Unsaturated polyester resin for preventing pattern divergence and preparation method of artificial stone

Abstract

The invention belongs to the technical field of high-molecular polymer materials, and particularly relates to unsaturated polyester resin for preventing pattern divergence and a preparation method of artificial stone. The unsaturated polyester resin is obtained by carrying out mixed esterification reaction on a hydroxyl-terminated liquid polybutadiene monomer grafted and modified by a silane coupling agent, saturated dihydric alcohol, unsaturated binary anhydride and saturated binary anhydride. The preparation method of the artificial stone comprises the following steps: uniformly mixing unsaturated polyester resin with styrene, pentaerythritol tetraacrylate and an accelerant to obtain a resin mixture; uniformly stirring with the aluminum powder, the titanium dioxide, the defoaming agent and the curing agent to obtain a main material; taking out a part of the main material, adding the color paste, uniformly stirring to obtain an auxiliary material, spreading the auxiliary material on the main material to form patterns, and baking, curing and forming to obtain the artificial stone capable of preventing the patterns from dispersing. According to the preparation process, pattern divergence of the artificial stone in the curing process can be prevented, and meanwhile, the artificial stone has excellent strength and toughness.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an unsaturated polyester resin for preventing pattern dispersion and a method for preparing artificial stone. Background Technology

[0002] The main components of artificial stone include resin, aluminum powder (aluminum hydroxide), pigments, and curing agents. Among them, products using unsaturated polyester resin are widely used due to their advantages such as good gloss, rich and vibrant colors, strong processability, good decorative effect, and ease of molding.

[0003] To achieve better decorative effects, artificial stone generally requires pattern design. This involves layering pigmented additives onto a gel-based base material to create specific patterns, followed by baking to solidify the material into slabs. These slabs are then removed from the mold, sanded, and polished to obtain the finished product. However, during the baking and curing process, pigment particles or molecules tend to displace and disperse, gradually forming irregular circles or other shapes, making it difficult to maintain the designed pattern. Therefore, most artificial stone on the market features naturally diffused patterns and textures, making precise control of the patterns difficult and unable to meet diverse market demands. Summary of the Invention

[0004] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a method for preparing an unsaturated polyester resin that prevents pattern dispersion.

[0005] Another object of the present invention is to provide a method for preparing artificial stone that prevents the pattern from scattering.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A method for preparing an unsaturated polyester resin that prevents pattern dispersion includes the following preparation steps:

[0008] (1) Hydroxyl-terminated liquid polybutadiene (HTPB) and hydrogen-containing silane coupling agent were subjected to an addition reaction under the conditions of hydrosilylation catalyst and organic solvent to obtain an unsaturated diol monomer.

[0009] (2) The unsaturated diol monomer from step (1) is mixed with saturated diol, unsaturated dicarboxylic acid anhydride and saturated dicarboxylic acid anhydride for esterification reaction to obtain unsaturated polyester resin that prevents pattern dispersion.

[0010] Furthermore, the number-average molecular weight of the hydroxyl-terminated liquid polybutadiene in step (1) is 1000~3000, and the 1,2-vinyl molar content is ≥20%.

[0011] Further, the hydrogen-containing silane coupling agent mentioned in step (1) is trimethoxysilane or triethoxysilane, and the amount of hydrogen-containing silane coupling agent added is 5 to 15% of the mass of the hydroxyl-terminated liquid polybutadiene.

[0012] Further, the hydrosilylation catalyst in step (1) is chloroplatinic acid or a platinum complex; the organic solvent is toluene or xylene.

[0013] Further, the saturated diol in step (2) is at least one of ethylene glycol, propylene glycol, and diethylene glycol; the unsaturated dicarboxylic acid anhydride is maleic anhydride; and the saturated dicarboxylic acid anhydride is phthalic anhydride.

[0014] Further, in step (2), the mass ratio of the unsaturated diol monomer to the saturated diol, the unsaturated dicarboxylic acid anhydride and the saturated dicarboxylic acid anhydride is 2~10:35~45:20~30:30~50.

[0015] Furthermore, the acid value of the product from the esterification reaction described in step (2) is controlled to be 15~35 mgKOH / g.

[0016] An unsaturated polyester resin that prevents pattern dispersion is prepared by the above method.

[0017] A method for preparing artificial stone that prevents pattern dispersion includes the following preparation steps:

[0018] S1. Mix the above-mentioned unsaturated polyester resin for preventing pattern dispersion with styrene, pentaerythritol tetraacrylate and accelerator to obtain a resin mixture;

[0019] S2. Mix the resin mixture with aluminum powder (aluminum hydroxide) and titanium dioxide evenly, then add defoamer and curing agent in sequence and mix evenly to obtain the main material;

[0020] S3. Take a portion of the main material, add color paste and stir evenly as an auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Vacuum defoaming and flattening. After the material has initially gelled and can no longer flow, bake and solidify to obtain artificial stone that prevents the pattern from spreading.

[0021] Further, in step S1, the amount of styrene used is 20-40% of the mass of the unsaturated polyester resin; the amount of pentaerythritol tetraacrylate used is 0.1-0.5% of the mass of the unsaturated polyester resin.

[0022] Further, the accelerator mentioned in step S1 is cobalt isooctanoate, and the amount of accelerator used is 0.5~1% of the mass of the unsaturated polyester resin.

[0023] Further, in step S2, the amount of aluminum powder used is 180-220% of the mass of the resin mixture; the amount of titanium dioxide used is 0.5-2% of the mass of the resin mixture.

[0024] Furthermore, the defoamer mentioned in step S2 is an organosilicon defoamer, and the amount of defoamer used is 0.5~1% of the mass of the resin mixture.

[0025] Further, the curing agent mentioned in step S2 is methyl ethyl ketone peroxide, and the amount of curing agent used is 0.5~1.5% of the mass of the resin mixture.

[0026] Furthermore, in step S3, the mass of the auxiliary material is 10-30% of the mass of the main material, and the amount of color paste added is 1-5% of the mass of the auxiliary material.

[0027] Furthermore, the baking and curing temperature in step S3 is 60~100℃, and the time is 1~2h.

[0028] An artificial stone that prevents the pattern from scattering is prepared by the above method.

[0029] The principle of this invention is as follows: Through the hydrosilylation reaction of HTPB with a hydrogen-containing silane coupling agent and subsequent esterification reaction, the coupling agent is directionally grafted onto the polyester molecular chain. Compared with conventional free silane coupling agents or silane coupling agents that undergo later free radical copolymerization, this significantly enhances the bonding force between the polyester resin and the pigment particles and aluminum powder, thereby limiting or inhibiting the displacement or dispersion of pigment particles during the baking and curing process, and improving the bonding strength. Furthermore, in the preparation of artificial stone, a tetrafunctional pentaerythritol tetraacrylate is used as a curing and crosslinking agent to increase the crosslinking density, achieving the following effects: 1. A high-density crosslinking network is formed during the curing process, further limiting the migration of pigment particles and preventing diffusion; 2. Since the introduction of long carbon chains in HTPB can reduce the strength and hardness of artificial stone, the tetrafunctional curing and crosslinking agent increases the degree of crosslinking, thereby avoiding the reduction of strength and hardness of artificial stone, while simultaneously improving the toughness of the artificial stone.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] (1) The unsaturated polyester resin and artificial stone of the present invention can prevent the pattern from scattering during the curing process and can accurately control the pattern of artificial stone to meet different market demands.

[0032] (2) The artificial stone obtained by the present invention has excellent strength and toughness. Attached Figure Description

[0033] Figure 1 This is a diagram showing the pattern and appearance of the artificial stone obtained in Example 2.

[0034] Figure 2The image shows the pattern and appearance of the artificial stone obtained in Comparative Example 1. Detailed Implementation

[0035] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0036] Example 1

[0037] (1) HTPB with a number average molecular weight of 2000 and a 1,2-vinyl molar content of 20% was added to toluene and mixed and dissolved with trimethoxysilane at a mass ratio of 100:5. Then, 100 ppm of isopropanol chloroplatinate solution catalyst was added and heated to 80 °C to carry out the addition reaction until the silane reaction was complete. The solvent was removed under reduced pressure to obtain the unsaturated diol monomer.

[0038] (2) The unsaturated diol monomer from step (1) is heated and mixed with ethylene glycol, maleic anhydride and phthalic anhydride in a mass ratio of 5:38:25:45. The mixture is heated to 180~200℃ for esterification until the product acid value is 30mgKOH / g, thus obtaining unsaturated polyester resin.

[0039] (3) Mix 800 parts by weight of the unsaturated polyester resin from step (2) with 200 parts of styrene, 3 parts of pentaerythritol tetraacrylate and 6 parts of cobalt isooctanoate accelerator to obtain a resin mixture.

[0040] (4) Mix the resin mixture from step (3) with 2000 parts aluminum powder (aluminum hydroxide) and 10 parts titanium dioxide evenly, then add 8 parts organosilicon defoamer and 10 parts methyl ethyl ketone peroxide curing agent and mix evenly to obtain the main material.

[0041] (5) Take 500 parts of the main material and add 15 parts of gray pigment paste and stir evenly as auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Push the mold with the material into the vacuum box and vacuum for about 5 minutes to remove air bubbles. After taking it out of the box, further process the pattern to form oblique straight lines. Wait for about 20 minutes. The oblique straight lines remain unchanged. After the material initially gels and cannot flow, push the mold with the material into the baking oven and bake at 80℃ for 1.5 hours to solidify and form. Take it out of the box, demold, grind and polish to obtain artificial stone that prevents the pattern from spreading.

[0042] The artificial stone obtained in this embodiment, tested (JC / T 908-2013), has a flexural strength of 45 MPa and an impact toughness of 6.4 kJ / m. 2 .

[0043] Example 2

[0044] (1) HTPB with a number average molecular weight of 2000 and a 1,2-vinyl molar content of 20% was added to toluene and mixed and dissolved with triethoxysilane at a mass ratio of 100:10. Then, 100 ppm of isopropanol chloroplatinate solution catalyst was added and heated to 80 °C to carry out the addition reaction until the silane reaction was complete. The solvent was removed under reduced pressure to obtain the unsaturated diol monomer.

[0045] (2) The unsaturated diol monomer from step (1) is heated and mixed with ethylene glycol, propylene glycol, maleic anhydride and phthalic anhydride in a mass ratio of 10:20:16:30:30. The mixture is heated to 180~200℃ for esterification until the acid value of the product is 15mgKOH / g, thus obtaining unsaturated polyester resin.

[0046] (3) Mix 750 parts by weight of the unsaturated polyester resin from step (2) with 250 parts of styrene, 4 parts of pentaerythritol tetraacrylate and 8 parts of cobalt isooctanoate accelerator to obtain a resin mixture.

[0047] (4) Mix the resin mixture from step (3) with 2000 parts aluminum powder (aluminum hydroxide) and 15 parts titanium dioxide evenly, then add 6 parts silicone defoamer and 12 parts methyl ethyl ketone peroxide curing agent and mix evenly to obtain the main material.

[0048] (5) Take 600 parts of the main material and add 20 parts of gray pigment paste and stir evenly as auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Push the mold with the material into the vacuum box and vacuum for about 5 minutes to remove air bubbles. After taking it out of the box, further process the pattern to form oblique straight lines. Wait for about 20 minutes. The oblique straight lines remain unchanged. After the material initially gels and cannot flow, push the mold with the material into the baking oven and bake at 80°C for 2 hours to solidify and form. Take it out of the box, demold, grind and polish to obtain artificial stone that prevents the pattern from spreading.

[0049] The artificial stone obtained in this embodiment, tested (JC / T 908-2013), has a flexural strength of 48 MPa and an impact toughness of 8.7 kJ / m. 2 .

[0050] The pattern and appearance of the artificial stone obtained in this embodiment are as follows: Figure 1 As shown. By Figure 1 As can be seen, the pattern is slanted and straight, without any divergence.

[0051] Example 3

[0052] (1) HTPB with a number average molecular weight of 3000 and a 1,2-vinyl molar content of 20% was added to toluene and mixed and dissolved with triethoxysilane at a mass ratio of 100:15. Then, 100 ppm of isopropanol chloroplatinate solution catalyst was added and heated to 80 °C to carry out the addition reaction until the silane reaction was complete. The solvent was removed under reduced pressure to obtain an unsaturated diol monomer.

[0053] (2) The unsaturated diol monomer from step (1) is heated and mixed with ethylene glycol, diethylene glycol, maleic anhydride and phthalic anhydride in a mass ratio of 2:20:25:20:48. The mixture is heated to 180~200℃ for esterification until the product acid value is 20mgKOH / g, thus obtaining unsaturated polyester resin.

[0054] (3) Mix 700 parts by weight of the unsaturated polyester resin from step (2) with 300 parts of styrene, 2 parts of pentaerythritol tetraacrylate and 5 parts of cobalt isooctanoate accelerator to obtain a resin mixture.

[0055] (4) Mix the resin mixture from step (3) with 1800 parts aluminum powder (aluminum hydroxide) and 8 parts titanium dioxide evenly, then add 10 parts silicone defoamer and 15 parts methyl ethyl ketone peroxide curing agent in sequence and mix evenly to obtain the main material.

[0056] (5) Take 700 parts of the main material and add 25 parts of gray pigment paste and stir evenly as auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Push the mold with the material into the vacuum box and vacuum for about 5 minutes to remove air bubbles. After taking it out of the box, further process the pattern to form oblique straight lines. Wait for about 20 minutes. The oblique straight lines remain unchanged. After the material initially gels and cannot flow, push the mold with the material into the baking oven and bake at 80°C for 2 hours to solidify and form. Take it out of the box, demold, grind and polish to obtain artificial stone that prevents the pattern from spreading.

[0057] The artificial stone obtained in this embodiment, tested (JC / T 908-2013), has a flexural strength of 52 MPa and an impact toughness of 5.5 kJ / m. 2 .

[0058] Comparative Example 1

[0059] (1) Ethylene glycol, propylene glycol, maleic anhydride and phthalic anhydride are heated and mixed evenly in a mass ratio of 20:16:30:30. The temperature is then raised to 180~200℃ for esterification until the acid value of the product is 15mgKOH / g, thus obtaining unsaturated polyester resin.

[0060] (2) Mix 750 parts by weight of the unsaturated polyester resin from step (2) with 250 parts of styrene, 10 parts of silane coupling agent KH570 (γ-methacryloyloxypropyltrimethoxysilane), 4 parts of methyl methacrylate and 8 parts of cobalt isooctanoate accelerator to obtain a resin mixture.

[0061] (3) Mix the resin mixture from step (2) with 2000 parts aluminum powder (aluminum hydroxide) and 15 parts titanium dioxide evenly, then add 6 parts organosilicon defoamer and 12 parts methyl ethyl ketone peroxide curing agent and mix evenly to obtain the main material.

[0062] (4) Take 600 parts of the main material and add 20 parts of gray pigment paste and stir evenly as auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Push the mold with the material into the vacuum box and vacuum for about 5 minutes to remove air bubbles. After taking it out of the box, further process the pattern to form oblique straight lines. Wait for about 20 minutes until the material initially gels and can no longer flow. Then push the mold with the material into the baking oven and bake at 80°C for 2 hours to solidify and form. Take it out of the box, demold, grind and polish to obtain artificial stone.

[0063] The artificial stone obtained in this comparative example was tested (JC / T 908-2013) and its flexural strength was 43 MPa, and its impact toughness was 4.9 kJ / m. 2 .

[0064] The pattern and appearance of the artificial stone obtained in this comparative example are as follows: Figure 2 As shown. By Figure 2 As can be seen, the pattern radiates outwards in a diagonal pattern.

[0065] The comparison between Comparative Example 1 and Example 2 shows that the artificial stone pattern prepared using conventional processes is prone to dispersion during the curing and molding process and has low toughness.

[0066] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing an unsaturated polyester resin to prevent pattern dispersion, characterized in that: The preparation steps include the following: (1) Hydroxyl-terminated liquid polybutadiene and hydrogen-containing silane coupling agent are subjected to addition reaction under hydrosilylation catalyst and organic solvent conditions to obtain unsaturated diol monomers. (2) The unsaturated diol monomer from step (1) is mixed with saturated diol, unsaturated dicarboxylic acid anhydride and saturated dicarboxylic acid anhydride for esterification reaction to obtain unsaturated polyester resin that prevents pattern dispersion.

2. The method for preparing an unsaturated polyester resin to prevent pattern dispersion according to claim 1, characterized in that: The number-average molecular weight of the hydroxyl-terminated liquid polybutadiene in step (1) is 1000~3000, and the molar content of 1,2-vinyl is ≥20%; the hydrogen-containing silane coupling agent is trimethoxysilane or triethoxysilane, and the amount of hydrogen-containing silane coupling agent added is 5~15% of the mass of the hydroxyl-terminated liquid polybutadiene; the hydrosilylation catalyst is chloroplatinic acid or platinum complex; and the organic solvent is toluene or xylene.

3. The method for preparing an unsaturated polyester resin to prevent pattern dispersion according to claim 1, characterized in that: In step (2), the saturated diol is at least one of ethylene glycol, propylene glycol, and diethylene glycol; the unsaturated dicarboxylic acid anhydride is maleic anhydride; the saturated dicarboxylic acid anhydride is phthalic anhydride; and the mass ratio of the unsaturated diol monomer to the saturated diol, unsaturated dicarboxylic acid anhydride, and saturated dicarboxylic acid anhydride is 2~10:35~45:20~30:30~50.

4. The method for preparing an unsaturated polyester resin to prevent pattern dispersion according to claim 1, characterized in that: The esterification reaction described in step (2) controls the acid value of the product to be 15~35 mgKOH / g.

5. An unsaturated polyester resin for preventing pattern diffusion, characterized in that: It is prepared by the method described in any one of claims 1 to 4.

6. A method for preparing artificial stone that prevents pattern dispersion, characterized in that: The preparation steps include the following: S1. The unsaturated polyester resin for preventing pattern dispersion as described in claim 5 is mixed evenly with styrene, pentaerythritol tetraacrylate and an accelerator to obtain a resin mixture; S2. Mix the resin mixture with aluminum powder and titanium dioxide evenly, then add defoamer and curing agent in sequence and mix evenly to obtain the main material; S3. Take a portion of the main material, add color paste and stir evenly as an auxiliary material. Pour the main material into the mold and spread it flat. Then spread the auxiliary material on the main material to form a pattern. Vacuum defoaming and flattening. After the material has initially gelled and can no longer flow, bake and solidify to obtain artificial stone that prevents the pattern from spreading.

7. The method for preparing artificial stone to prevent pattern dispersion according to claim 6, characterized in that: In step S1, the amount of styrene used is 20-40% of the mass of the unsaturated polyester resin; the amount of pentaerythritol tetraacrylate used is 0.1-0.5% of the mass of the unsaturated polyester resin; and the accelerator is cobalt isooctanoate, with an amount of 0.5-1% of the mass of the unsaturated polyester resin.

8. The method for preparing artificial stone to prevent pattern dispersion according to claim 6, characterized in that: In step S2, the amount of aluminum powder used is 180-220% of the mass of the resin mixture; the amount of titanium dioxide used is 0.5-2% of the mass of the resin mixture; the defoamer is an organosilicon defoamer, and the amount of defoamer used is 0.5-1% of the mass of the resin mixture; the curing agent is methyl ethyl ketone peroxide, and the amount of curing agent used is 0.5-1.5% of the mass of the resin mixture.

9. The method for preparing artificial stone to prevent pattern dispersion according to claim 6, characterized in that: In step S3, the mass of the auxiliary material is 10-30% of the mass of the main material, and the amount of color paste added is 1-5% of the mass of the auxiliary material; the baking and curing temperature is 60-100℃, and the time is 1-2 hours.

10. An artificial stone that prevents pattern diffusion, characterized in that: It is prepared by the method described in any one of claims 6 to 9.

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