ratio of the compound in step (2) to cyanuric chloride is (3.2-3.5):

1.

7. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 3, characterized in that, The preparation method of the adhesive includes the following steps: adding polyol and part of solvent into a reaction vessel, stirring at 300-400 rpm for 1-2 hours, and then adding isocyanate, crosslinking agent, catalyst and remaining solvent under nitrogen protection, stirring at room temperature for 1-2 hours to obtain the adhesive.

8. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 1, characterized in that, The filler is a mixture of barium sulfate and quartz sand.

9. The UV-resistant, low-radiation polymer imitation stone finishing material according to claim 1, characterized in that, The water-reducing agent is a polycarboxylate water-reducing agent.

10. A method for preparing a UV-resistant, low-radiation polymer-based stone-like finishing material according to any one of claims 1-9, characterized in that, Includes the following steps: The cement, binder, filler, water-retaining agent, water-reducing agent, expanding agent, hydroxypropyl cellulose ether, and water are stirred together for 1-2 hours to obtain the final product.

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