Resin-based artificial stone and method for producing the same

Abstract

The present application relates to the technical field of artificial stone preparation, in particular to a resin-based artificial stone and a preparation method thereof. The artificial stone comprises the following components in parts by mass: coal gangue 38-45 parts, carbide slag 28-34 parts, desulfurization gypsum 20-30 parts, mineral powder 18-26 parts, water-based epoxy resin 30-45 parts, diethylene triamine 5-10 parts, modified polyurethane fiber 10-15 parts, and quartz sand 220-260 parts. The present application uses solid waste such as coal gangue as a component of the artificial stone, realizes resource utilization, reduces cost, and adds modified polyurethane fiber to effectively improve the performance of the prepared artificial stone.

Description

Technical Field

[0001] This invention relates to the field of artificial stone preparation technology, specifically a resin-based artificial stone and its preparation method. Background Technology

[0002] Artificial stone is a new type of composite material composed of resin, fillers, and curing agents, processed through specific procedures. It boasts advantages such as being non-toxic, non-radioactive, flame-retardant, non-stick to oil, stain-resistant, antibacterial, mildew-proof, wear-resistant, impact-resistant, easy to maintain, seamlessly joined, and capable of being shaped into any form. It is gradually becoming a new favorite in the building materials market. Artificial stone products are simple to manufacture, have a short production cycle, low cost, and are widely used in various indoor and outdoor architectural decorations.

[0003] Existing artificial stone manufacturing costs are relatively high, generating a large amount of solid waste annually, primarily consisting of coal gangue, mineral powder, and carbide slag. If this solid waste could be utilized in a resource-based manner, such as through artificial stone production, it would not only reduce production costs but also decrease environmental pollution. Furthermore, this invention enhances the performance of artificial stone by adding modified polyurethane fibers, meeting the increasingly demanding requirements of the construction industry. Summary of the Invention

[0004] The purpose of this invention is to provide a resin-based artificial stone and its preparation method to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A resin-based artificial stone material, comprising the following components by weight:

[0007] 38-45 parts coal gangue, 28-34 parts calcium carbide slag, 20-30 parts desulfurized gypsum, 18-26 parts mineral powder, 30-45 parts waterborne epoxy resin, 5-10 parts diethylenetriamine, 10-15 parts modified polyurethane fiber, and 220-260 parts quartz sand.

[0008] The modified polyurethane fiber is prepared by the following method:

[0009] S101. Dissolve the polyurethane masterbatch in an organic solvent to prepare a polyurethane solution;

[0010] S102. The pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 0.5~1h.

[0011] S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -40~-80℃ for 20-40h.

[0012] S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane for 1-4 hours, and then vacuum dried at room temperature to obtain modified polyurethane fiber.

[0013] Furthermore, the organic solvent used in step S101 is N,N-dimethylformamide, and the mass ratio between polyurethane masterbatch and N,N-dimethylformamide is 1:(4~5).

[0014] Furthermore, the mass ratio between the pretreated nano-montmorillonite in step S102 and the polyurethane masterbatch in step S101 is 1:(5~10).

[0015] Furthermore, in step S104, the pH of the mixed solution of calcium hydroxide and aminopropyltriethoxysilane is 10-11, and the mass fraction of aminopropyltriethoxysilane is 0.5%.

[0016] Furthermore, the pretreatment steps for nano-montmorillonite in step S102 are as follows:

[0017] S201. Calcine the nano-montmorillonite at 300℃ for 3 hours. After calcination, disperse the nano-montmorillonite in a 2 mol / L hydrochloric acid solution and soak for 1.5 hours. Filter the solution and wash the filtered product with sufficient deionized water. Then, vacuum dry the product at room temperature.

[0018] S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 0.05~0.2mol / L calcium chloride and 0.05~0.2mol / L aluminum chloride for 8~10 hours, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite.

[0019] Furthermore, the hydrochloric acid solution used in step S201 is 20 times the mass of nano-montmorillonite, and the mixed solution of calcium chloride and aluminum chloride used in step S202 is 30 times the mass of nano-montmorillonite.

[0020] A method for preparing resin-based artificial stone includes the following steps:

[0021] S1. Coal gangue, carbide slag, desulfurized gypsum and mineral powder are placed into a muffle furnace according to the mass fraction and calcined at 1000℃ for 2 hours to obtain the first mixture;

[0022] S2. Add waterborne epoxy resin, diethylenetriamine, modified polyurethane fiber and quartz sand to water according to the mass ratio, stir evenly to obtain the second mixture;

[0023] S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

[0024] Furthermore, in step S2, the mass ratio of water to quartz sand is 4:1.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] 1. This invention effectively utilizes solid waste, saves resources, and reduces the production cost of artificial stone by adding coal gangue, carbide slag, desulfurized gypsum, and mineral powder as constituent materials of artificial stone.

[0027] 2. The artificial stone prepared by this invention incorporates modified polyurethane fibers, and nano-montmorillonite is added to the modified polyurethane fibers, which effectively improves the performance of the prepared artificial stone.

[0028] 3. The nano-montmorillonite used in this invention undergoes pretreatment. Through ion exchange properties, calcium and aluminum ions are loaded between the nano-montmorillonite layers, providing more nucleation sites and promoting hydration reactions. The nano-montmorillonite is prepared by spinning together with polyurethane. The polyurethane fiber acts as a load, improving the dispersion ability of the nano-montmorillonite, preventing agglomeration, and enhancing its performance of artificial stone. Attached Figure Description

[0029] Figure 1 This is a process flow diagram for preparing resin-based artificial stone in this invention;

[0030] Figure 2 This is a process flow diagram for preparing modified polyurethane fibers in this invention;

[0031] Figure 3 This is a process flow diagram for preparing pretreated nano-montmorillonite in this invention. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Please see Figures 1 to 3 The present invention provides: Example

[0034] A method for preparing resin-based artificial stone includes the following steps:

[0035] S1. 42g of coal gangue, 33g of carbide slag, 26g of desulfurized gypsum and 21g of mineral powder are put into a muffle furnace and calcined at 1000℃ for 2 hours to obtain the first mixture.

[0036] S2. Add 42g of waterborne epoxy resin, 8g of diethylenetriamine, 11g of modified polyurethane fiber and 240g of quartz sand to 60g of water and stir evenly to obtain the second mixture.

[0037] S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

[0038] The modified polyurethane fibers described above are prepared by the following method:

[0039] S101. Dissolve 25g of polyurethane masterbatch in 110g of organic solvent, the organic solvent being N,N-dimethylformamide, to prepare a polyurethane solution.

[0040] S102. 3.2g of pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 0.8h.

[0041] S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -65°C for 30 hours.

[0042] S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane with a pH of 10.5 for 3 hours. The mass fraction of aminopropyltriethoxysilane is 0.5%. Then, it is vacuum dried at room temperature to obtain modified polyurethane fiber.

[0043] The pretreatment steps for nano-montmorillonite in step S102 above are as follows:

[0044] S201. 5.2g of nano-montmorillonite was calcined at 300℃ for 3h. The calcined nano-montmorillonite was dispersed in 104g of hydrochloric acid solution with a concentration of 2mol / L and soaked for 1.5h. The filtered product was washed with sufficient deionized water and dried under vacuum at room temperature.

[0045] S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 156g of calcium chloride (0.1mol / L) and aluminum chloride (0.08mol / L) for 9 hours, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite. Example

[0046] A method for preparing resin-based artificial stone includes the following steps:

[0047] S1. 38g of coal gangue, 28g of carbide slag, 20g of desulfurized gypsum and 18g of mineral powder are put into a muffle furnace and calcined at 1000℃ for 2 hours to obtain the first mixture.

[0048] S2. Add 30g of waterborne epoxy resin, 5g of diethylenetriamine, 10g of modified polyurethane fiber and 220g of quartz sand to 55g of water and stir evenly to obtain the second mixture.

[0049] S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

[0050] The modified polyurethane fibers described above are prepared by the following method:

[0051] S101. Dissolve 25g of polyurethane masterbatch in 100g of organic solvent, the organic solvent being N,N-dimethylformamide, to prepare a polyurethane solution.

[0052] S102. 5g of pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 0.5h.

[0053] S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -40°C for 20 hours.

[0054] S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane with a pH of 10 for 1 hour. The mass fraction of aminopropyltriethoxysilane is 0.5%. Then, it is vacuum dried at room temperature to obtain modified polyurethane fiber.

[0055] The pretreatment steps for nano-montmorillonite in step S102 above are as follows:

[0056] S201. 5.2g of nano-montmorillonite was calcined at 300℃ for 3h. The calcined nano-montmorillonite was dispersed in 104g of hydrochloric acid solution with a concentration of 2mol / L and soaked for 1.5h. The filtered product was washed with sufficient deionized water and dried under vacuum at room temperature.

[0057] S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 156g of calcium chloride and aluminum chloride with a concentration of 0.05mol / L for 8h, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite. Example

[0058] A method for preparing resin-based artificial stone includes the following steps:

[0059] S1. 45g of coal gangue, 34g of carbide slag, 30g of desulfurized gypsum and 26g of mineral powder are put into a muffle furnace and calcined at 1000℃ for 2 hours to obtain the first mixture.

[0060] S2 adds 45g of waterborne epoxy resin, 10g of diethylenetriamine, 15g of modified polyurethane fiber and 260g of quartz sand to 65g of water and stirs evenly to obtain the second mixture.

[0061] S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

[0062] The modified polyurethane fibers described above are prepared by the following method:

[0063] S101. Dissolve 25g of polyurethane masterbatch in 125g of organic solvent, the organic solvent being N,N-dimethylformamide, to prepare a polyurethane solution.

[0064] S102. 2.5g of pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 1h.

[0065] S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -80°C for 40 hours.

[0066] S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane with a pH of 11 for 4 hours. The mass fraction of aminopropyltriethoxysilane is 0.5%. Then, it is vacuum dried at room temperature to obtain modified polyurethane fiber.

[0067] The pretreatment steps for nano-montmorillonite in step S102 above are as follows:

[0068] S201. 5.2g of nano-montmorillonite was calcined at 300℃ for 3h. The calcined nano-montmorillonite was dispersed in 104g of hydrochloric acid solution with a concentration of 2mol / L and soaked for 1.5h. The filtered product was washed with sufficient deionized water and dried under vacuum at room temperature.

[0069] S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 156g of calcium chloride and aluminum chloride with a concentration of 0.2mol / L for 10h, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite. Example

[0070] A method for preparing resin-based artificial stone includes the following steps:

[0071] S1. 42g of coal gangue, 33g of carbide slag, 28g of desulfurized gypsum and 24g of mineral powder are put into a muffle furnace and calcined at 1000℃ for 2 hours to obtain the first mixture.

[0072] S2. Add 44g of waterborne epoxy resin, 8g of diethylenetriamine, 14g of modified polyurethane fiber and 250g of quartz sand to 62.5g of water and stir evenly to obtain the second mixture.

[0073] S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

[0074] The modified polyurethane fibers described above are prepared by the following method:

[0075] S101. Dissolve 25g of polyurethane masterbatch in 115g of organic solvent, the organic solvent being N,N-dimethylformamide, to prepare a polyurethane solution.

[0076] S102. 4g of pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 0.8h.

[0077] S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -50°C for 32 hours.

[0078] S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane with a pH of 11 for 3 hours. The mass fraction of aminopropyltriethoxysilane is 0.5%. Then, it is vacuum dried at room temperature to obtain modified polyurethane fiber.

[0079] The pretreatment steps for nano-montmorillonite in step S102 above are as follows:

[0080] S201. Calcine the nano-montmorillonite at 300℃ for 3 hours. After calcination, disperse the nano-montmorillonite in 104g of 2mol / L hydrochloric acid solution and soak for 1.5 hours. Filter the solution and wash the filtered product with sufficient deionized water and then vacuum dry it at room temperature.

[0081] S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 156g of calcium chloride (0.15mol / L) and aluminum chloride (0.12mol / L) for 10h, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite.

[0082] Comparative Example 1

[0083] The difference between Comparative Example 1 and Example 1 is that step S202 of the pretreatment of nano-montmorillonite is omitted, while the remaining steps are exactly the same as in Example 1.

[0084] Comparative Example 2

[0085] The difference between Comparative Example 2 and Example 1 is that the pretreatment of nano-montmorillonite in step S102 was omitted, and instead 1.4g of pretreated montmorillonite was added directly in step S2. The remaining steps are exactly the same as in Example 1.

[0086] Comparative Example 3

[0087] The difference between Comparative Example 3 and Example 1 is that step S104 is omitted, while the remaining steps are exactly the same as in Example 1.

[0088] Comparative Example 4

[0089] The difference between Comparative Example 4 and Example 1 is that the addition of pretreatment nano-montmorillonite in step S102 was completely eliminated, while the remaining steps are exactly the same as in Example 1.

[0090] The coal gangue, carbide slag, desulfurized gypsum and mineral powder used in this invention are all sieved through a 40-mesh screen, and the quartz sand used is sieved through a 4-mesh screen.

[0091] The compressive strength and flexural strength of the resin-based artificial stone materials prepared in Examples 1-4 and Comparative Examples 1-4 were tested according to GB / T50081-2019 Standard for Test Methods of Physical and Mechanical Properties of Concrete. The test results are shown in Table 1 below:

[0092] Table 1: Test results of flexural and compressive strength of resin-based artificial stone materials prepared in Examples 1-4 and Comparative Examples 1-4

[0093] Flexural strength (MPa) Compressive strength (MPa) Example 1 23.2 176.4 Example 2 22.1 168.5 Example 3 24.8 179.1 Example 4 21.6 159.6 Comparative Example 1 20.8 156.9 Comparative Example 2 21.1 164.7 Comparative Example 3 20.4 157.2 Comparative Example 4 17.3 136.9

[0094] By comparing Comparative Example 1 and Example 1, it can be seen that the removal of calcium and aluminum ions from the nano-montmorillonite reduces the performance of concrete. By comparing Comparative Example 2 and Example 1, it can be seen that the small amount of pretreated nano-montmorillonite added in this invention is prepared by spinning it together with polyurethane fibers, which facilitates its dispersion. The addition of pretreated nano-montmorillonite in this invention promotes the performance improvement of artificial stone, and the further processing in step S104 enhances the performance improvement effect of modified polyurethane fibers on artificial stone.

[0095] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A resin-based artificial stone material, characterized by, By weight, it includes the following components: 38-45 parts coal gangue, 28-34 parts calcium carbide slag, 20-30 parts desulfurized gypsum, 18-26 parts mineral powder, 30-45 parts waterborne epoxy resin, 5-10 parts diethylenetriamine, 10-15 parts modified polyurethane fiber, and 220-260 parts quartz sand. The modified polyurethane fiber is prepared by the following method: S101. Dissolve the polyurethane masterbatch in an organic solvent to prepare a polyurethane solution; S102. The pretreated nano-montmorillonite is ultrasonically dispersed into the polyurethane solution in step S101 and continuously magnetically stirred for 0.5~1h. S103. The polyurethane solution from step S102 is subjected to wet spinning, and the product is freeze-dried at -40~-80℃ for 20-40h. S104. The product after freeze-drying in step S103 is immersed in a mixed solution of calcium hydroxide and aminopropyltriethoxysilane for 1-4 hours, and then vacuum dried at room temperature to obtain modified polyurethane fiber. The mass ratio between the pretreated nano-montmorillonite in step S102 and the polyurethane masterbatch in step S101 is 1:(5~10).

2. The resin-based artificial stone according to claim 1, characterized by The organic solvent used in step S101 is N,N-dimethylformamide, and the mass ratio between polyurethane masterbatch and N,N-dimethylformamide is 1:(4~5).

3. The resin-based artificial stone according to claim 1, characterized by In step S104, the pH of the mixed solution of calcium hydroxide and aminopropyltriethoxysilane is 10-11, and the mass fraction of aminopropyltriethoxysilane is 0.5%.

4. The resin-based artificial stone according to claim 1, characterized by The pretreatment steps for nano-montmorillonite in step S102 are as follows: S201. Calcine the nano-montmorillonite at 300℃ for 3 hours. After calcination, disperse the nano-montmorillonite in a 2 mol / L hydrochloric acid solution and soak for 1.5 hours. Filter the solution and wash the filtered product with sufficient deionized water. Then, vacuum dry the product at room temperature. S202. The nano-montmorillonite treated in step S201 is immersed in a mixed solution of 0.05~0.2mol / L calcium chloride and 0.05~0.2mol / L aluminum chloride for 8~10 hours, centrifuged and filtered, and the product is vacuum dried at room temperature to obtain pretreated nano-montmorillonite.

5. The resin-based artificial stone according to claim 4, characterized by The hydrochloric acid solution used in step S201 is 20 times the mass of nano-montmorillonite, and the mixed solution of calcium chloride and aluminum chloride used in step S202 is 30 times the mass of nano-montmorillonite.

6. A method for preparing resin-based artificial stone as described in any one of claims 1-5, characterized in that, Includes the following steps: S1. Coal gangue, carbide slag, desulfurized gypsum and mineral powder are placed into a muffle furnace according to the mass fraction and calcined at 1000℃ for 2 hours to obtain the first mixture; S2. Add waterborne epoxy resin, diethylenetriamine, modified polyurethane fiber and quartz sand to water according to the mass ratio, stir evenly to obtain the second mixture; S3. Add the first mixture from step S1 to the mixture from step S2 and continue stirring and mixing until uniform. The uniform product is cured for 28 days at 25°C and 95% relative humidity to obtain resin-based artificial stone.

7. The method of claim 6, wherein the resin-based artificial stone is prepared by mixing the resin composition and the filler composition, and then curing the mixture. In step S2, the mass ratio of water to quartz sand is 4:1.

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