Artificial stone waste residue modifier, modification method and application thereof

Abstract

The application discloses a kind of artificial stone waste residue modifier and its modification method and application, belong to calcium carbonate solid waste resource utilization technical field.Modifier component includes at least one of hydrophilic silicone oil and fatty acid phosphate ester sodium salt and maleic acid-acrylic acid copolymer.The modifier is mainly used to modify artificial stone waste residue.Modified artificial stone waste residue obtained by the above modifier is significantly reduced oil absorption value compared with unmodified artificial stone waste residue, can effectively improve the compatibility, dispersibility and stability of artificial stone waste residue powder in artificial stone product, realize its high proportion filling of 94wt% or more in artificial stone product.Its preparation method is simple, can significantly improve mechanical properties for artificial stone product, and significantly reduce production cost.

Description

Technical Field

[0001] This invention relates to the field of calcium carbonate solid waste resource utilization technology, and more specifically, to a modifier for artificial quartz stone waste residue, its modification method, and its application. Background Technology

[0002] Artificial engineered stone is made from raw materials such as calcite, marble, and limestone, using unsaturated resin as a binder, and adding appropriate amounts of curing agents, diluents, and accelerators. The mixture is then stirred, vacuum-pressed, and processed through cutting, polishing, and protection to create slabs of varying thicknesses or irregularly shaped decorative materials. However, the cutting and polishing process generates a large amount of waste stone slurry containing calcium carbonate residue. After sedimentation and drying, this solid waste comprises approximately 20% of the raw material mass; this portion is referred to as artificial engineered stone waste residue. The main components of this waste residue are calcium carbonate and unsaturated resin. Calcium carbonate particles are tightly coated with a three-dimensional network structure of unsaturated resin. This waste residue has a complex structure and is difficult to degrade. Currently, there is no low-cost method for large-scale resource utilization, and improper disposal can cause severe environmental pollution. At present, artificial engineered stone waste residue is generally disposed of through landfill and open-air dumping. This not only occupies a large amount of land but also generates large amounts of volatile organic compounds and wind-blown calcium carbonate powder, causing secondary pollution and representing a significant waste of resources. Therefore, there is an urgent need to make reasonable resource utilization of artificial quartz stone waste.

[0003] Reusing artificial quartz stone waste to produce new artificial quartz stone is a promising and economical solution for solid waste resource utilization. The waste typically contains 92%–93% calcium carbonate. Through drying and grinding, a large number of active organic groups can be generated on its surface. However, currently, the waste is limited by its strong hydrophobicity and uneven particle size distribution, making it unsuitable for producing new artificial quartz stone. Therefore, it is urgent to develop new modifiers and use surface modification methods to transform its hydrophobic surface into a hydrophilic surface. Simultaneously, effective particle size control should be achieved during the modification process to realize the reuse of artificial quartz stone waste and zero-waste discharge, turning waste into treasure.

[0004] Artificial quartz waste contains unsaturated polyester-based and heavy calcium carbonate composite particles. Its surface properties differ from those of pure heavy calcium carbonate, necessitating surface modification of the calcium carbonate / unsaturated resin particles to refining and optimize these properties, thereby achieving high-proportion filling and improving the quality of the composite material. Current technologies for surface organic modification of artificial quartz waste still utilize traditional surfactants such as stearic acid and its salts, titanate and aluminate coupling agents, and the final application systems are geared towards oleophilic PBT engineering plastics, PBS plastics, HDPE plastics, PTT plastics, sheet molding compounds, and plastic masterbatches (CN202010484123.2; CN202110661464.7; CN202110662859.9; CN202010976280.5; CN202010745620.3; CN202010484119.6). To date, there is no research on the hydrophilic organic modification of artificial quartz waste (calcium carbonate modified with unsaturated resin at a content of 7%–15%). Therefore, it is necessary to develop or research new hydrophilic organic modifiers that can significantly reduce the oil absorption value while ensuring that the modified artificial quartz waste retains its hydrophilicity, thereby further enhancing the compatibility and dispersibility of artificial quartz waste with unsaturated resin, achieving the goals of saving resin, reducing product costs, and protecting the environment.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] One of the objectives of this invention is to provide a modifier for modifying artificial quartz stone waste.

[0007] A second objective of this invention includes providing an application of the above-mentioned modifier.

[0008] A third objective of this invention is to provide a modified artificial quartz waste residue, which can effectively improve its compatibility, dispersibility and stability with unsaturated polyester, and achieve its high proportion of filling and secondary utilization in artificial quartz.

[0009] The fourth objective of this invention is to provide a method for preparing the above-mentioned modified artificial quartz waste residue, which is simple, has a short cycle, and is low in cost.

[0010] The fifth objective of this invention includes providing an application of the above-mentioned modified artificial quartz waste in the preparation of artificial quartz products.

[0011] The sixth objective of this invention includes providing an artificial quartz product containing the aforementioned modified artificial quartz waste residue in its raw materials.

[0012] The seventh objective of this invention includes providing a method for preparing artificial quartz products containing the above-mentioned modified artificial quartz waste residue.

[0013] This application can be implemented in the following ways:

[0014] First, this application provides a modified agent for artificial quartz waste, the components of which include at least one of hydrophilic silicone oil and sodium salt of fatty acid phosphate, and maleic acid-acrylic acid copolymer.

[0015] In an optional embodiment, the hydrophilic silicone oil includes at least one of hydroxyl silicone oil, amino silicone oil, and polyether-modified polydimethylsiloxane.

[0016] In an optional embodiment, the sodium salt of fatty acid phosphate includes at least one of sodium oleate phosphate, sodium stearate phosphate, and sodium lauryl phosphate.

[0017] Second, this application provides an application of the above-mentioned modifier for modifying artificial quartz stone waste.

[0018] Third, this application provides a modified artificial quartz waste residue, which is obtained by modifying artificial quartz waste residue with the above-mentioned modifier.

[0019] In an optional embodiment, the amount of modifier added is 0.1-1.5 wt% of the artificial quartz waste, preferably 0.3-0.8 wt%.

[0020] Fourth, this application provides a method for preparing modified artificial quartz waste residue as described in any of the foregoing embodiments, including modification at 80-120°C; the modification time not exceeding 60 minutes.

[0021] Fifth, this application provides the application of modified artificial quartz waste as described in any of the foregoing embodiments in artificial quartz products.

[0022] Sixth, this application provides an artificial quartz stone product, the raw materials of which include modified artificial quartz stone waste as described in any of the foregoing embodiments and unsaturated resin.

[0023] In an optional embodiment, the raw materials for the above-mentioned artificial granite products also include additives.

[0024] In an alternative embodiment, the additives include curing agents, accelerators, and diluents.

[0025] In an optional embodiment, the content of modified artificial quartz waste in the total amount of modified artificial quartz waste and unsaturated resin is not less than 94 wt%, preferably 94-95 wt%.

[0026] Seventh, this application provides a method for preparing the artificial granite product as described in the foregoing embodiments, comprising the following steps:

[0027] (1) Mix the raw materials: Mix them at room temperature for 10-60 minutes using a wet mixing method.

[0028] (2) The material after mixing in step (1) is subjected to vacuum high pressure molding: curing temperature 40-80℃, curing time 3-6h.

[0029] (3) After the artificial stone blocks in step (2) have been formed and solidified, they are subjected to sawing, polishing, cutting and other operations.

[0030] The beneficial effects of this application include:

[0031] This application proposes a modifier that can effectively increase the filling amount of artificial quartz stone waste in artificial quartz stone. The artificial quartz stone waste is modified by using at least one of hydrophilic silicone oil and sodium fatty acid phosphate salt, as well as a maleic acid-acrylic acid copolymer modifier. The modifier utilizes the -OH, -NH-, and PO4 groups in the hydrophilic silicone oil or sodium fatty acid phosphate salt. 3- And the ether structure and Ca in artificial quartz waste 2+ Chemical bonding and arrangement occur, achieving organic coating modification of the surface of the artificial quartz waste powder. This significantly reduces the oil absorption value of the artificial quartz waste powder, thereby effectively improving its compatibility, dispersibility, and stability in artificial quartz, achieving a high filling ratio of over 94 wt% in artificial quartz. The preparation method of the modified artificial quartz waste provided in this application is simple, has a short cycle time, and is low in cost. Using this modified artificial quartz waste powder to prepare artificial quartz products can effectively save resin usage and significantly reduce production costs. Attached Figure Description

[0032] Figure 1 The image below is a scanning electron microscope image of the modified artificial quartz waste obtained in Example 1. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0034] The following is a detailed description of the artificial quartz waste residue modifier, its modification method, and its application provided in this application.

[0035] Existing surface modification methods and surface modifier formulations often focus only on the modification of artificial quartz waste and its application in plastic materials, lacking research on the modification and reuse of artificial quartz waste in the preparation of artificial quartz products. Through long-term research, the inventors have creatively proposed modifying artificial quartz waste with specific modifiers to improve the dispersibility and filling capacity of artificial quartz waste powder particles in artificial quartz products, enhance its bonding force with unsaturated resins, and improve the various properties of artificial quartz waste powder used in the preparation of artificial quartz.

[0036] The modifiers used in this application include hydrophilic silicone oil, sodium salt of fatty acid phosphate, and maleic acid-acrylic acid copolymer.

[0037] In some embodiments, the modifier contains hydrophilic silicone oil and a maleic acid-acrylic acid copolymer, wherein the mass ratio of the hydrophilic silicone oil to the maleic acid-acrylic acid copolymer may be, but is not limited to, 1:1, and may also be any mass ratio within the range of 10:1 to 1:10. In some embodiments, the modifier contains sodium salt of fatty acid phosphate and a maleic acid-acrylic acid copolymer, wherein the mass ratio of the sodium salt of fatty acid phosphate and the maleic acid-acrylic acid copolymer may be, but is not limited to, 1:1, and may also be any mass ratio within the range of 10:1 to 1:10. In some embodiments, the modifier simultaneously contains hydrophilic silicone oil, sodium salt of fatty acid phosphate, and a maleic acid-acrylic acid copolymer, wherein the mass ratio of the three components may be 1:1:1, or may be any mass ratio within the range of 1-10:1-10:1-10.

[0038] In this application, in optional embodiments, the hydrophilic silicone oil includes at least one of hydroxyl silicone oil, amino silicone oil, and polyether-modified polydimethylsiloxane.

[0039] In an optional embodiment, the sodium salt of fatty acid phosphate includes sodium oleate phosphate (C... 18 H 35 Na2O6P), sodium stearate phosphate (C 18 H 35 Na2O6P), sodium lauryl phosphate (C 12 H 23 At least one of Na2O6P.

[0040] The above-mentioned modifiers are mainly used to modify artificial quartz stone waste residue, which can effectively improve the compatibility, dispersibility and stability of artificial quartz stone waste residue in artificial quartz stone products, and increase the filling ratio of artificial quartz stone waste residue.

[0041] The modified artificial quartz waste proposed in this application is obtained by modifying artificial quartz waste with a modifier.

[0042] In optional embodiments, the amount of modifier added is 0.1-1.5 wt% of the artificial quartz waste, such as 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, or 1.5 wt%, or any other value within the range of 0.1-1.5 wt%. In some preferred embodiments, the amount of modifier added is 0.3-0.8 wt% of the artificial quartz waste. Modified artificial quartz waste obtained after modification at the preferred addition amount has a lower oil absorption value while maintaining good hydrophilicity, exhibiting stronger compatibility, better dispersibility, and better stability in artificial quartz products.

[0043] For reference, the preferred particle size of artificial quartz waste is d. 97 ≤45μm.

[0044] This application utilizes hydrophilic silicone oil, sodium salt of fatty acid phosphate, and maleic acid-acrylic acid copolymer for the modification of artificial quartz waste. Through the complexation effect between hydroxyl groups, amides, phosphate salts, and ethers, a superior surface modification effect is achieved, thereby significantly reducing the oil absorption value. Specifically, the complexation process utilizes the -OH and -NH- groups in the hydrophilic silicone oil and the PO4 groups in the sodium salt of fatty acid phosphate. 3- With Ca in artificial quartz waste 2+ Chemical bonding and arrangement occur, improving the compatibility, dispersibility, and stability of artificial quartz waste in artificial quartz products. Maleic acid-acrylic acid copolymers also enhance the effect of CO3... 2- The original resin molecules have a strong dispersing effect, which can enhance compatibility and synergistic effect, thereby increasing the filling ratio of artificial quartz stone waste residue, and the various properties of the obtained artificial quartz stone products are significantly enhanced, and the production cost is significantly reduced.

[0045] Correspondingly, this application provides a method for preparing the above-mentioned modified artificial quartz waste, which may specifically include the following steps: modifying the artificial quartz waste with a modifier.

[0046] In optional embodiments, the modification temperature can be 80-120℃ (e.g., 80℃, 90℃, 100℃, 110℃, or 120℃). The modification time is preferably no more than 60 minutes, and more preferably 10-20 minutes.

[0047] Furthermore, this application provides the application of the above-mentioned modified artificial quartz waste in artificial quartz products.

[0048] Correspondingly, this application provides an artificial quartz product prepared from modified artificial quartz waste as raw material, the raw material of which includes the above-mentioned modified artificial quartz waste and unsaturated resin.

[0049] Furthermore, the raw materials for the aforementioned artificial granite products may also include additives, such as curing agents, accelerators, and diluents. In optional embodiments, additives may include methyl ethyl ketone, cobalt solution, styrene, and color pastes.

[0050] In an optional embodiment, the content of modified artificial quartz waste in the total amount of modified artificial quartz waste and unsaturated resin is not less than 94 wt%, preferably 94-95 wt%, such as 94.2 wt%, 94.4 wt%, 94.6 wt%, 94.8 wt%, or 95.0 wt%. That is, the filling amount of artificial quartz waste is 94-95 wt%.

[0051] In an optional embodiment, the amount of the additive can be 5-20 wt% of the unsaturated resin, such as 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, or 15 wt%.

[0052] As mentioned above, the artificial quartz stone products significantly reduce costs due to the high content of modified artificial quartz stone waste. Furthermore, based on the high filling amount of modified artificial quartz stone waste, these products also possess numerous superior properties, such as impact strength, flexural strength, and flame retardant properties.

[0053] In addition, this application also provides a method for preparing the above-mentioned artificial granite products, which may include the following steps: mixing raw materials.

[0054] In an optional embodiment, mixing is carried out by wet mixing, which is a simple and quick process.

[0055] For reference, mixing can be carried out at room temperature for 5-60 minutes (e.g., 5 min, 10 min, 20 min, 30 min or 60 min).

[0056] Furthermore, the mixed materials are subjected to vacuum high-pressure molding and demolding.

[0057] For reference, the curing temperature can be 40-80℃, such as 40℃, 50℃, 60℃, 70℃ or 80℃. The curing time can be 3-6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or 6 hours.

[0058] Furthermore, the solidified artificial stone products are subjected to sawing, polishing, and cutting operations.

[0059] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0060] Example 1

[0061] This embodiment provides a method for preparing artificial quartz products from artificial quartz waste, which is obtained through the following steps:

[0062] (1) Weigh 1 kg of particles with a particle size of d 97 Artificial quartz waste powder with a particle size ≤45μm was added to a powder surface modifier. At 100℃, 7g of a composite modifier (composed of sodium fatty acid phosphate and maleic acid-acrylic acid copolymer, with a mass ratio of 1:1) was added to modify the surface of the artificial quartz waste powder for 10 minutes, resulting in modified artificial quartz waste. The scanning electron microscope image of the modified artificial quartz waste is shown below. Figure 1 As shown.

[0063] (2) Weigh 920g of the above modified artificial quartz waste, 60g of unsaturated resin, and 20g of additives (the mass ratio of methyl ethyl ketone, cobalt water, styrene, and color paste is 2:2:1:1) and wet mix them at room temperature to obtain a uniform mixture (mixing time 20min). The filling amount of artificial quartz waste is 94wt%.

[0064] (3) The mixed materials are subjected to vacuum high-pressure molding and demolding. The curing temperature is 60℃ and the curing time is 3h;

[0065] (4) The solidified artificial stone products are subjected to sawing, polishing, and cutting operations. Impact strength and flexural strength performance tests are also conducted.

[0066] Example 2

[0067] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste. The only difference between this method and Example 1 is that the modifier in step (1) is replaced with hydroxyl silicone oil and maleic acid-acrylic acid copolymer in a mass ratio of 1:1; and the curing temperature in step (3) is 50°C and the curing time is 4 hours.

[0068] Example 3

[0069] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste residue. The only difference between this method and Example 1 is that the amount of modifier added in step (1) is 3g.

[0070] Example 4

[0071] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste residue. The only difference between this method and Example 1 is that the amount of modifier added in step (1) is 10g.

[0072] Example 5

[0073] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste residue. The only difference between this method and Example 1 is that in step (2), 930g of modified artificial quartz waste residue and 50g of unsaturated resin are used, while the rest remain unchanged.

[0074] Comparative Example 1

[0075] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste residue. The only difference between this method and Example 1 is that no modifier is added in step (1).

[0076] Comparative Example 2

[0077] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste residue. The only difference between this method and Example 1 is that the modifier in step (1) is replaced with stearic acid.

[0078] Comparative Example 3

[0079] This embodiment also provides a method for preparing artificial quartz products from artificial quartz waste, which differs from Example 1 only in that the modifier in step (1) is replaced with an aluminate coupling agent.

[0080] Test case

[0081] The oil absorption value and activation index of the modified artificial quartz waste powder obtained in Examples 1-5 and Comparative Examples 1-3 were tested, and the results are shown in Table 1; the mechanical properties of the artificial quartz products were tested, and the results are shown in Table 2.

[0082] Table 1. Results of oil absorption value and activation index tests

[0083] sample Oil absorption value (mL / g) Activation index (%) Example 1 0.20 7.8 Example 2 0.19 5.6 Example 3 0.23 4.5 Example 4 0.18 8.1 Example 5 0.20 7.8 Comparative Example 1 0.28 8.2 Comparative Example 2 0.24 92.3 Comparative Example 3 0.25 96.7

[0084] Table 2 Mechanical property test results

[0085] sample <![CDATA[Impact strength (kJ / m 2 )]]> Bending strength (MPa) Example 1 6.2 47.3 Example 2 6.0 46.8 Example 3 4.7 40.3 Example 4 6.1 47.0 Example 5 5.8 45.2 Comparative Example 1 3.2 31.6

[0086] As can be seen from Table 1, by comparing Example 1 and Comparative Examples 1-3, it can be found that the modified artificial quartz waste residue modified by the modifier used in this application has a significantly lower oil absorption value compared with unmodified artificial quartz waste residue and artificial quartz waste residue modified by conventional modifiers (stearic acid, aluminate, etc.), while maintaining a low activation index range (4.5% to 7.8%).

[0087] As can be seen from Table 2, by comparing Example 1 and Comparative Example 1, it can be found that the artificial quartz products prepared by modifying the artificial quartz waste residue with the modifier used in this application have significantly improved mechanical properties compared with artificial quartz products prepared by unmodified artificial quartz waste residue.

[0088] In summary, the technical solution provided in this application has at least the following advantages:

[0089] (1) It can significantly increase the filling ratio of artificial quartz stone waste. Compared with the existing filling ratio of artificial quartz stone products (92%~93wt%), the filling amount is significantly increased (up to 94-95wt%), thereby achieving the purpose of reducing the amount of unsaturated resin, saving resin, reducing product cost and protecting the environment.

[0090] (2) The modifier molecules used are at least one of hydrophilic silicone oil, sodium salt of fatty acid phosphate and maleic acid-acrylic acid copolymer, and the optimized dosage of the formulation is significantly reduced (0.3-0.8 wt%).

[0091] (3) It can maintain good mechanical properties even with a high filling ratio (the filling ratio of artificial quartz waste reaches 94-95 wt%).

[0092] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A modifier for artificial quartz stone waste, characterized in that, The components include at least one of hydrophilic silicone oil and sodium salt of fatty acid phosphate, and maleic acid-acrylic acid copolymer; the mass ratio of hydrophilic silicone oil to maleic acid-acrylic acid copolymer is 10:1-1:10 or the mass ratio of sodium salt of fatty acid phosphate to maleic acid-acrylic acid copolymer is 10:1-1:10 or the mass ratio of hydrophilic silicone oil, sodium salt of fatty acid phosphate to maleic acid-acrylic acid copolymer is 1-10:1-10:1-10.

2. The modifier according to claim 1, characterized in that, The hydrophilic silicone oil includes at least one of hydroxyl silicone oil, amino silicone oil, and polyether-modified polydimethylsiloxane.

3. The modifier according to claim 1, characterized in that, The sodium salt of fatty acid phosphate includes at least one of sodium oleate phosphate, sodium stearate phosphate, and sodium lauryl phosphate.

4. The application of the modifier as described in claim 1, characterized in that, Used for modifying artificial quartz stone waste.

5. A modified artificial quartz stone waste residue, characterized in that, It is obtained by modifying artificial quartz waste residue with the modifier described in any one of claims 1-3; the amount of the modifier added is 0.1-1.5 wt% of the mass of the artificial quartz waste residue.

6. The modification method for modified artificial quartz waste as described in claim 5, characterized in that, The artificial quartz waste residue is modified with the modifier at 80-120°C for a time not exceeding 60 minutes.

7. The application of the modified artificial quartz waste as described in claim 5 in the preparation of artificial quartz products, characterized in that, The raw materials for the artificial quartz stone products include the modified artificial quartz stone waste as described in claim 5 and unsaturated resin, and also include curing agent, accelerator and diluent; the content of the modified artificial quartz stone waste in the total mass of the modified artificial quartz stone waste and unsaturated resin is not less than 94 wt%.

8. A type of artificial granite product, characterized in that, The raw materials for the artificial quartz stone product include the modified artificial quartz stone waste as described in claim 5 and unsaturated resin, and also include a curing agent, an accelerator, and a diluent; the content of the modified artificial quartz stone waste in the total mass of the modified artificial quartz stone waste and the unsaturated resin is not less than 94 wt%; its preparation method includes the following steps: (1) Mixing the raw materials: Mix the raw materials by wet mixing at room temperature for 10-60 minutes; (2) The material mixed in step (1) is subjected to vacuum high pressure molding: curing temperature 40~80℃, curing time 3~6h; (3) After the artificial stone blocks in step (2) have been formed and solidified, they are sawed, polished and cut.

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