Environmentally friendly zero-silica stone based on bio-based resin and method for its preparation

Abstract

The present application belongs to the technical field of artificial stone, and particularly relates to an environment-friendly zero-silica stone based on bio-based resin and a preparation method thereof.The environment-friendly zero-silica stone according to the present application contains, by weight percentage, 63-70% of zero-silica stone recycling material, 20-25% of amorphous silicon dioxide powder and 8-12% of resin, wherein the resin is composed of unsaturated polyester resin and bio-based resin, and the amount of the bio-based resin is 10-30% of the total weight of the resin.The environment-friendly zero-silica stone uses zero-silica stone recycling material and amorphous silicon dioxide powder as main aggregate fillers, and uses unsaturated polyester resin and bio-based resin as a combined adhesive matrix, so that the curing performance, mechanical strength and economy are considered, and the obtained product has high compactness, stable physicochemical properties and is green and environment-friendly.

Description

Technical Field

[0001] This invention belongs to the field of artificial stone technology, specifically relating to an environmentally friendly zero-silica stone based on bio-based resin and its preparation method. Background Technology

[0002] With the increasing demand for environmentally friendly artificial stone in fields such as building decoration and home countertops, the application of traditional quartz stone is becoming increasingly limited due to the easy generation of silica crystal dust during production and processing.

[0003] To address the problem of silica crystal dust hazards, the market has developed and promoted zero-silica stone, which contains no silica crystals, eliminating the risk of silica crystal dust generation at the source. It combines environmental friendliness, safety, and decorative practicality, and has gradually become the mainstream alternative to quartz stone, with market sales and application scale expanding rapidly.

[0004] With the large-scale production and processing of silica-free stone, the amount of scrap and waste generated in the production, cutting, and shaping processes is increasing. If such waste is directly discarded or disposed of in a simple manner, it will not only waste raw material resources and increase the production costs of enterprises, but also occupy space and cause environmental pollution. There is an urgent need for efficient, economical, harmless treatment and resource reuse methods.

[0005] Currently, the main methods for treating zero-silica waste are conventional landfilling and low-value-added recycling. There is no efficient recycling technology that is adapted to the characteristics of zero-silica raw materials and can be directly recycled for raw material production. Problems such as poor adaptability of recycling processes, inability of recycled materials to meet production requirements, and high recycling costs exist, which restrict the green and closed-loop development of the zero-silica industry. Summary of the Invention

[0006] To address one of the aforementioned problems, this invention proposes an environmentally friendly zero-silica stone material based on bio-based resin and its preparation method. This solution allows zero-silica waste to be directly recycled and reused in zero-silica production after being crushed.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solution: This invention provides an environmentally friendly zero-silica stone material based on bio-based resin. By weight percentage, its raw materials include: 63-70% recycled zero-silica stone material, 20-25% amorphous silica powder, and 8-12% resin. The resin is composed of unsaturated polyester resin and bio-based resin, and the bio-based resin accounts for 10-30% of the total weight of the resin.

[0008] The present invention relates to an environmentally friendly zero-silica stone material based on bio-based resin. It uses recycled zero-silica stone material and amorphous silica powder as the main aggregate fillers, and uses unsaturated polyester resin and bio-based resin as a binder matrix. It takes into account curing performance, mechanical strength and economy. The resulting product has high density, stable physical and chemical properties, and is green and environmentally friendly.

[0009] In some preferred embodiments, the particle size of the zero-silica stone recycled material is composed of zero-silica stone recycled material with a particle size greater than 8 mesh and less than or equal to 6 mesh, zero-silica stone recycled material with a particle size greater than 16 mesh and less than or equal to 8 mesh, zero-silica stone recycled material with a particle size greater than 26 mesh and less than or equal to 16 mesh, zero-silica stone recycled material with a particle size greater than 40 mesh and less than or equal to 40 mesh, and zero-silica stone recycled material with a particle size greater than 70 mesh and less than or equal to 40 mesh. The weight percentage of each component in the total raw material of the environmentally friendly zero-silica stone based on bio-based resin is as follows: zero-silica stone recycled material with a particle size greater than 8 mesh and less than or equal to 6 mesh 14-18%, zero-silica stone recycled material with a particle size greater than 16 mesh and less than or equal to 8 mesh 18-25%, zero-silica stone recycled material with a particle size greater than 26 mesh and less than or equal to 16 mesh 8-13%, zero-silica stone recycled material with a particle size greater than 40 mesh and less than or equal to 26 mesh 5-10%, and zero-silica stone recycled material with a particle size greater than 70 mesh and less than or equal to 40 mesh 5-10%. By properly grading zero-silica recycled stone materials, a dense structure can be formed, resulting in slabs with good impact resistance, impact toughness, and compressive strength.

[0010] In some preferred embodiments, the amorphous silica powder is one or more combinations of glass powder, fused silica powder, and frit powder. The particle size of the amorphous silica powder is 10-80 mesh.

[0011] In some preferred embodiments, the unsaturated polyester resin is an phthalic unsaturated polyester resin. More preferably, the phthalic unsaturated polyester resin is prepared by polycondensation of maleic anhydride, phthalic anhydride, and alcohols as monomers to synthesize an unsaturated polyester, which is then physically blended, dissolved, and diluted with styrene; wherein the weight ratio of styrene: maleic anhydride: phthalic anhydride: alcohols is 30-36:15-18:22-26:25-30. In some specific embodiments, the phthalic unsaturated polyester resin can be 968D general-purpose phthalic unsaturated polyester resin.

[0012] In some preferred embodiments, the bio-based resin comprises a bio-based phthalic unsaturated polyester resin, such as PO-4698-25.

[0013] Furthermore, in some preferred embodiments, the bio-based resin further includes a bio-based polyol resin, which, when combined with a bio-based phthalic unsaturated polyester resin, can further improve the performance of the stone.

[0014] In some preferred embodiments, the bio-based resin is composed of a bio-based phthalic unsaturated polyester resin and a bio-based polyol resin, wherein the mass ratio of the bio-based phthalic unsaturated polyester resin to the bio-based polyol resin is 1-3:1. In some specific embodiments, the bio-based phthalic unsaturated polyester resin PO-4698-25 is compounded with one of the following bio-based polyol resins: LC-450, LC-320, LC-150, LC-160, or LC-170, in a weight ratio of 1:1, 2:1, or 3:1, etc.

[0015] In some preferred embodiments, the raw materials of the bio-based resin-based environmentally friendly zero-silica stone material further include, by weight percentage, 0.1-0.3% curing agent, 0.05-0.1% coupling agent, and 0-1% titanium dioxide. The curing agent can be benzoyl peroxide, etc., and the coupling agent can be a silane coupling agent, such as KH570, KH610, etc. Titanium dioxide is mainly used to adjust the whiteness of the product and can be added as needed.

[0016] A second aspect of the present invention also provides a method for preparing the above-mentioned environmentally friendly zero-silica stone based on bio-based resin, comprising the steps of: Dry mix amorphous silica powder with zero-silica recycled stone material evenly; Add to the resin and mix wet to obtain a uniformly coated mixture; The mixture is fed into a mold and then pressed into shape by vacuum vibration. The environmentally friendly, silica-free stone material based on bio-based resin is obtained through curing, demolding, maintenance, thickness determination, and polishing.

[0017] This invention utilizes a compound system of bio-based resin and conventional unsaturated polyester resin, combined with recycled zero-silica stone materials and amorphous silica powder, to prepare environmentally friendly zero-silica stone, which has the following beneficial effects: 1) It avoids the hazards of crystalline silica dust at the source, resulting in higher occupational safety; 2) The zero-silica scraps and waste generated during the production process are crushed and directly reused as recycled aggregates, which greatly reduces raw material consumption and solid waste emissions, lowers production costs, and realizes resource recycling throughout the entire life cycle of stone production, resulting in outstanding environmental benefits. 3) The amorphous silica powder and recycled material have a reasonable particle size distribution, which can form a dense structure under vacuum vibration molding. The board has excellent hardness, wear resistance and stain resistance, and uniform and stable color. It can be widely used in kitchen countertops, bathroom countertops, decorative boards and other fields, replacing traditional quartz stone and artificial stone.

[0018] 4) The use of bio-based unsaturated polyester resin in combination with conventional resin can effectively increase the proportion of renewable raw materials in the product, reduce dependence on petroleum-based chemical raw materials, reduce carbon emissions throughout the product's life cycle, make the product more in line with low-carbon and sustainable development, and enhance the product's green certification and market competitiveness.

[0019] 5) The synergistic effect of bio-based resin and ordinary unsaturated polyester resin retains the advantages of conventional resins, such as fast curing speed, high bonding strength, and good formability, while improving the compressive strength of the system through bio-based components. Furthermore, the combination of multiple bio-based resins can synergistically improve the strength and toughness of stone.

[0020] 6) The overall preparation process of this invention is highly compatible with existing zero-silica and artificial stone production lines, and can achieve large-scale production without major equipment modifications. Attached Figure Description

[0021] Figure 1 The image shows a stone product obtained in Embodiment 1 of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. Additional aspects and advantages of this invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It should be understood that the following description is merely illustrative and not intended to limit the invention.

[0023] The terms “comprising,” “including,” “containing,” or any other variations thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0024] When equivalents, concentrations, or other values ​​or parameters in this document are expressed as ranges, preferred ranges, or a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0025] The specific embodiments of the present invention will be described in detail below.

[0026] Raw material description: Bio-based phthalic unsaturated polyester resin: Covestro PO-4698-25; Bio-based polyol resins: Dongguan Longchi New Materials LC450, LC-320, LC-160; Unsaturated polyester resin: 968D general-purpose phthalic unsaturated polyester resin, obtained by dehydration condensation of 16.2 parts by weight of maleic anhydride, 24.5 parts by weight of phthalic anhydride, and 27.7 parts by weight of propylene glycol, followed by physical mixing with 34.5 parts by weight of styrene.

[0027] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0028] Example 1 This embodiment provides an environmentally friendly zero-silica stone material, which, according to Table 1, is composed of the following raw materials: 1263g (approximately 66%) of zero-silica stone recycled material, 440g (approximately 23%) of 10-80 mesh glass powder (amorphous silica powder), 195g (approximately 10.19%) of resin, 1.9g (approximately 0.1%) of benzoyl peroxide curing agent, 1g (approximately 0.05%) of KH570 coupling agent, and 12g (approximately 0.63%) of titanium dioxide, totaling 1912.9g.

[0029] The zero-silica stone recycled material consists of 325g of zero-silica stone recycled material with a mesh size greater than 8 and less than or equal to 6, 408g of zero-silica stone recycled material with a mesh size greater than 16 and less than or equal to 8, 225g of zero-silica stone recycled material with a mesh size greater than 26 and less than or equal to 16, 145g of zero-silica stone recycled material with a mesh size greater than 40 and less than or equal to 26, and 160g of zero-silica stone recycled material with a mesh size greater than 70 and less than or equal to 40; the resin consists of 175.5g of 968D phthalic unsaturated polyester resin and 19.5g of bio-based phthalic unsaturated polyester resin PO-4698-25.

[0030] The environmentally friendly zero-silica stone preparation method of this embodiment includes the following steps: 1) Dry mix the glass powder and the zero-silica stone recycled material evenly; 2) Mix unsaturated polyester resin 968D and bio-based resin to obtain a mixed resin solution; 3) Add the dry material obtained in step 1) to the resin liquid obtained in step 2) and mix wet to obtain a uniformly coated mixture; 4) The mixture is fed into the mold, and after the mixture is flattened in the mold frame and vacuumed by a high-frequency vibration press, it is pressed into shape; 5) After curing at 95℃, demolding, and maintenance, the material is then subjected to thickness determination and polishing to obtain the environmentally friendly, silica-free stone material based on bio-based resin. The resulting stone product image is shown below. Figure 1 As shown.

[0031] Example 2 Referring to Table 1, the difference from Example 1 is that the resin is composed of 156g of 968D phthalic unsaturated polyester resin and 39g of bio-based phthalic unsaturated polyester resin PO-4698-25; the rest is the same as in Example 1.

[0032] Example 3 Referring to Table 1, the difference from Example 1 is that the resin is composed of 136.5g of 968D phthalic unsaturated polyester resin and 58.5g of bio-based phthalic unsaturated polyester resin PO-4698-25; the rest is the same as in Example 1.

[0033] Example 4 Referring to Table 1, the difference from Example 1 is that the resin is composed of 156g of 968D phthalic unsaturated polyester resin, 19.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC450; the rest is the same as in Example 1.

[0034] Example 5 Referring to Table 1, the difference from Example 1 is that the resin is composed of 136.5g of 968D phthalic unsaturated polyester resin, 39g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC450; the rest is the same as in Example 1.

[0035] Example 6 Referring to Table 1, the difference from Example 1 is that the resin is composed of 137g of 968D phthalic unsaturated polyester resin, 43.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 14.5g of bio-based polyol resin LC450; the rest is the same as in Example 1.

[0036] Example 7 Referring to Table 1, the difference from Example 1 is that the resin is composed of 156g of 968D phthalic unsaturated polyester resin, 19.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC320; the rest is the same as in Example 1.

[0037] Example 8 Referring to Table 1, the difference from Example 1 is that the resin is composed of 136.5g of 968D phthalic unsaturated polyester resin, 39g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC320; the rest is the same as in Example 1.

[0038] Example 9 Referring to Table 1, the difference from Example 1 is that the resin is composed of 137g of 968D phthalic unsaturated polyester resin, 43.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 14.5g of bio-based polyol resin LC320; the rest is the same as in Example 1.

[0039] Example 10 Referring to Table 1, the difference from Example 1 is that the resin is composed of 156g of 968D phthalic unsaturated polyester resin, 19.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC160; the rest is the same as in Example 1.

[0040] Example 11 Referring to Table 1, the difference from Example 1 is that the resin is composed of 136.5g of 968D phthalic unsaturated polyester resin, 39g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 19.5g of bio-based polyol resin LC160; the rest is the same as in Example 1.

[0041] Example 12 Referring to Table 1, the difference from Example 1 is that the resin is composed of 137g of 968D phthalic unsaturated polyester resin, 43.5g of bio-based phthalic unsaturated polyester resin PO-4698-25, and 14.5g of bio-based polyol resin LC160; the rest is the same as in Example 1.

[0042] Comparative Example 1 Referring to Table 1, the difference from Example 1 is that the resin does not contain bio-based resin; otherwise, it is the same as Example 1.

[0043] Comparative Example 2 Referring to Table 1, the difference from Comparative Example 1 is that the zero-silica stone recycling waste consists only of zero-silica stone recycling material with a mesh size greater than 16 and less than or equal to 8; the rest is the same as in Example 1.

[0044] Table 1. Raw material composition table for each embodiment and comparative example

[0045] The stone materials prepared in each embodiment and comparative example were subjected to performance tests, and the results are shown in Table 2.

[0046] Table 2. Test results of stone performance in each embodiment and comparative example.

[0047] The test results above show that adding 10wt%-30wt% of bio-based phthalic unsaturated polyester resin to traditional phthalic unsaturated polyester resin results in products with performance essentially close to that of traditional resins, meeting the requirements of GB / T 35157-2017 "Resin-based Synthetic Stone Slabs," and improving compressive strength. Furthermore, by adding bio-based polyol resin in combination with bio-based phthalic unsaturated polyester resin, the toughness, impact strength, and curing time of the stone can be further improved. In particular, when bio-based phthalic unsaturated polyester resin PO-4698-25 is combined with bio-based polyol resin LC320, the stone performance is optimal, with impact strength, impact toughness, and compressive strength all superior to that of a single traditional unsaturated polyester resin, and the curing time is also shorter. In addition, the particle size distribution of zero-silica stone recycled material also has a significant impact on the strength and toughness of the stone. Specifically, combining the results of Comparative Example 2 and Comparative Example 1, it can be seen that compared with recycled material of a single particle size, the impact resistance and compressive toughness of the stone are significantly improved by using recycled material with different particle sizes. This may be because the reasonable combination of different particle sizes can form a dense structure under vacuum vibration molding, thereby improving the impact resistance and compressive toughness of the slab.

[0048] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. An environmentally friendly, zero-silica stone material based on bio-based resin, characterized in that, By weight percentage, its raw materials include: 63-70% zero-silica stone recycled material, 20-25% amorphous silica powder, and 8-12% resin, wherein the resin is composed of unsaturated polyester resin and bio-based resin, and the bio-based resin accounts for 10-30% of the total weight of the resin.

2. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 1, characterized in that, The zero-silica stone recycled material comprises zero-silica stone recycled material with particle sizes greater than 8 mesh and less than or equal to 6 mesh, zero-silica stone recycled material with particle sizes greater than 16 mesh and less than or equal to 8 mesh, zero-silica stone recycled material with particle sizes greater than 26 mesh and less than or equal to 16 mesh, zero-silica stone recycled material with particle sizes greater than 40 mesh and less than or equal to 26 mesh, and zero-silica stone recycled material with particle sizes greater than 70 mesh and less than or equal to 40 mesh. The weight percentage of each component in the total raw materials of the bio-based resin-based environmentally friendly zero-silica stone is as follows: 14-18% of the recycled silica stone is between 8 mesh and 6 mesh. 18-25% of the recycled silica stone is between 16 mesh and 8 mesh. 8-13% of zero-silica stone recycled material is between 26 mesh and 16 mesh. 5-10% of zero-silica stone recycled material with a mesh size greater than 40 and less than or equal to 26 mesh. 5-10% of zero-silica stone recycled material with a mesh size greater than 70 and less than or equal to 40.

3. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 1, characterized in that, The amorphous silica powder is one or more of glass powder, fused silica powder, and frit powder, and the particle size of the amorphous silica powder is 10-80 mesh.

4. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 1, characterized in that, The unsaturated polyester resin is an orthophthalic unsaturated polyester resin.

5. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 4, characterized in that, The phthalic unsaturated polyester resin is prepared by polycondensation of maleic anhydride, phthalic anhydride and alcohol as reactants to synthesize unsaturated polyester, and then physically blending, dissolving and diluting the obtained unsaturated polyester with styrene; wherein the weight ratio of styrene: maleic anhydride: phthalic anhydride: alcohol is 30-36:15-18:22-26:25-30.

6. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 1, characterized in that, The bio-based resin includes a bio-based phthalic unsaturated polyester resin.

7. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 6, characterized in that, The bio-based resin also includes bio-based polyol resin.

8. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 7, characterized in that, The bio-based resin is composed of bio-based phthalic unsaturated polyester resin and bio-based polyol resin, wherein the mass ratio of bio-based phthalic unsaturated polyester resin to bio-based polyol resin is 1-3:

1.

9. The environmentally friendly zero-silica stone material based on bio-based resin according to claim 1, characterized in that, According to weight percentage, the raw materials of the bio-based resin-based environmentally friendly zero-silica stone also include 0-0.3% curing agent, 0-0.1% coupling agent, and 0-1% titanium dioxide.

10. A method for preparing stone, used to prepare environmentally friendly zero-silica stone based on bio-based resin as described in any one of claims 1-9, characterized in that, Including the following steps: Dry mix amorphous silica powder with zero-silica recycled stone material evenly; Add to the resin and mix wet to obtain a uniformly coated mixture; The mixture is fed into a mold and then pressed into shape by vacuum vibration. The environmentally friendly, silica-free stone material based on bio-based resin is obtained through curing, demolding, maintenance, thickness determination, and polishing.

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