CN116218119B - Flame-retardant solid surface material and preparation method thereof - Google Patents

Flame-retardant solid surface material and preparation method thereof Download PDF

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CN116218119B
CN116218119B CN202310198879.4A CN202310198879A CN116218119B CN 116218119 B CN116218119 B CN 116218119B CN 202310198879 A CN202310198879 A CN 202310198879A CN 116218119 B CN116218119 B CN 116218119B
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aluminum hydroxide
flame
peroxydicarbonate
surface material
retardant solid
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CN116218119A (en
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赵益方
周海涛
王勇刚
杨代明
陈树华
胥勋奇
朱祖治
潘玫宏
李南生
童银秀
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Guangdong Relang New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses a flame-retardant solid surface material and a preparation method thereof, wherein the flame-retardant solid surface material comprises the following raw materials in parts by weight: 30-40 parts of acrylic resin, 60-80 parts of modified aluminum hydroxide, 0.3-0.5 part of cross-linking agent and 0.5-1 part of peroxidation curing agent, wherein the modified aluminum hydroxide is prepared by reacting hyperbranched polysiloxane grafted beta-cyclodextrin with aluminum hydroxide according to the weight ratio of 1-2:12-16; according to the solid panel, the hyperbranched polysiloxane grafted beta-cyclodextrin modified aluminum hydroxide is added into the acrylic resin, so that the problem that the solid panel is easy to crack is solved, the compatibility between the aluminum hydroxide and the resin is enhanced, the problem that the solid panel is easy to generate gaps and crack is solved, the flame retardant property, the compressive strength and the bending strength of the solid panel are improved, and the hyperbranched polysiloxane chain segment in the hyperbranched polysiloxane grafted beta-cyclodextrin and the aluminum hydroxide are mutually coordinated to play a synergistic flame retardant effect.

Description

Flame-retardant solid surface material and preparation method thereof
Technical Field
The application belongs to the field of building materials, and particularly relates to a flame-retardant solid surface material and a preparation method thereof.
Background
The artificial stone is a polymer composite material which is formed by taking organic polymer materials such as methyl methacrylate (MMA, common name acrylic) and Unsaturated Polyester Resin (UPR) as a matrix, taking natural ore powder and particles as fillers, adding pigments and other auxiliary agents, and carrying out vacuum casting or compression molding.
Aluminum hydroxide is generally used as a filler, is odorless, tasteless and nontoxic white powder, contains crystal water in molecules, is both the filler and the flame retardant in the solid panel, and can produce the artificial stone with semitransparent texture similar to jade due to high refractive index. However, the binding force between acrylic resin (acrylic ester) and aluminum hydroxide is low, so that on one hand, the aluminum hydroxide is easy to run off in the process of preparing and using the solid panel; on the other hand, the resin and the filler have poor compatibility and uneven mixing, and the prepared solid panel is easy to generate gaps and crack; resulting in the produced solid facestock having low flame retardant properties, compressive strength and flexural strength.
Disclosure of Invention
Aiming at the defects in the prior art, the application prepares the flame-retardant solid surface material, and the hyperbranched polysiloxane grafted beta-cyclodextrin modified aluminum hydroxide is added into the acrylic resin to solve the problem that the solid surface material is easy to crack, enhance the compatibility between the aluminum hydroxide and the resin, solve the problem that the solid surface material is easy to crack and improve the flame-retardant property, the compressive strength and the bending strength of the solid surface material, and the hyperbranched polysiloxane chain segment in the hyperbranched polysiloxane grafted beta-cyclodextrin and the aluminum hydroxide are mutually coordinated to play a role in synergistically enhancing the flame retardance.
The application aims to provide a flame-retardant solid surface material, which comprises the following raw materials in parts by weight:
the modified aluminum hydroxide is prepared by reacting hyperbranched polysiloxane grafted beta-cyclodextrin with aluminum hydroxide according to the weight ratio of 1-2:12-16.
According to the application, hyperbranched polysiloxane grafted beta-cyclodextrin is adopted to modify aluminum hydroxide, firstly, hyperbranched polysiloxane chain segments in the hyperbranched polysiloxane grafted beta-cyclodextrin penetrate through the aluminum hydroxide to fill gaps of the aluminum hydroxide, the prepared solid panel has compact structure, the problem that the solid panel is easy to crack is solved, and the compressive strength and the bending strength of the solid panel are improved; secondly, the hyperbranched polysiloxane grafted beta-cyclodextrin is combined with the aluminum hydroxide in a chemical bonding mode, so that the compatibility between the aluminum hydroxide and the resin is enhanced, the problem that a solid panel is easy to generate gaps and crack is solved, and the flame retardant property, the compressive strength and the bending strength of the solid panel are improved; furthermore, the beta-cyclodextrin contains a ring structure, so that the compressive strength and the bending strength of the solid panel can be enhanced; finally, hyperbranched polysiloxane segments in the hyperbranched polysiloxane grafted beta-cyclodextrin and aluminum hydroxide are mutually coordinated to play a role in synergistically enhancing the flame retardance.
Preferably, the flame-retardant solid surface material comprises the following raw materials in parts by weight:
the modified aluminum hydroxide is prepared by reacting hyperbranched polysiloxane grafted beta-cyclodextrin with aluminum hydroxide according to the weight ratio of 1:10.
Preferably, the flame retardant solid facestock further comprises 0.3 to 0.5 parts by weight of magnesium oxide and 0.5 to 1.5 parts by weight of pigment.
More preferably, the flame retardant solid facestock further comprises 0.4 parts by weight of magnesium oxide and 1 part by weight of pigment.
The application further improves the flame retardance of the solid panel by adding magnesium oxide into the solid panel.
Preferably, the particle size of the magnesium oxide is 5-15 nm.
More preferably, the particle size of the magnesium oxide is 10nm.
Preferably, the pigment is at least one selected from carbon black, iron oxide yellow, iron oxide red, iron oxide black and titanium dioxide.
The application further aims at providing a preparation method of acrylic resin, which comprises the following steps:
mixing acrylic monomers, chain transfer agent and solvent, heating to 85-95 ℃, dripping initiator, reacting for 1-1.8 hours, and adding polymerization inhibitor to obtain acrylic resin.
On one hand, the acrylic monomer is adopted to prepare the acrylic resin, so that the prepared acrylic resin molecular chain contains carboxyl, the carboxyl on the acrylic resin molecular chain has hydrogen bond action with the hydroxyl of the hyperbranched polysiloxane grafted beta-cyclodextrin modified aluminum hydroxide and the hydroxyl on the surface of the aluminum hydroxide which does not react completely, the binding force of the acrylic resin and the aluminum hydroxide is enhanced, the problem that the aluminum hydroxide is easy to run off in the preparation and use processes of the solid panel is solved, and the flame retardance of the solid panel is longer; on the other hand, in the solid panel curing process, aluminum hydroxide, magnesium hydroxide and pigment which do not react completely must be kept in a suspension state to avoid deposition layering, if the viscosity value of the acrylic resin is low, the aluminum hydroxide, magnesium hydroxide and pigment which do not react completely are easy to sink to form a layering state, so that uneven mixing of the resin and the aluminum hydroxide, magnesium hydroxide and pigment which do not react completely is caused, gaps are easy to be generated in the manufactured solid panel, and the compressive strength and the bending strength of the manufactured solid panel are reduced; if the viscosity value of the acrylic resin is higher, the proportion of the resin consumed for producing the solid panel to the filler such as strong alumina is increased, more resin is consumed, and the raw material cost is increased. Therefore, in the process of preparing the acrylic resin, the chain transfer agent and the polymerization inhibitor are added to control the molecular weight of the acrylic resin, so that the viscosity of the acrylic resin is controlled, the prepared acrylic resin has a proper viscosity value, the cost is saved, and the entity panel can maintain better compressive strength and bending strength.
Preferably, the acrylic monomer is at least one selected from methyl methacrylate, butyl methacrylate, isobutyl methacrylate, butyl acrylate and isooctyl acrylate.
Preferably, the acrylic monomer is at least one selected from acrylic acid and methacrylic acid.
Preferably, the weight ratio of the acrylic ester monomer to the acrylic acid monomer to the chain transfer agent to the initiator to the polymerization inhibitor is 388-400:8-20:6-10:0.04-0.08:0.05-0.1.
More preferably, the weight ratio of the acrylic monomer to the chain transfer agent to the initiator to the polymerization inhibitor is 392:16:8:0.06:0.08.
Preferably, the chain transfer agent is selected from dodecyl mercaptan.
Preferably, the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisobutyryl peroxide, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, and bis (2-ethylhexyl) peroxydicarbonate.
Preferably, the polymerization inhibitor is at least one selected from hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone.
Preferably, the solvent is selected from toluene.
Preferably, the cross-linking agent is selected from at least one of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate.
Preferably, the peroxygen curing agent is selected from at least one of dibenzoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, pivaloyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1, 3-tetramethylbutyl peroxypivaloate, and pivaloate.
The application also provides a preparation method of the flame-retardant solid surface material, which comprises the following steps:
s1, fully mixing and dissolving hyperbranched polysiloxane grafted beta-cyclodextrin, aluminum hydroxide and a solvent, adding isocyanate and a catalyst, heating to react, and regulating pH to be acidic to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing acrylic resin and a peroxide curing agent, heating, stirring, cooling to room temperature to obtain a prepolymer, adding the modified aluminum hydroxide, the cross-linking agent, the magnesium oxide and the pigment prepared in the step S1, and stirring in vacuum to obtain a mixture;
and S3, pouring the mixture obtained in the step S2 into a mold, heating for solidification, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Preferably, in step S1, the isocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate.
Preferably, in step S1, the catalyst is selected from dibutyltin dilaurate.
Preferably, in step S1, the particle size of the aluminum hydroxide is 150 to 300 mesh.
More preferably, in step S1, the particle size of the aluminum hydroxide is 200 mesh.
Preferably, in step S1, the solvent is selected from mixed solvents with a volume ratio of polar solvent to nonpolar solvent of 1:1-2.
More preferably, in step S1, the solvent is selected from mixed solvents with a volume ratio of polar solvent to nonpolar solvent of 1:1.5.
Preferably, the polar solvent is at least one selected from ethanol, methanol, isopropanol, acetone, dioxane.
More preferably, the polar solvent is selected from dioxane.
Preferably, the nonpolar solvent is selected from at least one of toluene, n-hexane, carbon tetrachloride, dichloroethane.
More preferably, the non-polar solvent is selected from carbon tetrachloride.
Preferably, in step S1, hydrochloric acid is used to adjust the pH.
Preferably, in step S1, the pH is 2 to 6.
Preferably, in step S1, the time for the temperature-raising reaction is 1 to 3 hours.
Preferably, in the step S1, the weight ratio of the catalyst to the hyperbranched polysiloxane grafted beta-cyclodextrin is 0.02-0.05:1.
More preferably, in step S1, the weight ratio of the catalyst to hyperbranched polysiloxane grafted β -cyclodextrin is 0.03:1.
Preferably, in the step S1, the weight ratio of the isocyanate to the hyperbranched polysiloxane grafted beta-cyclodextrin is 0.04-0.1:1.
More preferably, in step S1, the weight ratio of isocyanate to hyperbranched polysiloxane grafted β -cyclodextrin is 0.08:1.
Preferably, in step S2, the temperature is raised to 85 to 90 ℃.
Preferably, in step S2, the stirring time is 30 to 40 minutes.
Preferably, in the step S2, the vacuum degree of the vacuum stirring is-0.08 to-0.1 MPa, and the time is 1 to 2 hours.
Preferably, in the step S3, the temperature of the heating and curing is 80-90 ℃; the time is 4-6 hours.
Detailed Description
In order to better understand the technical solutions of the present application, the following description will clearly and completely describe the technical solutions of the embodiments of the present application in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Hyperbranched polysiloxane grafted beta-cyclodextrin was purchased from the Siamiliaz biotechnology Co.
Polydimethylsiloxane was purchased from vantai silicone rubber limited.
Beta-cyclodextrin was purchased from Shanghai Ala Biochemical technologies Co.
Example 1: and (3) preparing acrylic resin.
350kg of methyl methacrylate, 50kg of butyl methacrylate, 8kg of methacrylic acid, 10kg of dodecyl mercaptan and 300L of toluene are added into a 500L jacketed reaction kettle, stirred, the temperature of the reactants is controlled to be 85 ℃ by using steam and cooling water after mixing, 0.04kg of azodiisobutyronitrile is slowly added for reaction for 1.5 hours, and 0.05kg of hydroquinone is added after the reaction is finished, so that the acrylic resin is obtained. The acrylic resin was measured to have a viscosity of 530cps at 25 ℃.
Example 2: and (3) preparing acrylic resin.
388kg of butyl methacrylate, 20kg of acrylic acid, 6kg of dodecyl mercaptan and 300L of toluene are added into a 500L jacketed reaction kettle, stirred, mixed, steam and cooling water are used for controlling the temperature of reactants to be 95 ℃, 0.08kg of azodiisobutyronitrile is slowly added for reaction for 1.8 hours, and after the reaction is finished, 0.1kg of hydroquinone is added to obtain the acrylic resin. The acrylic resin was measured to have a viscosity of 850cps at 25 ℃.
Example 3: and (3) preparing acrylic resin.
392kg of isooctyl acrylate, 16kg of methacrylic acid, 8kg of dodecyl mercaptan and 300L of toluene are added into a 500L jacketed reaction kettle, stirred, mixed, steam and cooling water are used for controlling the temperature of a reactant to be 90 ℃, 0.06kg of azodiisobutyronitrile is slowly added for reaction for 1.5 hours, and after the reaction is finished, 0.08kg of hydroquinone is added to obtain the acrylic resin. The acrylic resin was measured to have a viscosity of 750cps at 25 ℃.
Example 4: and (3) preparing the flame-retardant solid surface material.
S1, fully mixing and dissolving 10kg of hyperbranched polysiloxane grafted beta-cyclodextrin, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of toluene diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of the acrylic resin prepared in the example 1 and 0.7kg of dibenzoyl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in the step S1, 0.4kg of trimethylolpropane trimethacrylate, 0.4kg of magnesium oxide with the particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Example 5: and (3) preparing the flame-retardant solid surface material.
S1, fully mixing and dissolving 10kg of hyperbranched polysiloxane grafted beta-cyclodextrin, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of diphenylmethane diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of acrylic resin prepared in the example 2 and 0.7kg of diisobutyryl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in the step S1, 0.4kg of ethylene glycol dimethacrylate, 0.4kg of magnesium oxide with the particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Example 6: and (3) preparing the flame-retardant solid surface material.
S1, fully mixing and dissolving 10kg of hyperbranched polysiloxane grafted beta-cyclodextrin, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of dicyclohexylmethane diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of acrylic resin prepared in example 3 and 0.7kg of cumyl peroxyneodecanoate, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in step S1, 0.4kg of trimethylol propyl methacrylate, 0.4kg of magnesia with the particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Comparative example 1: and (3) preparing the flame-retardant solid surface material.
The difference from example 4 is that the hyperbranched polysiloxane grafted beta-cyclodextrin is not used for modifying the aluminum hydroxide, and the specific steps are as follows:
s1, weighing raw materials according to parts by weight, mixing 36kg of acrylic resin prepared in the embodiment 1 and 0.7kg of dibenzoyl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of aluminum hydroxide, 0.4kg of trimethylolpropane trimethacrylate, 0.4kg of magnesium oxide with the particle size of 10nm and 1kg of carbon black, and stirring in vacuum for 1-2 hours under the pressure of-0.08 to-0.1 MPa to obtain a mixture;
s2, pouring the mixture obtained in the step S1 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Comparative example 2: and (3) preparing the flame-retardant solid surface material.
The difference from example 4 is that the modification of aluminium hydroxide with polydimethylsiloxane is carried out as follows:
s1, fully mixing and dissolving 10kg of polydimethylsiloxane, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of toluene diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of the acrylic resin prepared in the example 1 and 0.7kg of dibenzoyl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in the step S1, 0.4kg of trimethylolpropane trimethacrylate, 0.4kg of magnesium oxide with the particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Comparative example 3: and (3) preparing the flame-retardant solid surface material.
The difference from example 4 is that the modification of aluminium hydroxide with beta-cyclodextrin is carried out as follows:
s1, fully mixing and dissolving 10kg of beta-cyclodextrin, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of toluene diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of the acrylic resin prepared in the example 1 and 0.7kg of dibenzoyl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in the step S1, 0.4kg of trimethylolpropane trimethacrylate, 0.4kg of magnesium oxide with the particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
Comparative example 4: and (3) preparing the flame-retardant solid surface material.
The difference from example 4 is that the physical panel is prepared by using acrylic resin with different viscosity values, and the specific steps are as follows:
s1, fully mixing and dissolving 10kg of hyperbranched polysiloxane grafted beta-cyclodextrin, 100kg of 200-mesh aluminum hydroxide and 3L of dioxane/carbon tetrachloride (v/v=1:1.5), adding 0.8kg of toluene diisocyanate and 0.3kg of dibutyltin dilaurate, heating to 30 ℃ for reacting for 2 hours, and regulating the pH to 2-6 by using hydrochloric acid to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing 36kg of acrylic resin with a viscosity value of 400cps and 0.7kg of dibenzoyl peroxide, heating to 85-90 ℃, stirring for 30-40 minutes, cooling to room temperature to obtain a prepolymer, adding 74kg of modified aluminum hydroxide prepared in the step S1, 0.4kg of trimethylolpropane trimethacrylate, 0.4kg of magnesium oxide with a particle size of 10nm and 1kg of carbon black, and stirring for 1-2 hours under vacuum at-0.08-0.1 MPa to obtain a mixture;
s3, pouring the mixture obtained in the step S2 into a mold, solidifying for 4-6 hours at 80-90 ℃, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
And (5) testing performance.
Flame retardancy test: the flame retardancy of the flame retardant solid surface materials prepared in examples 3 to 6 and comparative examples 1 to 4 was measured respectively with reference to GB 8624-2012 "classification of combustion properties of building materials and articles", and the higher the classification, the better the flame retardancy.
Compressive strength test: the compressive strength of the flame retardant solid facestock prepared in examples 3 to 6 and comparative examples 1 to 4 was measured by referring to GB/T1448-2005 method for testing compression Property of fiber reinforced plastics, respectively.
Flexural Strength test: the flexural strength of the flame retardant solid facestock prepared in examples 3 to 6 and comparative examples 1 to 4 was measured by referring to GB/T1449-2005 method for testing flexural Property of fiber reinforced plastics, respectively.
Table 1. Results of performance test of flame retardant solid facestock.
As can be seen from Table 1, the flame retardant solid surface materials prepared in examples 4 to 6 have good flame retardance, compressive strength and bending strength; the comparative example 1 does not adopt hyperbranched polysiloxane grafted beta-cyclodextrin to carry out the reaction on aluminum hydroxide, the compatibility of the aluminum hydroxide and acrylic resin is poor, the binding force is poor, and the flame retardance, the compressive strength and the bending strength are greatly reduced; in the comparative example 2, the polydimethylsiloxane is adopted to modify the aluminum hydroxide, the polydimethylsiloxane and the aluminum hydroxide do not have chemical reaction, the aluminum hydroxide has poor compatibility and poor binding force with the acrylic resin, the polydimethylsiloxane does not contain hyperbranched structures and cyclic structures and cannot penetrate between the aluminum hydroxide, the effect of filling gaps of the aluminum hydroxide cannot be achieved, the compressive strength and the bending strength are greatly reduced, but the polydimethylsiloxane enhances the flame retardance of the aluminum hydroxide to a certain extent, so that the flame retardance is slightly reduced; in the comparative example 3, beta-cyclodextrin is adopted to modify aluminum hydroxide, hydroxyl on a beta-cyclodextrin molecular chain and hydroxyl on the surface of the aluminum hydroxide react through isocyanate, so that the compatibility and the binding force of the aluminum hydroxide and acrylic resin are enhanced, the beta-cyclodextrin contains a cyclic structure, the compressive strength and the bending strength of the solid panel are improved to a certain extent, but the beta-cyclodextrin does not contain hyperbranched structures and cannot penetrate between the aluminum hydroxide, the gap of the aluminum hydroxide cannot be filled, the compressive strength and the bending strength are slightly reduced, hyperbranched polysiloxane is not contained in the comparative example 3, and the flame retardance of the solid panel can be improved to a certain extent, so that the flame retardant property of the prepared solid panel is slightly reduced; in comparative example 4, an acryl resin having a viscosity value of 400cps was used to prepare a solid panel, the viscosity value of the acryl resin was low, and aluminum hydroxide, magnesium hydroxide and pigment, which did not react completely, were easily sunk to form a layered state, resulting in uneven mixing of the resin with aluminum hydroxide, magnesium hydroxide and pigment, which did not react completely, and resulted in easy generation of gaps in the prepared solid panel, and a great decrease in compressive strength and flexural strength of the prepared solid panel.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present application after reading the present specification, and these modifications and variations do not depart from the scope of the application as claimed in the pending claims.

Claims (7)

1. The flame-retardant solid surface material is characterized by comprising the following raw materials in parts by weight:
the viscosity of the acrylic resin is 530cps to 850cps;
the modified aluminum hydroxide is prepared by reacting hyperbranched polysiloxane grafted beta-cyclodextrin with aluminum hydroxide according to the weight ratio of 1-2:12-16;
the preparation method of the acrylic resin comprises the following steps:
mixing acrylic monomers, chain transfer agent and solvent, heating to 85-95 ℃, dripping initiator, reacting for 1-1.8 hours, and adding polymerization inhibitor to obtain acrylic resin;
the preparation method of the flame-retardant solid surface material comprises the following steps:
s1, fully mixing and dissolving hyperbranched polysiloxane grafted beta-cyclodextrin, aluminum hydroxide and a solvent, adding isocyanate and a catalyst, heating to react, and regulating pH to be acidic to obtain modified aluminum hydroxide;
s2, weighing raw materials according to parts by weight, mixing acrylic resin and a peroxide curing agent, heating, stirring, cooling to room temperature to obtain a prepolymer, adding the modified aluminum hydroxide, the cross-linking agent, the magnesium oxide and the pigment prepared in the step S1, and stirring in vacuum to obtain a mixture;
and S3, pouring the mixture obtained in the step S2 into a mold, heating for solidification, cooling to room temperature, and demolding to obtain the flame-retardant solid surface material.
2. The flame retardant solid facestock according to claim 1, wherein the acrylate monomer is selected from at least one of methyl methacrylate, butyl methacrylate, isobutyl methacrylate, butyl acrylate, isooctyl acrylate; the acrylic monomer is at least one selected from acrylic acid and methacrylic acid.
3. The flame retardant solid surface material according to claim 1, wherein the weight ratio of acrylic monomer, chain transfer agent, initiator and polymerization inhibitor is 388-400:8-20:6-10:0.04-0.08:0.05-0.1.
4. The flame retardant solid facestock according to claim 1, wherein the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisobutyryl peroxide, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate.
5. The flame retardant solid facestock according to claim 1, wherein the cross-linking agent is selected from at least one of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol propyl trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethylacrylate.
6. The flame retardant solid facestock according to claim 1, wherein the peroxygen curing agent is selected from at least one of dibenzoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, pivaloyl peroxyneodecanoate, bis-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, t-butyl peroxy2-ethylhexanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1, 3-tetramethylbutyl peroxypivaloate, and tervalyl peroxypivaloate.
7. The flame retardant solid facestock according to claim 1, wherein in step S1, the isocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate; the catalyst is selected from dibutyl tin dilaurate.
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