High-flame-retardant decorative material as well as preparation method and application thereof

Abstract

The invention discloses a high-flame-retardant decorative material as well as a preparation method and application thereof, belongs to the technical field of preparation of decorative materials, and aims to solve the technical problem that the flame retardance and wear resistance of a decorative material in the prior art need to be further improved. The composite polyolefin material comprises the following raw materials in parts by weight: 80-100 parts of composite polyolefin and 10-15 parts of auxiliary materials, a surface modifier which takes siloxane inlaid by silicon-hydrogen bonds and double bonds as a circulating chain segment and takes double bonds as a sealing end is prepared through telomerization reaction, and a surface modifier which takes phosphonitrilic chloride trimer and 2, 4, 6-trihydroxy-1, 3, 5-triazine as a matrix and takes siloxane inlaid by silicon-hydrogen bonds and double bonds as a sealing end is prepared through telomerization reaction. The preparation method comprises the following steps: performing surface modification on a flame-retardant microsphere blank filled with aluminum isopropoxide to obtain a composite flame-retardant microsphere, combining the composite flame-retardant microsphere with flame-retardant polyolefin to obtain composite polyolefin, and mixing, melting and extruding the composite polyolefin and auxiliary materials to obtain the high-flame-retardant decorative material.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of decorative materials, and particularly relates to a highly flame-retardant decorative material, a preparation method thereof, and an application thereof. Background Art

[0002] The development of highly flame-retardant decorative materials has been accompanied by continuous attention to safety. From early flammable materials such as wood and fabric to the application of natural flame retardants later, the flame retardant technology has been gradually improved. Initially, chlorides and phosphates were used to improve the fire resistance of materials, but the effect was limited. After the 20th century, with the progress of chemical technology, synthetic materials began to use a variety of new flame retardants, such as fluorides, phosphorus-based compounds, and siloxanes. These flame retardants effectively improve the fire safety of materials and reduce the release of toxic gases. In addition, environmental protection and non-toxicity have become new requirements for modern flame retardant materials. In recent years, with the improvement of building safety standards, highly flame-retardant decorative materials have been widely used in the fields of architecture, home decoration, and transportation. Generally speaking, the development of highly flame-retardant decorative materials has experienced a technological innovation from basic flame retardancy to high efficiency and environmental protection, and will continue to move forward in a safer and greener direction in the future.

[0003] For example, the prior art CN104847082B discloses a flame-retardant PVC floor, which includes a substrate layer, a decorative layer located above the substrate layer, and a wear-resistant layer located above the decorative layer. The material of the substrate layer includes PVC powder, a flame retardant, and a coupling agent. The decorative layer is a decorative paper treated with melamine. The material of the wear-resistant layer includes PVC powder and a flame retardant, and at least one of the materials of the substrate layer and the wear-resistant layer includes a smoke suppressant. This flame-retardant PVC floor has good flame retardant and smoke suppression effects. However, in the above invention, the flame retardant is added to the UV coating, and after being mixed evenly, it is made into a coating, and the coating is coated on the semi-finished product formed after hot pressing, so as to improve the flame retardant performance of the material. However, the flame retardant used is a small molecule material and has a large polarity difference from the UV coating, resulting in a weak interfacial bonding force with the coating, and ultimately resulting in insufficient wear resistance of the material. Moreover, the flame retardant component of the material only exists on the surface of the material, and it is difficult to prevent the spread of flames during combustion, resulting in the need to further improve the flame retardant performance of the material. Summary of the Invention

[0004] The purpose of the present invention is to provide a highly flame-retardant decorative material, a preparation method thereof, and an application thereof, which are used to solve the technical problem that the flame retardant performance and wear resistance of decorative materials in the prior art need to be further improved.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A highly flame-retardant decorative material, comprising the following raw material components by weight: 80-100 parts of composite polyolefin and 10-15 parts of auxiliary materials; The auxiliary materials are composed of the following raw materials by weight: 5-6 parts of toughening agent, 1-3 parts of antioxidant, 2-3 parts of ultraviolet absorber and 2-3 parts of lubricant; The preparation method of the composite polyolefin comprises the following steps: A1. Add the hybrid polyolefin, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum chloride and N,N-dimethylacetamide into a reaction kettle, raise the temperature of the reaction kettle to 40-60 °C, keep the temperature for reaction for 1-3 h, and perform post-treatment to obtain the flame-retardant polyolefin; A2. Add the flame-retardant polyolefin, flame-retardant microspheres and N,N-dimethylformamide into a reaction kettle and stir, raise the temperature of the reaction kettle to 60-80 °C, add azobisisobutyronitrile into the reaction kettle, keep the temperature for reaction for 2-3 h, and perform post-treatment to obtain the composite polyolefin.

[0006] The reaction equation for preparing the composite polyolefin is:

[0007] In the formula: ; " " represents the flame-retardant microspheres.

[0008] The reaction principle for preparing the modified polyolefin is: under the catalysis of a Lewis acid and heating conditions, the P-H bond on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide preferentially undergoes a P-H addition reaction with the C=N double bond on the hybrid polyolefin. By controlling the dosage of the reactants, a large number of C=C double bond structures are retained on the prepared flame-retardant polyolefin. Finally, through a radical addition reaction, the flame-retardant microspheres are uniformly dispersed inside the flame-retardant polyolefin, thereby obtaining the composite polyolefin.

[0009] Furthermore, the toughening agent is one or both of dioctyl phthalate and dioctyl adipate; the antioxidant is one or both of triphenyl phosphite and dilauryl sulfide; the ultraviolet absorber is 2-hydroxy-4-octyloxybenzophenone; the lubricant is one or more of calcium stearate and polyethylene wax.

[0010] Furthermore, in step A1, the dosage ratio of the hybrid polyolefin, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum chloride and N,N-dimethylacetamide is 8-10 g: 2-3 g: 0.3-0.5 g: 50-54 mL. The post-treatment includes: after the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 60-80 °C, and perform vacuum distillation until no liquid is collected, then obtain the flame-retardant polyolefin; Further, in step A2, the dosage ratio of the flame-retardant polyolefin, flame-retardant microspheres, N,N-dimethylformamide, and azobisisobutyronitrile is 10-12 g: 2-3 g: 40-48 mL: 0.3-0.5 g. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 60-80 °C, and perform vacuum distillation until no liquid is collected, then the composite polyolefin is obtained.

[0011] Further, the preparation method of the hybrid polyolefin includes the following steps: B1. Add phenyl acrylate, 2-vinyl-4,6-diamino-1,3,5-triazine, 2-methylacrolein, and N,N-dimethylformamide to a reaction kettle and stir. Raise the temperature of the reaction kettle to 60-80 °C, add azobisisobutyronitrile to the reaction kettle, and keep the temperature for reaction for 2-3 h. After post-treatment, the modified polyolefin is obtained; B2. Add the modified polyolefin, 4-aminobutyltriethoxysilane, 3-buten-1-amine, triethylamine, and N,N-dimethylformamide to a reaction kettle. After introducing nitrogen protection, raise the temperature of the reaction kettle to 60-80 °C, and keep the temperature for reaction for 40-60 min. After post-treatment, the hybrid polyolefin is obtained.

[0012] The reaction equation for preparing the hybrid polyolefin is:

[0013] In the formula: ; ; .

[0014] The reaction principle for preparing the hybrid polyolefin is: under the catalysis of a radical initiator and high temperature, phenyl acrylate, 2-vinyl-4,6-diamino-1,3,5-triazine, and 2-methylacrolein undergo a radical addition reaction to form a long-chain structure, and the modified polyolefin is obtained. The nitrogen atom of the amino group on 4-aminobutyltriethoxysilane and 3-buten-1-amine uses the lone pair of electrons as a nucleophile to attack the positively charged carbonyl carbon in the aldehyde group of the modified polyolefin to form a tetrahedral intermediate. Subsequently, this intermediate completes dehydration by eliminating a molecule of water to generate a stable conjugated carbon-nitrogen double bond structure, thereby obtaining the hybrid polyolefin.

[0015] Further, in step B1, the dosage ratio of phenyl acrylate, 2-vinyl-4,6-diamino-1,3,5-triazine, 2-methylacrolein, N,N-dimethylformamide and azobisisobutyronitrile is 8-10 g: 2-3 g: 3-4 g: 60-64 mL: 0.5-0.8 g. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 60-80 °C, and distill under reduced pressure until no liquid is collected, then a modified polyolefin is obtained; Further, in step B2, the dosage ratio of the modified polyolefin, 4-aminobutyltriethoxysilane, 3-buten-1-amine, triethylamine and N,N-dimethylformamide is 8-12 g: 6-8 g: 1-2 g: 0.4-0.6 g: 80-84 mL. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 60-80 °C, and distill under reduced pressure until no liquid is collected, then a hybrid polyolefin is obtained.

[0016] Further, the preparation method of the flame retardant microspheres includes the following steps: C1. Add hexachlorocyclotriphosphazene and chloroform into a reaction kettle, ultrasonically disperse for 15-20 min, then add 2,4,6-trihydroxy-1,3,5-triazine to the reaction kettle, continue ultrasonic treatment for 10-15 min, and under ultrasonic conditions, slowly dropwise add triethylamine to the reaction kettle. After ultrasonic dropwise addition for 2-3 h, continue to add aluminum isopropoxide, and obtain a flame retardant microsphere blank after post-treatment; C2. Add the flame retardant microsphere blank, surface modifier and N,N-dimethylformamide into a reaction kettle. After the reaction kettle is protected by nitrogen, add tris(pentafluorophenyl)borane to the reaction kettle and raise the temperature of the reaction kettle to 80-100 °C, keep the temperature for reaction for 60-80 min, and obtain the flame retardant microspheres after post-treatment.

[0017] The reaction principle for preparing the flame retardant microspheres is as follows: under the catalysis of triethylamine, the hydroxyl groups on 2,4,6-trihydroxy-1,3,5-triazine react with the phosphorus-chlorine bonds on hexachlorocyclotriphosphazene, form a spatial spherical structure under ultrasonic conditions and are modified by aluminum isopropoxide to obtain a flame retardant microsphere precursor, and finally obtain the flame retardant microspheres through the modification of the surface modifier.

[0018] Further, in step C1, the dosage ratio of hexachlorocyclotriphosphazene, chloroform, 2,4,6-trihydroxy-1,3,5-triazine, triethylamine and aluminum isopropoxide is 3-4 g: 40-60 mL: 1-2 g: 0.3-0.4 g: 0.5-0.8 g. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, filter the reaction solution to collect the filter cake. After washing the precipitate 3-5 times with absolute ethanol and deionized water, transfer the filter cake to a drying oven at 60 °C and vacuum dry it to constant weight to obtain the flame retardant microsphere blank. Further, in step C2, the dosage ratio of the flame retardant microsphere blank, surface modifier, N,N-dimethylformamide and tris(pentafluorophenyl)borane is 4-5 g: 1-2 g: 20-24 mL: 0.3-0.5 g. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, filter the reaction solution to collect the filter cake. After washing the precipitate 3-5 times with absolute ethanol and deionized water, transfer the filter cake to a drying oven at 60 °C and vacuum dry it to constant weight to obtain the flame retardant microspheres.

[0019] Further, the preparation method of the surface modifier is as follows: Add methylhydrogen polysiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and ether into the reaction kettle and stir. After stirring at room temperature for 15-20 min, add 98.0%wt concentrated sulfuric acid into the reaction kettle and stir. After stirring at room temperature for 8-10 h, add sodium bicarbonate powder into the reaction kettle and adjust the system pH = 8-9. The surface modifier is obtained after post-treatment.

[0020] The reaction principle for preparing the surface modifier is as follows: Under the catalysis of sulfuric acid, methylhydrogen polysiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane undergo telomerization reaction, thereby preparing a surface modifier with active silicon-hydrogen structure and active double bond structure.

[0021] Further, the dosage ratio of methylhydrogen polysiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane, ether and 98.0%wt concentrated sulfuric acid is 6-8 g: 7-9 g: 2-3 g: 50-80 mL: 9-10 mL. The post-treatment includes: after the reaction is completed, when the temperature of the reaction kettle drops to room temperature, transfer the reaction solution to a rotary evaporator. Raise the temperature of the rotary evaporator to 60-80 °C and distill under reduced pressure until no liquid is collected to obtain the surface modifier.

[0022] The present invention also provides a method for preparing a highly flame-retardant decorative material, which includes the following steps: adding composite polyolefin and auxiliary materials into a twin-screw extruder, melt-extruding, and obtaining the highly flame-retardant decorative material after natural curing.

[0023] Further, the temperatures of the eight temperature zones of the twin-screw extruder from the feed port towards the discharge port are 170°C, 185, 185°C, 200°C, 200°C, 210°C, 210°C in sequence. The main machine speed of the twin-screw extruder is 120 - 160 rpm, and the pressure is 80 - 120 bar.

[0024] The present invention also provides an application of a highly flame-retardant decorative material, applying the highly flame-retardant decorative material prepared by a method for preparing a highly flame-retardant decorative material to the preparation of decorative materials.

[0025] The present invention has the following beneficial effects: 1. The flame-retardant microspheres based on hexachlorocyclotriphosphazene and triazine ring prepared by the present invention decompose and release nitrogen-containing free radicals at high temperatures, capture active free radicals in the combustion chain reaction through the gas-phase quenching effect, and inhibit flame propagation. At the same time, the aluminum isopropoxide filler in the microspheres is dehydrated by heat to generate alumina, which delays the thermal decomposition of the material by absorbing heat and reducing the temperature, and forms a dense ceramicized protective layer in the condensed phase to isolate oxygen and heat. Secondly, the silicon-hydrogen bond and double-bond-embedded siloxane structure in the surface modifier crosslink to form a three-dimensional network during combustion, synergistically enhancing the physical isolation effect with the carbonized layer on the surface of the microspheres. At the same time, the silica generated by the pyrolysis of the siloxane further strengthens the stability of the carbon layer. The thermal stability of the triazine ring in the modified polyolefin inhibits the initial decomposition of the matrix, and the introduced phosphoric acid structure releases phosphorus-oxygen free radicals in the gas phase through phosphorus-hydrogen addition, and captures combustion free radicals in cooperation with the carbon-nitrogen double bond. The crosslinked network formed by aldehyde-amine condensation promotes the increase in melt viscosity and reduces the dripping phenomenon. Finally, the flame-retardant microspheres are uniformly dispersed in the polyolefin matrix through free radical addition reaction. When combustion occurs, the siloxane-ceramic composite layer on the surface isolates the external heat source, the phosphorus-nitrogen system in the middle layer synergistically provides flame retardancy, and the internal crosslinked network delays thermal decomposition, achieving a significant improvement in the flame retardant performance of the material.

[0026] 2. In the surface modifier prepared by the present invention, the siloxane segments with embedded silicon-hydrogen bonds and double bonds form a crosslinked network through telomerization reaction, constructing a three-dimensional rigid and tough framework on the matrix surface. This not only enhances the surface hardness to resist friction and wear, but also buffers external force impacts through elastic deformation. Secondly, the flame-retardant microspheres are based on hexachlorocyclotriphosphazene and triazine rings, and their rigid heteroaromatic ring structures are strengthened by filling with aluminum isopropoxide. After uniform dispersion, a filling structure is formed, which acts as a rigid support point in the matrix to inhibit crack propagation. The triazine rings introduced into the modified polyolefin strengthen the molecular chain rigidity through covalent bonds, and the siloxane structure formed by aldehyde-amine condensation further enhances the intermolecular interaction through hydrogen bonds and van der Waals forces, forming a dense and ordered arrangement, improving the cohesive energy of the material. The chain extension reaction prolongs the molecular chain and increases the entanglement density, enabling the material to absorb energy through molecular chain slippage and orientation when impacted, avoiding brittle fracture. Finally, the melt extrusion process promotes the formation of a dispersed structure between the flame-retardant microspheres and the polyolefin matrix. The dense crosslinked network on the surface resists wear, and the internal microsphere-long chain interpenetrating network disperses the impact stress, achieving a synergistic improvement in wear resistance and impact resistance.

[0027] 3. In the surface modifier prepared by the present invention, the siloxane segments with embedded silicon-hydrogen bonds and double bonds form a crosslinked network through telomerization reaction, forming a dense protective layer on the material surface. The silicon-oxygen bonds in its siloxane structure have strong ultraviolet absorption ability, thus converting high-energy ultraviolet rays into heat energy for dissipation. After the aluminum isopropoxide filler on the microsphere surface is excited by ultraviolet rays, the light energy is converted into lattice heat energy through lattice vibration, thereby improving the ultraviolet resistance of the material. The covalent crosslinked network formed by the triazine ring addition reaction in the modified polyolefin enhances the rigid arrangement of the molecular chains. The introduced siloxane structure forms hydrogen bond interactions with the carbon-nitrogen double bonds, and the phosphate groups introduced by phosphine-hydrogen addition participate in free radical capture, thereby reducing the ultraviolet penetration depth. The flame-retardant microspheres are chemically bonded to the polyolefin through free radical addition of the surface double bonds, realizing uniform dispersion of the microspheres in the matrix, thus forming a surface silicon oxide-aluminum oxide composite layer that preferentially absorbs / scatters ultraviolet rays, a middle layer where the triazine ring and phosphate structure cooperate to capture residual ultraviolet rays, and an internal crosslinked network that reduces the ultraviolet penetration depth through molecular chain rigidity, ultimately significantly improving the ultraviolet resistance of the material. Detailed Embodiments

[0028] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] The methyl hydrogen polysiloxane used in the present invention was purchased from Anhui Mingyi Silicon Industry Co., Ltd., and the product number is MY202 high hydrogen content polysiloxane; the calcium stearate used in the present invention was purchased from Tianjin Sino-US Biochemical Technology Co., Ltd., and the product number is C-08652+500g.

[0030] Example 1 This example provides a preparation method of flame retardant microspheres for preparing high flame retardant decorative materials, including the following preparation methods: Step I: Prepare the surface modifier Weigh: 60.0 g of methyl hydrogen polysiloxane, 70.0 g of 1,3,5,7-tetraethenyl-1,3,5,7-tetramethylcyclotetrasiloxane, 20.0 g of 1,3-dimethyl-1,1,3,3-tetraethenyldisiloxane and 500.0 mL of ether and add them to the reaction kettle for stirring. After stirring at room temperature for 15 min, add 90.0 mL of 98.0% wt concentrated sulfuric acid to the reaction kettle and stir. After stirring at room temperature for 8 h, add sodium bicarbonate powder to the reaction kettle to adjust the system pH = 8. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 60 °C, and distill under reduced pressure until no liquid is collected, then obtain the surface modifier.

[0031] Step II: Prepare the flame retardant microsphere blank Weigh: 30.0 g of hexachlorocyclotriphosphazene and 400.0 mL of chloroform and add them to the reaction kettle. After ultrasonic dispersion for 15 min, add 10.0 g of 2,4,6-trihydroxy-1,3,5-triazine to the reaction kettle, continue ultrasonic for 10 min, and then slowly add 3.0 g of triethylamine dropwise to the reaction kettle under ultrasonic conditions. After ultrasonic dropping for 2 h, continue to add 5.0 g of aluminum isopropoxide. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution to collect the filter cake, wash the precipitate 3 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight, then obtain the flame retardant microsphere blank.

[0032] Step III: Prepare the flame retardant microspheres Weigh: 40.0 g of flame retardant microsphere blank, 10.0 g of surface modifier and 200.0 mL of N,N-dimethylformamide and add them to the reaction kettle. After the reaction kettle is protected by nitrogen, add 3.0 g of tris(pentafluorophenyl)borane to the reaction kettle and raise the temperature of the reaction kettle to 80 °C, keep the temperature for reaction for 60 min. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution to collect the filter cake, wash the precipitate 3 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight, then obtain the flame retardant microspheres.

[0033] Example 2 This embodiment provides a preparation method of flame-retardant microspheres for preparing high-flame-retardant decorative materials, including the following preparation methods: Step Ⅰ. Prepare the surface modifier Weigh: 80.0 g of methylhydrogen polysiloxane, 90.0 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 30.0 g of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and 800.0 mL of ether and add them to the reaction kettle for stirring. After stirring at room temperature for 20 min, add 100.0 mL of 98.0%wt concentrated sulfuric acid to the reaction kettle for stirring. After stirring at room temperature for 10 h, add sodium bicarbonate powder to the reaction kettle to adjust the system pH = 9. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 80 °C, and distill under reduced pressure until no liquid is collected, then obtain the surface modifier.

[0034] Step Ⅱ. Prepare the flame-retardant microsphere blank Weigh: 40.0 g of hexachlorocyclotriphosphazene and 600.0 mL of chloroform and add them to the reaction kettle. After ultrasonic dispersion for 20 min, add 20.0 g of 2,4,6-trihydroxy-1,3,5-triazine to the reaction kettle, continue ultrasonic treatment for 15 min, and then slowly dropwise add 4.0 g of triethylamine to the reaction kettle under ultrasonic conditions. After ultrasonic dropping for 3 h, continue to add 8.0 g of aluminum isopropoxide. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution by suction to collect the filter cake, wash the precipitate 5 times with absolute ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight, and then obtain the flame-retardant microsphere blank.

[0035] Step Ⅲ. Prepare the flame-retardant microspheres Weigh: 50.0 g of flame-retardant microsphere blanks, 20.0 g of surface modifier and 240.0 mL of N,N-dimethylformamide and add them to the reaction kettle. After the reaction kettle is protected by nitrogen, add 5.0 g of tris(pentafluorophenyl)borane to the reaction kettle and raise the temperature of the reaction kettle to 100 °C, keep the temperature for reaction for 80 min. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution by suction to collect the filter cake, wash the precipitate 5 times with absolute ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight, and then obtain the flame-retardant microspheres.

[0036] Example 3 This embodiment provides a preparation method of flame-retardant microspheres for preparing high-flame-retardant decorative materials, including the following preparation methods: Step Ⅰ. Prepare the surface modifier Weigh: 72.0 g of methyl hydrogen polysiloxane, 84.0 g of 1,3,5,7 - tetravinyl - 1,3,5,7 - tetramethylcyclotetrasiloxane, 24.0 g of 1,3 - dimethyl - 1,1,3,3 - tetravinyldisiloxane and 720.0 mL of ether and add them to a reaction kettle for stirring. After stirring at room temperature for 18 min, add 96.0 mL of 98.0% wt concentrated sulfuric acid to the reaction kettle for stirring. After stirring at room temperature for 9 h, add sodium bicarbonate powder to the reaction kettle and adjust the pH of the system to 9. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 70 °C, and distill under reduced pressure until no liquid is collected to obtain a surface modifier.

[0037] Step II: Preparation of flame - retardant microsphere blanks Weigh: 36.0 g of hexachlorocyclotriphosphazene and 540.0 mL of chloroform and add them to a reaction kettle. After ultrasonic dispersion for 18 min, add 16.0 g of 2,4,6 - trihydroxy - 1,3,5 - triazine to the reaction kettle. After continuing ultrasonic treatment for 12 min, under ultrasonic conditions, slowly drop 3.6 g of triethylamine into the reaction kettle. After ultrasonic dropping for 3 h, continue to add 7.2 g of aluminum isopropoxide. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution by suction to collect the filter cake, wash the precipitate 4 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight to obtain flame - retardant microsphere blanks.

[0038] Step III: Preparation of flame - retardant microspheres Weigh: 48.0 g of flame - retardant microsphere blanks, 16.0 g of surface modifier and 210.0 mL of N,N - dimethylformamide and add them to a reaction kettle. After the reaction kettle is protected by nitrogen, add 4.0 g of tris(pentafluorophenyl)borane to the reaction kettle and raise the temperature of the reaction kettle to 90 °C, and keep the temperature for reaction for 70 min. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution by suction to collect the filter cake, wash the precipitate 4 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 60 °C for vacuum drying to constant weight to obtain flame - retardant microspheres.

[0039] Example 4 This example provides a preparation method of a composite polyolefin for preparing a high - flame - retardant decorative material, including the following preparation methods: Step ①: Preparation of modified polyolefin Weigh: 80.0 g of phenyl acrylate, 20.0 g of 2-vinyl-4,6-diamino-1,3,5-triazine, 30.0 g of 2-methylacrolein and 600.0 mL of N,N-dimethylformamide were added to a reaction kettle and stirred. The temperature of the reaction kettle was raised to 60 °C, and 5.0 g of azobisisobutyronitrile was added to the reaction kettle. After holding the reaction for 2 h, after the reaction was completed and the temperature of the reaction kettle was lowered to room temperature, the reaction solution was transferred to a rotary evaporator. The temperature of the rotary evaporator was raised to 60 °C, and after vacuum distillation until no liquid was collected, a modified polyolefin was obtained.

[0040] Step ②, Preparation of hybrid polyolefin Weigh: 80.0 g of modified polyolefin, 60.0 g of 4-aminobutyltriethoxysilane, 10.0 g of 3-buten-1-amine, 4.0 g of triethylamine and 800.0 mL of N,N-dimethylformamide were added to a reaction kettle. After purging with nitrogen, the temperature of the reaction kettle was raised to 60 °C, and the reaction was held for 40 min. After the reaction was completed and the temperature of the reaction kettle was lowered to room temperature, the reaction solution was transferred to a rotary evaporator. The temperature of the rotary evaporator was raised to 60 °C, and after vacuum distillation until no liquid was collected, a hybrid polyolefin was obtained.

[0041] Step ③, Preparation of flame-retardant polyolefin Weigh: 80.0 g of hybrid polyolefin, 20.0 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3.0 g of aluminum chloride and 500.0 mL of N,N-dimethylacetamide were added to a reaction kettle. The temperature of the reaction kettle was raised to 40 °C, and the reaction was held for 1 h. After the reaction was completed and the temperature of the reaction kettle was lowered to room temperature, the reaction solution was transferred to a rotary evaporator. The temperature of the rotary evaporator was raised to 60 °C, and after vacuum distillation until no liquid was collected, a flame-retardant polyolefin was obtained.

[0042] Step ④, Preparation of composite polyolefin Weigh: 100.0 g of flame-retardant polyolefin, 20.0 g of the flame-retardant microspheres prepared in Example 1 and 400.0 mL of N,N-dimethylformamide were added to a reaction kettle and stirred. The temperature of the reaction kettle was raised to 60 °C, and 3.0 g of azobisisobutyronitrile was added to the reaction kettle. After holding the reaction for 2 h, after the reaction was completed and the temperature of the reaction kettle was lowered to room temperature, the reaction solution was transferred to a rotary evaporator. The temperature of the rotary evaporator was raised to 60 °C, and after vacuum distillation until no liquid was collected, a composite polyolefin was obtained.

[0043] Example 5 This example provides a preparation method of a composite polyolefin for preparing a high flame-retardant decorative material, including the following preparation methods: Step ①, Preparation of modified polyolefin Weigh: 100.0 g of phenyl acrylate, 30.0 g of 2-vinyl-4,6-diamino-1,3,5-triazine, 40.0 g of 2-methylacrolein and 640.0 mL of N,N-dimethylformamide and add them to a reaction kettle for stirring. The temperature of the reaction kettle is raised to 80 °C, 8.0 g of azobisisobutyronitrile is added to the reaction kettle, and the reaction is carried out under heat preservation for 3 h. After the reaction is completed, when the temperature of the reaction kettle is lowered to room temperature, the reaction solution is transferred to a rotary evaporator. The temperature of the rotary evaporator is raised to 80 °C, and vacuum distillation is carried out until no liquid is collected, and then modified polyolefin is obtained.

[0044] Step ②, Preparation of hybrid polyolefin Weigh: 120.0 g of modified polyolefin, 80.0 g of 4-aminobutyltriethoxysilane, 20.0 g of 3-buten-1-amine, 6.0 g of triethylamine and 840.0 mL of N,N-dimethylformamide and add them to a reaction kettle. After introducing nitrogen protection, the temperature of the reaction kettle is raised to 80 °C, and the reaction is carried out under heat preservation for 60 min. After the reaction is completed, when the temperature of the reaction kettle is lowered to room temperature, the reaction solution is transferred to a rotary evaporator. The temperature of the rotary evaporator is raised to 80 °C, and vacuum distillation is carried out until no liquid is collected, and then hybrid polyolefin is obtained.

[0045] Step ③, Preparation of flame-retardant polyolefin Weigh: 100.0 g of hybrid polyolefin, 30.0 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5.0 g of aluminum chloride and 540.0 mL of N,N-dimethylacetamide and add them to a reaction kettle. The temperature of the reaction kettle is raised to 60 °C, and the reaction is carried out under heat preservation for 3 h. After the reaction is completed, when the temperature of the reaction kettle is lowered to room temperature, the reaction solution is transferred to a rotary evaporator. The temperature of the rotary evaporator is raised to 80 °C, and vacuum distillation is carried out until no liquid is collected, and then flame-retardant polyolefin is obtained.

[0046] Step ④, Preparation of composite polyolefin Weigh: 120.0 g of flame-retardant polyolefin, 30.0 g of flame-retardant microspheres prepared in Example 2 and 480.0 mL of N,N-dimethylformamide and add them to a reaction kettle for stirring. The temperature of the reaction kettle is raised to 60 - 80 °C, 5.0 g of azobisisobutyronitrile is added to the reaction kettle, and the reaction is carried out under heat preservation for 3 h. After the reaction is completed, when the temperature of the reaction kettle is lowered to room temperature, the reaction solution is transferred to a rotary evaporator. The temperature of the rotary evaporator is raised to 80 °C, and vacuum distillation is carried out until no liquid is collected, and then composite polyolefin is obtained.

[0047] Example 6 This example provides a preparation method of composite polyolefin for preparing a high flame-retardant decorative material, including the following preparation methods: Step ①, Preparation of modified polyolefin Weigh: 96.0 g of phenyl acrylate, 24.0 g of 2-vinyl-4,6-diamino-1,3,5-triazine, 36.0 g of 2-methylacrolein and 640.0 mL of N,N-dimethylformamide and add them to a reaction kettle for stirring. Raise the temperature of the reaction kettle to 70 °C, add 6.0 g of azobisisobutyronitrile to the reaction kettle, keep the temperature for reaction for 3 h. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 70 °C, and distill under reduced pressure until no liquid is collected, then obtain the modified polyolefin.

[0048] Step ②, prepare hybrid polyolefin Weigh: 100.0 g of modified polyolefin, 64.0 g of 4-aminobutyltriethoxysilane, 16.0 g of 3-buten-1-amine, 5.0 g of triethylamine and 810.0 mL of N,N-dimethylformamide and add them to a reaction kettle. After introducing nitrogen protection, raise the temperature of the reaction kettle to 70 °C, keep the temperature for reaction for 50 min. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 70 °C, and distill under reduced pressure until no liquid is collected, then obtain the hybrid polyolefin.

[0049] Step ③, prepare flame-retardant polyolefin Weigh: 90.0 g of hybrid polyolefin, 24.0 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4.0 g of aluminum chloride and 540.0 mL of N,N-dimethylacetamide and add them to a reaction kettle. Raise the temperature of the reaction kettle to 50 °C, keep the temperature for reaction for 2 h. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 70 °C, and distill under reduced pressure until no liquid is collected, then obtain the flame-retardant polyolefin.

[0050] Step ④, prepare composite polyolefin Weigh: 108.0 g of flame-retardant polyolefin, 24.0 g of flame-retardant microspheres prepared in Example 3 and 480.0 mL of N,N-dimethylformamide and add them to a reaction kettle for stirring. Raise the temperature of the reaction kettle to 70 °C, add 4.0 g of azobisisobutyronitrile to the reaction kettle, keep the temperature for reaction for 3 h. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, transfer the reaction solution to a rotary evaporator, raise the temperature of the rotary evaporator to 70 °C, and distill under reduced pressure until no liquid is collected, then obtain the composite polyolefin.

[0051] Example 7 This example provides a preparation method of a highly flame-retardant decorative material, including the following preparation methods: Weighing: Add 80 parts of the composite polyolefin prepared in Example 4, 5 parts of dioctyl phthalate, 1 part of triphenyl phosphite, 2 parts of 2-hydroxy-4-octyloxybenzophenone, and 3 parts of calcium stearate into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 170 °C, 185, 185 °C, 200 °C, 200 °C, 210 °C, 210 °C in sequence. The main machine speed of the twin-screw extruder is 120 pm, the pressure is 80 bar, melt extrusion is carried out, and a high flame-retardant decorative material is obtained after natural curing.

[0052] Example 8 This example provides a preparation method of a high flame-retardant decorative material, including the following preparation method: Weighing: Add 90 parts of the composite polyolefin prepared in Example 5, 6 parts of dioctyl phthalate, 2 parts of triphenyl phosphite, 4 parts of 2-hydroxy-4-octyloxybenzophenone, and 3 parts of calcium stearate into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 170 °C, 185, 185 °C, 200 °C, 200 °C, 210 °C, 210 °C in sequence. The main machine speed of the twin-screw extruder is 160 rpm, the pressure is 120 bar, melt extrusion is carried out, and a high flame-retardant decorative material is obtained after natural curing.

[0053] Example 9 This example provides a preparation method of a high flame-retardant decorative material, including the following preparation method: Weighing: Add 100 parts of the composite polyolefin prepared in Example 6, 5 parts of dioctyl phthalate, 2 parts of triphenyl phosphite, 3 parts of 2-hydroxy-4-octyloxybenzophenone, and 2 parts of calcium stearate into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 170 °C, 185, 185 °C, 200 °C, 200 °C, 210 °C, 210 °C in sequence. The main machine speed of the twin-screw extruder is 150 rpm, the pressure is 100 bar, melt extrusion is carried out, and a high flame-retardant decorative material is obtained after natural curing.

[0054] Comparative Example 1 The difference between this comparative example and Example 9 is that in the process of preparing the composite polyolefin used in this comparative example, steps I and III in the preparation of the flame-retardant microspheres are cancelled, and the flame-retardant microsphere blanks are used to replace the flame-retardant microspheres in equal amounts.

[0055] Comparative Example 2 The difference between this comparative example and Example 9 is that in the process of preparing the composite polyolefin used in this comparative example, step ③ is cancelled, and the hybrid polyolefin prepared in step ② is used to replace the flame-retardant polyolefin in step ④ in equal amounts.

[0056] Comparative Example 3 The difference between this comparative example and Example 9 is that during the preparation of the composite polyolefin used in this comparative example, the use of flame retardant particles was cancelled.

[0057] Performance test: Referring to the standard GB / T 26526-2011 "Plastics - Determination of flammability by the oxygen index - Part 2: Ambient temperature test", the limiting oxygen index of the highly flame-retardant decorative materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested; Referring to the standard GB / T 9867-2008 "Rubber, vulcanized or thermoplastic - Determination of abrasion resistance (rotary roller abrasion testing machine method)", the volume abrasion of the highly flame-retardant decorative materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested; Referring to the standard GB / T 1843-2008 "Plastics - Determination of izod impact strength", the izod impact strength of the highly flame-retardant decorative materials prepared in Examples 7-9 and Comparative Examples 1-3 was determined; Referring to the standard GB / T 16422.3-2022 "Plastics - Methods of exposure to laboratory light sources - Part 3: Fluorescent UV lamps", the highly flame-retardant decorative materials prepared in Examples 7-9 and Comparative Examples 1-3 were subjected to ultraviolet aging test. Referring to the standards GB / T 9867-2008 and GB / T 1843-2008, the volume abrasion retention rate and the izod notched impact strength retention rate of the highly flame-retardant decorative materials after ultraviolet aging were calculated respectively. The specific data are shown in Table 1; Table 1 - Performance test data table of each specimen

[0058] Data analysis: Comparative analysis of the data in Table 1 shows that the limiting oxygen index of the highly flame-retardant decorative material prepared by the present invention is 40.1%, the volume abrasion is 8.8 mm 3 and the izod impact strength is 76 kJ·m -2 . While the volume abrasion retention rate is 101.5% and the izod impact strength retention rate is 99.1%. All data are better than those of the comparative examples; By comparing the data in Table 1, it can be found that the data of the highly flame-retardant decorative material prepared in Comparative Example 2 decreased slightly. It shows that the phosphoric acid structure introduced in the flame-retardant polyolefin material releases phosphorus-oxygen free radicals in the gas phase through phosphorus-hydrogen addition and cooperates with the carbon-nitrogen double bond to capture combustion free radicals. The lack of activation of the phosphoric acid structure will cause the carbonized layer structure generated during the combustion of the composite polyolefin to be loose, resulting in the need to further improve the flame-retardant performance of the material; However, the decline in the flame retardancy of the highly flame-retardant decorative materials prepared in Comparative Example 1 and Comparative Example 3 is even more drastic. This shows that the flame-retardant microspheres with hexachlorocyclotriphosphazene and triazine ring as the matrix decompose at high temperatures to release nitrogen-containing free radicals, which capture the active free radicals in the combustion chain reaction through the gas-phase quenching effect, inhibiting flame propagation. At the same time, the aluminum isopropoxide filler in the microspheres is dehydrated by heat to form alumina, which delays the thermal decomposition of the material by absorbing heat and cooling, and forms a dense ceramic-like protective layer in the condensed phase to isolate oxygen and heat. Secondly, the silicon-hydrogen bond and double-bond-embedded siloxane structure in the surface modifier crosslink to form a three-dimensional network during combustion, synergistically enhancing the physical isolation effect with the carbonized layer on the surface of the microspheres. At the same time, the silica generated by the pyrolysis of the siloxane further strengthens the stability of the carbon layer, thereby significantly improving the flame retardancy of the material.

[0059] By comparing the data in Table 1, it can be found that the wear resistance and impact resistance of the highly flame-retardant decorative materials prepared in Comparative Example 1 and Comparative Example 3 have decreased significantly, indicating that: Compared with Comparative Example 1, in Example 3, the silicon-hydrogen bond and double-bond-embedded siloxane segments in the surface modifier on the surface of the flame-retardant microspheres form a crosslinked network through telomerization reaction, constructing a three-dimensional rigid and tough skeleton on the surface of the matrix. This not only enhances the surface hardness to resist friction and wear, but also buffers the external force impact through elastic deformation, thereby improving the wear resistance and impact resistance of the material. On this basis, compared with Comparative Example 3, in Example 3, the flame-retardant microspheres in the structure have hexachlorocyclotriphosphazene and triazine ring as the matrix, and its rigid heteroaromatic ring structure is enhanced by filling with aluminum isopropoxide. After uniform dispersion, a filling structure is formed, which acts as a rigid support point in the matrix to inhibit crack propagation. At the same time, the double bonds on the surface of the microspheres form chemical bonding with the free radicals of polyolefins, improving the interfacial bonding strength to prevent peeling caused by stress concentration, thereby significantly improving the wear resistance and impact resistance of the material.

[0060] By comparing the data in Table 1, it can be found that the ultraviolet resistance of the highly flame-retardant decorative materials prepared in Comparative Example 1 and Comparative Example 3 has decreased significantly, indicating that: The silicon-hydrogen bond and double-bond-embedded siloxane segments in the surface modifier prepared in the present invention form a crosslinked network through telomerization reaction, forming a dense protective layer on the surface of the material. The silicon-oxygen bond in its siloxane structure has strong ultraviolet absorption ability, thereby converting high-energy ultraviolet rays into heat energy and dissipating it. After the aluminum isopropoxide filler on the surface of the microspheres is excited by ultraviolet rays, the light energy is converted into lattice heat energy through lattice vibration, thereby significantly improving the ultraviolet resistance of the material.

[0061] It is described that the present invention prepares a surface modifier with a siloxane embedded with silicon-hydrogen bonds and double bonds as the cyclic chain segment and double bonds as the end groups through a telomerization reaction. The surface of a flame-retardant microsphere blank based on hexachlorocyclotriphosphazene and 2,4,6-trihydroxy-1,3,5-triazine as the matrix and aluminum isopropoxide as the filler is modified, thereby obtaining a composite flame-retardant microsphere. Through a radical addition reaction, a modified polyolefin with a flame-retardant triazine ring structure is prepared, and with it as the carrier, a siloxane structure is introduced through an aldehyde-amine condensation reaction to obtain a hybrid polyolefin with an active carbon-nitrogen double bond structure. Further through a phosphine-hydrogen addition reaction, a phosphoric acid structure is introduced onto the long-chain structure, and finally through a radical addition reaction with the double bond structure on the surface of the flame-retardant microsphere, the flame-retardant microspheres are uniformly dispersed on the surface of the matrix and the long-chain structure is chain-extended. Finally, a composite polyolefin is prepared, and the composite polyolefin and auxiliary materials are mixed and melt-extruded to obtain a highly flame-retardant decorative material.

[0062] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A highly flame-retardant decorative material, characterized in that, It comprises raw materials in the following parts by weight: 80 - 100 parts of composite polyolefin and 10 - 15 parts of auxiliary materials; The auxiliary materials comprise raw materials in the following parts by weight: 5 - 6 parts of toughening agent, 1 - 3 parts of antioxidant, 2 - 3 parts of ultraviolet absorber and 2 - 3 parts of lubricant; The preparation method of the composite polyolefin comprises the following steps: A1. Add hybrid polyolefin, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, aluminum chloride and N,N - dimethylacetamide into a reaction kettle, raise the temperature of the reaction kettle to 40 - 60 °C, keep the temperature for reaction for 1 - 3 h, and perform post - treatment to obtain flame - retardant polyolefin; A2. Add the flame - retardant polyolefin, flame - retardant microspheres and N,N - dimethylformamide into a reaction kettle and stir, raise the temperature of the reaction kettle to 60 - 80 °C, add azobisisobutyronitrile into the reaction kettle, keep the temperature for reaction for 2 - 3 h, and perform post - treatment to obtain composite polyolefin.

2. The high flame-retardant decorative material according to claim 1, characterized in that, In step A1, the dosage ratio of the hybrid polyolefin, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, aluminum chloride and N,N - dimethylacetamide is 8 - 10 g: 2 - 3 g: 0.3 - 0.5 g: 50 - 54 mL; in step A2, the dosage ratio of the flame - retardant polyolefin, flame - retardant microspheres, N,N - dimethylformamide and azobisisobutyronitrile is 10 - 12 g: 2 - 3 g: 40 - 48 mL: 0.3 - 0.5 g.

3. A highly flame-retardant decorative material according to claim 1, characterized in that The preparation method of the hybrid polyolefin comprises the following steps: B1. Add phenyl acrylate, 2 - vinyl - 4,6 - diamino - 1,3,5 - triazine, 2 - methylacrolein and N,N - dimethylformamide into a reaction kettle and stir, raise the temperature of the reaction kettle to 60 - 80 °C, add azobisisobutyronitrile into the reaction kettle, keep the temperature for reaction for 2 - 3 h, and perform post - treatment to obtain modified polyolefin; B2. Add the modified polyolefin, 4 - aminobutyltriethoxysilane, 3 - butene - 1 - amine, triethylamine and N,N - dimethylformamide into a reaction kettle, after introducing nitrogen protection, raise the temperature of the reaction kettle to 60 - 80 °C, keep the temperature for reaction for 40 - 60 min, and perform post - treatment to obtain hybrid polyolefin.

4. A highly flame-retardant decorative material according to claim 3, characterized in that, In step B1, the dosage ratio of the phenyl acrylate, 2 - vinyl - 4,6 - diamino - 1,3,5 - triazine, 2 - methylacrolein, N,N - dimethylformamide and azobisisobutyronitrile is 8 - 10 g: 2 - 3 g: 3 - 4 g: 60 - 64 mL: 0.5 - 0.8 g; in step B2, the dosage ratio of the modified polyolefin, 4 - aminobutyltriethoxysilane, 3 - butene - 1 - amine, triethylamine and N,N - dimethylformamide is 8 - 12 g: 6 - 8 g: 1 - 2 g: 0.4 - 0.6 g: 80 - 84 mL.

5. A highly flame-retardant decorative material according to claim 3, characterized in that, The preparation method of the flame - retardant microspheres comprises the following steps: C1. Add hexachlorocyclotriphosphazene and chloroform into a reaction kettle. After ultrasonic dispersion for 15 - 20 min, add 2,4,6 - trihydroxy - 1,3,5 - triazine into the reaction kettle. After continuing ultrasonic treatment for 10 - 15 min, under the condition of ultrasonic treatment, slowly dropwise add triethylamine into the reaction kettle. After ultrasonic dropwise addition for 2 - 3 h, continue to add aluminum isopropoxide, and perform post - treatment to obtain a flame - retardant microsphere blank body; C2. Add the flame - retardant microsphere blank body, surface modifier, and N,N - dimethylformamide into a reaction kettle. After the reaction kettle is protected by nitrogen, add tris(pentafluorophenyl)borane into the reaction kettle and raise the temperature of the reaction kettle to 80 - 100 °C. Keep the temperature for reaction for 60 - 80 min, and perform post - treatment to obtain flame - retardant microspheres.

6. A highly flame-retardant decorative material according to claim 5, characterized in that In step C1, the dosage ratio of hexachlorocyclotriphosphazene, chloroform, 2,4,6 - trihydroxy - 1,3,5 - triazine, triethylamine, and aluminum isopropoxide is 3 - 4 g:40 - 60 mL:1 - 2 g:0.3 - 0.4 g:0.5 - 0.8 g; in step C2, the dosage ratio of the flame - retardant microsphere blank body, surface modifier, N,N - dimethylformamide, and tris(pentafluorophenyl)borane is 4 - 5 g:1 - 2 g:20 - 24 mL:0.3 - 0.5 g.

7. A highly flame-retardant decorative material according to claim 5, characterized in that, The preparation method of the surface modifier is as follows: Add methyl hydrogen - rich silicone oil, 1,3,5,7 - tetraethenyl - 1,3,5,7 - tetramethylcyclotetrasiloxane, 1,3 - dimethyl - 1,1,3,3 - tetraethenyldisiloxane, and ether into a reaction kettle and stir. After stirring at room temperature for 15 - 20 min, add 98.0%wt concentrated sulfuric acid into the reaction kettle and stir. After stirring at room temperature for 8 - 10 h, add sodium bicarbonate powder into the reaction kettle and adjust the pH of the system to 8 - 9, and perform post - treatment to obtain the surface modifier.

8. A method for preparing a highly flame-retardant decorative material according to any one of claims 1-7, characterized in that, It includes the following steps: Add composite polyolefin and auxiliary materials into a twin - screw extruder, melt - extrude, and obtain a high - flame - retardant decorative material after natural curing.

9. Application of a highly flame-retardant decorative material, characterized in that, Apply the high - flame - retardant decorative material according to any one of claims 1 - 7 to the preparation of ornaments.

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