A flame-retardant quartz slab and its preparation method

Abstract

This invention discloses a flame-retardant quartz slab and its preparation method, relating to the field of quartz slab technology. The flame-retardant quartz slab is prepared from raw materials comprising the following parts by weight: 70-120 parts quartz particles, 5-15 parts unsaturated polyester resin, 10-30 parts organophosphorus flame retardant, 2-5 parts silane coupling agent, 0.5-2 parts curing agent, 0.1-0.5 parts accelerator, 2-8 parts inorganic filler, and 0.5-3 parts color paste. This invention uses a novel organophosphorus flame retardant, which, compared to traditional flame retardants, effectively improves the flame retardancy rating of the quartz slab, avoids the release of toxic and harmful gases during combustion, and does not require large-dose addition, overcoming the shortcomings of low efficiency of inorganic flame retardants and the environmental unfriendliness of bromine-based flame retardants.

Description

Technical Field

[0001] This invention relates to the field of quartz slab technology, specifically to a flame-retardant quartz slab and its preparation method. Background Technology

[0002] Quartz slabs, thanks to the natural properties of quartz particles, possess advantages such as high hardness, strong wear resistance, stain and corrosion resistance, and excellent decorative properties, and have been widely used in various fields such as building decoration, furniture manufacturing, and public space decoration. Their core components are quartz particles and unsaturated polyester resin. The resin acts as a binder, giving the slab its molding properties. However, traditional unsaturated polyester resin is a flammable material, easily releasing dense smoke and toxic gases when burning. This makes it difficult for conventional quartz slabs to meet fire safety requirements in terms of flame retardancy.

[0003] In fire scenarios, untreated quartz slabs are easily ignited, and the flames spread rapidly, not only exacerbating the fire but also posing a serious threat to personnel escape and rescue efforts due to the toxic gases released. With continuously improving building safety standards, especially in densely populated areas such as shopping malls, hospitals, and high-rise buildings, stricter requirements have been placed on the flame retardancy rating of decorative materials. The limited flame retardancy of conventional quartz slabs has become a key factor restricting their application.

[0004] To improve the flame retardant properties of quartz slabs, existing technologies mostly employ modification by adding flame retardants. Inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide, while environmentally friendly and low-cost, require large doses to achieve the desired effect. This leads to a decrease in the mechanical properties and toughness of the slab, and also affects its processing, shaping, and surface gloss. Traditional organic flame retardants, such as bromine-based flame retardants, have high flame retardant efficiency, but they produce toxic and harmful substances during combustion, which is inconsistent with environmental trends. Furthermore, they suffer from problems such as easy migration and poor durability, and their flame retardant effect significantly diminishes with long-term use.

[0005] Furthermore, some flame retardants exhibit poor compatibility with the matrix resin of quartz slabs, easily leading to uneven dispersion and agglomeration. This not only fails to effectively exert their flame-retardant effect but also further impacts the overall performance of the slab. Therefore, developing a flame-retardant quartz slab with high flame-retardant efficiency, good environmental performance, strong compatibility with the slab matrix, and the ability to maintain the original mechanical properties and decorative effects of the quartz slab has become a pressing technical challenge in the industry. This is of great significance for expanding the application scenarios of quartz slabs and improving the level of building fire safety. Summary of the Invention

[0006] The purpose of this invention is to address the problems existing in the prior art by providing a flame-retardant quartz slab and its preparation method. This flame-retardant quartz slab exhibits high flame-retardant efficiency, good environmental performance, and strong compatibility with the substrate. It maintains the original high hardness, wear resistance, and decorative properties of quartz slabs while ensuring flame-retardant effects, meeting the fire safety and performance requirements of densely populated areas and other similar scenarios.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a quartz slab with flame-retardant properties, prepared from raw materials comprising the following parts by weight: 70-120 parts quartz particles, 5-15 parts unsaturated polyester resin, 10-30 parts organophosphorus flame retardant, 2-5 parts silane coupling agent, 0.5-2 parts curing agent, 0.1-0.5 parts accelerator, 2-8 parts inorganic filler, and 0.5-3 parts color paste;

[0008] The organophosphorus flame retardant is a compound represented by Formula 1;

[0009] The structure of Equation 1 is as follows: ;

[0010] In Formula 1, R1 is a substituent, and R1 is an alkyl group having 1-5 carbon atoms. , Any one of them;

[0011] * indicates that the link is a dot.

[0012] Furthermore, the quartz particles are composed of 40-70 parts by weight of 40-80 mesh coarse particles and 30-50 parts by weight of 100-200 mesh fine particles.

[0013] Furthermore, the unsaturated polyester resin is 196 unsaturated polyester resin or 191 unsaturated polyester resin.

[0014] Furthermore, the organophosphorus flame retardant is any one of the compounds shown in the following structures:

[0015] ;

[0016] .

[0017] Furthermore, the silane coupling agent is KH550 or KH560.

[0018] Furthermore, the curing agent is one or more of tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide-2-ethylhexanoate, or tert-butyl peroxycarbonate-2-ethylhexyl ester.

[0019] Furthermore, the accelerator is cobalt isooctanoate.

[0020] Furthermore, the inorganic filler is silicon dioxide.

[0021] A method for preparing a flame-retardant quartz slab includes the following steps:

[0022] S1. Mixing: The quartz particles, organophosphorus flame retardant, inorganic filler and silane coupling agent are put into a mixer and mixed at high speed for 15-50 minutes to obtain a mixture. The unsaturated polyester resin, accelerator and color paste are added into the mixture and stirred at low speed for 15-20 minutes to obtain a resin mixture.

[0023] S2. Vacuum stirring: Vacuum the resin mixture, add the curing agent, and stir under vacuum for 5-15 minutes to obtain a flowing slurry;

[0024] S3. Fabrication and Pressing: Pour the slurry into the mold, spread it out, and then perform vacuum vibration pressing; heat and cure the pressed slab at a temperature of 80-120℃ for 30-90 minutes; demold the cured slab, and then perform thickness determination, grinding, and polishing to obtain the quartz slab with flame-retardant properties.

[0025] Furthermore, S1 is performed under a nitrogen atmosphere.

[0026] This invention addresses the issues of insufficient flame retardancy in traditional quartz slabs and performance imbalances in existing flame retardant modification technologies through synergistic formulation of raw materials and coordinated preparation processes. It utilizes a novel organophosphorus flame retardant as its core, exhibiting high flame retardant efficiency and releasing no toxic or harmful gases during combustion, thus avoiding the environmental hazards of bromine-based flame retardants and the drawbacks of requiring large doses of inorganic flame retardants. The combination of quartz particles—40-80 mesh coarse particles and 100-200 mesh fine particles—maintains the original high hardness and wear resistance of the slab while providing a structural basis for the uniform dispersion of the flame retardant. The silane coupling agent effectively enhances the performance of the organophosphorus flame retardant, silica inorganic filler, and 196 / 1... The compatibility of Type 91 unsaturated polyester resin prevents flame retardant agglomeration, ensuring uniform flame retardant effect without affecting the processing and surface gloss of the board. The curing agent, accelerator and resin system work synergistically to form a stable cross-linked structure under curing conditions of 80-120℃. Combined with mixing and vacuum stirring processes under nitrogen protection, the bonding force of each component is further strengthened. Ultimately, it achieves a synergistic unity of flame retardant performance (meeting the fire safety requirements of densely populated places) with mechanical properties and decorative properties. It not only solves the core pain points of traditional boards being flammable and releasing toxic gases when burning, but also overcomes the problems of reduced board toughness, poor processability and reduced flame retardant effect caused by existing flame retardant modifications.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] 1. Superior flame retardancy and environmental friendliness: The new organophosphorus flame retardant is used, which can effectively improve the flame retardancy rating of quartz slabs compared with traditional flame retardants. It can also avoid the release of toxic and harmful gases during combustion, and does not require large doses. It overcomes the shortcomings of low efficiency of inorganic flame retardants and non-environmentally friendly bromine flame retardants.

[0029] 2. Core performance remains unchanged: While enhancing flame retardancy, the original high hardness, wear resistance and decorative properties of quartz slabs can be retained through the compounding of quartz particles and optimization of component compatibility, avoiding problems such as decreased mechanical properties and reduced toughness caused by existing flame retardant modifications.

[0030] 3. Enhanced processing and durability: Utilizing silane coupling agents and specialized processes, the uniformity of flame retardant dispersion in the matrix is ​​improved, reducing agglomeration. At the same time, it solves the problem of easy migration of traditional flame retardants, ensuring the processing and forming effect of the board and the flame retardant stability during long-term use. Attached Figure Description

[0031] Figure 1 This is the NMR spectrum of the organophosphorus flame retardant 1 described in this invention. Detailed Implementation

[0032] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely 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] Preparation Example 1

[0034] Preparation of organophosphorus flame retardant 1:

[0035] ;

[0036] Under nitrogen protection, 5.00 g of compound 1, 2.56 g of compound 2, and 60 ml of dry toluene were added sequentially to the reaction system. After stirring until homogeneous, 3.26 g of sodium tert-butoxide, 0.46 g of tris(dibenzylacetone)dipalladium, and 0.1 g of tri-tert-butylphosphine were added sequentially. After stirring until homogeneous, the mixture was heated to 110 °C and refluxed for 10 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered through silica gel. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. Purification was performed by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent. The eluent containing the target product compound 3 was collected and concentrated to obtain 4.87 g of compound 3. HPLC showed a purity of 99.9%, and mass spectrometry (MS+H) was performed. + 366.

[0037] ;

[0038] Under nitrogen protection, 4.87 g of compound 3, 3.06 g of compound 4, and 60 ml of N,N-dimethylformamide were added sequentially to the reaction system. After stirring until homogeneous, 1.52 g of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride was slowly added, and the mixture was stirred at 35 °C for 12 h. After the reaction was complete, 80 ml of water was added and stirred for 30 min. The mixture was allowed to stand and separated, retaining the organic phase. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated using a rotary evaporator to obtain a crude powder. Purification was performed by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate as the eluent. The eluent containing the target product, organophosphorus flame retardant 1, was collected and concentrated to obtain 5.59 g of organophosphorus flame retardant 1. HPLC showed a purity of 99.9%, and mass spectrometry (MS+H) was performed. + 577, see MRI Figure 1 .

[0039] Preparation Examples 2-4

[0040] In Preparation Examples 2-4, organophosphorus flame retardant 2-organophosphorus flame retardant 4 were prepared sequentially, following the preparation method of Example 1, except that compound 2 was replaced, and the rest remained the same as in Preparation Example 1. See Table 1 for details.

[0041]

[0042] Example 1

[0043] Preparation of a quartz slab with flame-retardant properties:

[0044] 1. Raw material components

[0045] Quartz granules: 90 parts (composed of 50 parts of 40-80 mesh coarse granules and 40 parts of 100-200 mesh fine granules);

[0046] Unsaturated polyester resin: 10 parts (196 unsaturated polyester resin).

[0047] Organophosphorus flame retardant: 20 parts (organophosphorus flame retardant 1 prepared in Preparation Example 1);

[0048] Silane coupling agent: 3 parts (KH550);

[0049] Curing agent: 1 part (tert-butyl peroxide);

[0050] Accelerator: 0.3 parts (cobalt isooctanoate);

[0051] Inorganic filler: 5 parts (silicon dioxide);

[0052] Color paste: 1 part (white color paste).

[0053] 2. Preparation method

[0054] S1. Mixing: Under nitrogen protection, the weighed quartz particles, organophosphorus flame retardant, silica inorganic filler, and KH550 silane coupling agent are sequentially added to a high-speed mixer. The speed is controlled at 1500 r / min, and the mixture is mixed at high speed for 30 minutes to obtain a uniform mixture. Then, 196 unsaturated polyester resin, cobalt isooctanoate accelerator, and white pigment are slowly added to the mixture. The speed is adjusted to 500 r / min, and the mixture is stirred at low speed for 18 minutes to make the resin uniformly coat the solid particles and obtain a stable resin mixture.

[0055] S2. Vacuum stirring: Transfer the above resin mixture to a vacuum mixing tank, start the vacuum system to evacuate to -0.09MPa, maintain the vacuum state and add tert-butyl peroxide curing agent, stir at 80r / min for 10 minutes to fully remove air bubbles in the mixture and obtain a fluid slurry;

[0056] S3. Fabrication and Pressing: The above-mentioned flowing slurry is evenly poured into a steel mold of a preset size, and manually assisted in spreading it. Then it is sent into a vacuum vibration press and vacuum vibration is performed for 3 minutes at a pressure of 0.8MPa and a vibration frequency of 50Hz. The pressed slab is sent into a constant temperature curing oven, and the curing temperature is controlled at 100℃. The curing is completed by holding the temperature for 60 minutes. After curing, the slab is allowed to cool naturally to room temperature. The slab is then demolded from the mold and successively subjected to fixed thickness sanding (thickness controlled at 20mm), fine grinding, and mirror polishing to obtain the quartz slab with flame-retardant properties.

[0057] Examples 2-4

[0058] The preparation of a quartz slab with flame-retardant properties is carried out by referring to the preparation method of Example 1, except that the organophosphorus flame retardant is replaced sequentially with organophosphorus flame retardant 2-organophosphorus flame retardant 4, and the rest is the same as in Example 1.

[0059] Comparative Example 1

[0060] A quartz slab with flame-retardant properties was prepared by referring to the preparation method of Example 1, except that the organophosphorus flame retardant was replaced with: (Commonly used organophosphorus flame retardants), the rest is the same as in Example 1.

[0061] Comparative Example 2

[0062] A quartz slab with flame-retardant properties was prepared by referring to the preparation method of Example 1, except that the organophosphorus flame retardant was replaced with: (Commonly used organophosphorus flame retardants), the rest is the same as in Example 1.

[0063] Comparative Example 3

[0064] The preparation of a quartz slab with flame-retardant properties is carried out by referring to the preparation method of Example 1, except that the organophosphorus flame retardant is replaced with tris(2,6-dimethylphenyl) phosphate (a commonly used organophosphorus flame retardant), and the rest is the same as in Example 1.

[0065] Comparative Example 4

[0066] The preparation of a quartz slab with flame-retardant properties is the same as in Example 1, except that the organophosphorus flame retardant is not added.

[0067] Performance testing:

[0068] Test sample: A quartz slab with flame-retardant properties prepared in the examples and comparative examples.

[0069] 1. The flammability rating of the samples was tested in accordance with GB / T 8624-2012 using the horizontal burning method. The flammability rating was determined according to the standard, and the data are shown in Table 2.

[0070] 2. The oxygen index (LOI) of the test sample was determined according to GB / T 2406.2-2009. The oxygen concentration of the oxygen-nitrogen mixture was adjusted to gradually determine the minimum oxygen concentration required for the sample to maintain combustion. The data are shown in Table 2.

[0071]

[0072] Examples 1-4 used the novel organophosphorus flame retardant of this invention, and all achieved a flammability rating of B1 (flame-retardant) according to GB / T 8624-2012 standard. The oxygen index (LOI) was stable at 34.1%-34.5%, significantly higher than the critical value for flame-retardant materials (LOI≥32%), proving that the novel organophosphorus flame retardant has high flame retardant efficiency and can meet the fire safety requirements of densely populated places. Comparative Examples 1-3 used commonly used organophosphorus flame retardants, and the flammability rating was only B2 (combustible), with an LOI between 28.9%-29.3%, lower than the examples, reflecting the limitation of traditional organophosphorus flame retardants in the flame retardant effect of quartz slab systems. Comparative Example 4 did not add any flame retardant, and the flammability rating was B3 (flammable), with an LOI of only 23.0%, which directly confirms the core role of flame retardants in improving the flame retardant performance of quartz slabs. Overall data comparison shows that the novel organophosphorus flame retardant of the present invention can improve the flame retardant performance of quartz slabs more efficiently than commonly used flame retardants. At the same time, the LOI values ​​of Examples 1-4 fluctuate less, indicating that the novel flame retardant has strong compatibility with the slab matrix and is evenly dispersed, further verifying the rationality and stability of the formulation and process of the present invention.

[0073] 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 quartz slab with flame-retardant properties, characterized in that, It is prepared from the following raw materials in parts by weight: 70-120 parts quartz particles, 5-15 parts unsaturated polyester resin, 10-30 parts organophosphorus flame retardant, 2-5 parts silane coupling agent, 0.5-2 parts curing agent, 0.1-0.5 parts accelerator, 2-8 parts inorganic filler, and 0.5-3 parts color paste. The organophosphorus flame retardant is a compound represented by Formula 1; The structure of Equation 1 is as follows: ; In Formula 1, R1 is a substituent, and R1 is an alkyl group having 1-5 carbon atoms. , Any one of them; * indicates that the link is a dot.

2. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The quartz particles are composed of 40-70 parts by weight of 40-80 mesh coarse particles and 30-50 parts by weight of 100-200 mesh fine particles.

3. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The unsaturated polyester resin is 196 unsaturated polyester resin or 191 unsaturated polyester resin.

4. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The organophosphorus flame retardant is any one of the compounds shown in the following structures: ； 。 5. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The silane coupling agent is KH550 or KH560.

6. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The curing agent is one or more of the following: tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide-2-ethylhexanoate, or tert-butyl peroxycarbonate-2-ethylhexyl ester.

7. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The accelerator is cobalt isooctanoate.

8. A quartz slab with flame-retardant properties according to claim 1, characterized in that, The inorganic filler is silicon dioxide.

9. A method for preparing a flame-retardant quartz slab according to any one of claims 1-8, characterized in that, Includes the following steps: S1. Mixing: The quartz particles, organophosphorus flame retardant, inorganic filler and silane coupling agent are put into a mixer and mixed at high speed for 15-50 minutes to obtain a mixture. The unsaturated polyester resin, accelerator and color paste are added into the mixture and stirred at low speed for 15-20 minutes to obtain a resin mixture. S2. Vacuum stirring: Vacuum the resin mixture, add the curing agent, and stir under vacuum for 5-15 minutes to obtain a flowing slurry; S3. Fabrication and Pressing: Pour the slurry into the mold, spread it out, and then perform vacuum vibration pressing; heat and cure the pressed slab at a temperature of 80-120℃ for 30-90 minutes; demold the cured slab, and then perform thickness determination, grinding, and polishing to obtain the quartz slab with flame-retardant properties.

10. A method for preparing a flame-retardant quartz slab according to claim 9, characterized in that, Step S1 is performed under a nitrogen atmosphere.

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