High-wear-resistance automobile interior decoration material and preparation method thereof

Abstract

The invention discloses a high-wear-resistance automobile interior decoration material and a preparation method thereof, and belongs to the technical field of plastic decoration material processing, the high-wear-resistance automobile interior decoration material specifically comprises the following components by weight: 100 parts of high density polyethylene, 10-20 parts of crosslinked polyethylene, 30-40 parts of a functional reinforcing agent, 0.5 part of an initiator and 1 part of an auxiliary additive, the high-density polyethylene is reinforced by the cross-linked high-density polyethylene and the functional reinforcing agent consisting of the triazine polycondensate, the DOPO modified polysiloxane and the functional filler, so that the wear resistance, the tensile strength and the impact resistance of the decorative material are effectively improved, the flame retardance of the material is also improved, and the decorative material does not contain halogen and is environment-friendly. The safety is higher.

Description

Technical Field

[0001] The present invention relates to the technical field of plastic decorative material processing, and in particular to a highly wear-resistant automobile interior decorative material and a preparation method thereof. Background Art

[0002] Automotive interior decorative materials are materials used for automotive interior decoration and functions. They not only determine the visual effects and comfort of the car interior, but also affect the passengers' riding experience and safety performance. Polyolefin plastic materials have good formability and are easy to process into various shapes and textures. They are widely used in automotive interior materials. As the automotive industry develops towards lightweight and intelligent development, interior decorative materials need to have high wear resistance, excellent mechanical properties and environmentally friendly flame retardant properties.

[0003] However, polyolefin plastic decorative materials in the existing technology are prone to wear, scratches, and even cracks in high-wear environments, such as frequent use, contact with hard objects, or friction, which seriously affects the durability and aesthetics of automobile interiors. To improve the wear resistance of plastic decorative materials, a common method is to add wear-resistant additives to the plastic substrate, such as inorganic particles such as nano-silica and alumina. These inorganic particles can be evenly dispersed in the base material to form a physical barrier that effectively resists external friction and wear. However, the amount of inorganic particles added is subject to certain restrictions. Excessive addition will lead to a decrease in the mechanical strength of the material and even agglomeration, affecting the uniformity and aesthetics of the material. In addition, plastic decorative materials are widely used in traditional automobile interiors. Although they have certain flame retardant properties, they still cannot meet the strict safety requirements in high temperature or fire conditions. Traditional flame retardant decorative materials, such as plastics added with halogen flame retardants, although they improve flame retardancy to a certain extent, produce toxic and corrosive gases when burned, which still poses a threat to the environment and human health.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a highly wear-resistant automotive interior decoration material and a preparation method thereof, so as to solve the technical problem that the wear resistance, mechanical strength and flame retardancy of polyolefin plastic decorative materials for automotive decoration in the prior art need to be further improved.

[0006] The object of the present invention can be achieved by the following technical solution: A highly wear-resistant automotive interior decoration material, comprising the following components in parts by weight: 100 parts of high-density polyethylene, 10-20 parts of cross-linked polyethylene, 30-40 parts of a functional reinforcing agent, 0.5 parts of an initiator, and 1 part of an auxiliary additive; The cross-linked polyethylene is obtained by mixing and cross-linking high-density polyethylene; The preparation method of the functional reinforcing agent is as follows: triazine polycondensate, DOPO modified polysiloxane, functional filler, catalyst and toluene are placed in a closed environment filled with ethylene, mixed and stirred, ethylene is continuously introduced, the pressure of the reaction system is controlled at 0.7-0.8 MPa, the temperature of the reaction system is increased to 50-60°C, the temperature and pressure are maintained, the reaction is carried out for 60-80 minutes, and post-processing is performed to obtain the functional reinforcing agent.

[0007] The synthetic reaction mechanism of the functional reinforcing agent is: During the reaction process, vanadium trichloride is used as the main catalyst, diethylaluminum chloride is used as the co-catalyst, and ethyl trichloroacetate is used as the ligand. In an ethylene atmosphere, the catalyst initiates coordination polymerization of ethylene to form active chain segments, and triazine condensation products, DOPO-modified polysiloxanes, and olefin double bonds modified on functional fillers copolymerize with the active chain ends of ethylene to form a cross-linked network, thereby preparing a functional reinforcing agent of a multi-material copolymer cross-linked with polyethylene.

[0008] Furthermore, the triazine polycondensate, DOPO-modified polysiloxane, functionalized filler, catalyst, and toluene are used in a ratio of 5 g:3 g:7 g:0.2 g:50 mL. The catalyst is composed of vanadium trichloride, diethylaluminum chloride, and ethyl trichloroacetate in a weight ratio of 1:10:5. The post-treatment includes: after the reaction is completed, the reaction system is restored to room temperature and pressure, anhydrous ethanol is added to the reaction system, stirred and dispersed for 30-50 minutes, filtered, and the filter cake is washed three times with hydrochloric acid and then twice with a 10 vol% ethanol aqueous solution. The filter cake is transferred to a drying oven at a temperature of 60-70° C. and vacuum dried to constant weight to obtain a functional reinforcing agent.

[0009] Furthermore, the preparation method of the triazine condensation polymer is as follows: under nitrogen protection, 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], triethylamine and acetonitrile are mixed and stirred, the temperature of the reaction system is raised to 75-80°C, and the system is stirred until it is dissolved. 3-aminoethyl-4-aminobutyric acid solution is added dropwise to the reaction system, and the reaction is kept warm for 6-8 hours. 3-isocyanate propylene is added to the reaction system, and the reaction is kept warm for 50-60 minutes. Post-treatment is performed to obtain a triazine condensation polymer.

[0010] The synthetic reaction formula of triazine polycondensate is:

[0011] Where:

[0012] The synthesis reaction mechanism of triazine polycondensate is: During the reaction, triethylamine serves as a catalyst. The amino group in 3-aminoethyl-4-aminobutyric acid acts as a nucleophile, undergoing a nucleophilic substitution reaction with the electrophilic chlorine atom on the triazine ring to form a linear or branched polycondensate. Triethylamine neutralizes HCl, promoting the forward reaction and forming long triazine chains. The isocyanate group on the 3-isocyanatopropylene molecule has good reactivity with both imino and carboxyl groups. During the reaction, the isocyanate group condenses with the carboxyl or imino group to form an olefin double bond modification, resulting in the preparation of a triazine polycondensate.

[0013] Furthermore, the amount ratio of the 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], triethylamine, and acetonitrile is 1 g:0.3 mL:5 mL, and the amount ratio of the 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], 3-aminoethyl-4-aminobutyric acid, and 3-isocyanate propylene is 1 mol. :1.1mol:0.2mol, the 3-aminoethyl-4-aminobutyric acid solution is composed of 3-aminoethyl-4-aminobutyric acid and acetonitrile at 1g:2mL, and the post-treatment comprises: after the reaction is completed, the temperature of the reaction system is lowered to room temperature, a 2wt% aqueous solution of sodium lauryl sulfate is added to the reaction system, stirred and dispersed for 30-50min, filtered, the filter cake is washed three times with a 50vol% ethanol aqueous solution and then dried, the filter cake is transferred to a drying oven at a temperature of 60-70°C, and vacuum dried to constant weight to obtain a triazine polycondensate.

[0014] Furthermore, DOPO-modified polysiloxane is obtained by the following steps: A1. D4, γ-aminopropylmethyldiethoxysilane, and a catalyst were mixed and stirred, the reaction system temperature was raised to 95-100°C, and the reaction was kept warm for 2-3 hours. Diallyltetramethyldisiloxane was added to the reaction system, and the reaction was kept warm for 3-5 hours. After post-treatment, polysiloxane was obtained. A2. Mix polysiloxane, DOPO, triethylamine and N,N-dimethylformamide, raise the temperature of the reaction system to 85-90°C, keep the reaction for 4-5 hours, and post-treat to obtain DOPO-modified polysiloxane.

[0015] The synthetic reaction formula of DOPO modified polysiloxane is:

[0016] The synthetic reaction mechanism of DOPO modified polysiloxane is: During the reaction, the siloxane bonds of D4 are ring-opened in an alkaline environment to form linear siloxane chains. Simultaneously, the siloxane bonds on the γ-aminopropylmethyldiethoxysilane molecules are hydrolyzed to form silanol groups. The silanol groups copolymerize with the linear siloxane chains to introduce amino groups into the polymer chains. Simultaneously, the siloxane bonds on the diallyltetramethyldisiloxane molecules are hydrolyzed to form a monosilanol-terminated olefin-containing end-capping agent, which acts as a chain terminator to form an olefin-terminated modification at the end of the polymer chain to prepare a polysiloxane. The amino groups on the polysiloxane molecular chain act as nucleophilic reaction sites and undergo nucleophilic substitution reaction with the acidic PH bond on the DOPO molecule to generate PN, thereby introducing DOPO into the polysiloxane chain. Triethylamine neutralizes the HCl generated in the reaction, promoting the reaction forward to prepare DOPO-modified polysiloxane.

[0017] Further, in step A1, the amount ratio of D4, γ-aminopropylmethyldiethoxysilane and diallyltetramethyldisiloxane is 5 mol: 2 mol: 0.8 mol, the amount ratio of D4 and catalyst is 1 g: 0.1 mL, the catalyst is a 3 wt% potassium hydroxide aqueous solution, and the post-treatment includes: after the reaction is completed, the temperature of the reaction system is lowered to room temperature, hydrochloric acid is added to the reaction system, the pH of the system is adjusted to 7, the liquid is allowed to stand, and the organic phase is treated with saturated sodium bicarbonate. The solution was washed twice and then once with purified water. The organic phase was transferred to a rotary evaporator with a water bath temperature of 75-85° C., and low-boiling substances were removed under reduced pressure to obtain polysiloxane. In step A2, the amount ratio of the polysiloxane, DOPO, triethylamine, and N,N-dimethylformamide was 10 g:2 g:0.5 g:30 mL. The post-treatment included: after the reaction was completed, the reaction system temperature was raised to 100-110° C., and low-boiling substances were removed under reduced pressure to obtain DOPO-modified polysiloxane.

[0018] Furthermore, the functionalized filler is processed by the following steps: B1. Add nano-silica, graphite, and γ-methacryloxypropyltrimethoxysilane into a ball mill and mill for 60-80 minutes to obtain a mixed filler; B2. Add the mixed filler into a hydrochloric acid solution at a temperature of 50-60° C., keep the temperature to react for 60-80 minutes, and perform post-treatment to obtain a functionalized filler.

[0019] The synthetic reaction mechanism of functionalized fillers is: During the reaction process, the mechanical force of ball milling is used to refine the nano-silica and graphite particles, while promoting the adsorption of γ-methacryloxypropyltrimethoxysilane on the filler surface. In a hydrochloric acid solution, the siloxane bonds on the γ-methacryloxypropyltrimethoxysilane molecules are hydrolyzed to form silanol groups that combine with the active reaction sites on the mixed filler to form unsaturated olefin modifications, thereby preparing a functionalized filler.

[0020] Furthermore, in step B1, the amount ratio of the nano-silica, graphite, and γ-methacryloxypropyltrimethoxysilane is 5g:2g:2g; in step B2, the amount ratio of the mixed filler and the hydrochloric acid solution is 1g:6mL, and the hydrochloric acid solution is composed of 3-5mol / L hydrochloric acid and anhydrous ethanol in a volume ratio of 5:3. The post-treatment includes: after the reaction is completed, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, and the filter cake is transferred to a drying oven at a temperature of 70-80°C and vacuum dried to constant weight to obtain a functional filler.

[0021] The present invention also provides a method for preparing a highly wear-resistant automotive interior decoration material, comprising the following steps: S1. Add high-density polyethylene and initiator into an internal mixer and mix for 9-10 minutes to obtain cross-linked polyethylene; S2. Add cross-linked polyethylene, high-density polyethylene, functional reinforcing agent, initiator and auxiliary additives into an internal mixer, mix for 9-10 minutes, transfer to a flat plate vulcanizer, press into 5-6 mm thin sheets to obtain a decorative material.

[0022] Furthermore, in step S1, the weight ratio of the high-density polyethylene to the initiator is 50:0.1, the initiator is dicumyl peroxide, the mixing temperature is 175-185°C, and the mixer speed is 50-60r / min; in step S2, the mixer temperature is 175-185°C, the mixer speed is 50-60r / min, the pressing pressure of the flat vulcanizer is 10-12MPa, the vulcanization temperature is 180-190°C, and the vulcanization time is 6-8min.

[0023] The present invention has the following beneficial effects: 1. The present invention uses high-density polyethylene as raw material, performs banburying cross-linking on it, initiates a cross-linking reaction of high-density polyethylene, increases the density of CC covalent bond network in high-density polyethylene, and then reinforces the high-density polyethylene with cross-linked polyethylene and functional reinforcing agent to improve the mechanical strength and flame retardant properties of the decorative material. In the decorative material, the three-dimensional network structure of the cross-linked polyethylene can prevent molecular chain slippage, improve the surface hardness of the decorative material, and use the cross-linking points as stress transfer nodes to disperse local friction stress to the entire material system through the covalent bond network, reduce the generation of surface microcracks, and improve tensile strength and impact resistance. In addition, the cross-linked network is more likely to form a continuous and dense carbon layer during combustion, reduce the oxygen diffusion coefficient through physical barrier, and improve the flame retardant properties of the decorative material.

[0024] 2. The present invention uses ethylene as raw material, and forms a polyethylene copolymer bonding coating in triazine polycondensate, DOPO modified polysiloxane, and functional filler through in-situ polycondensation to prepare a functional reinforcing agent. The polyethylene bonding coating layer enables the triazine polycondensate, DOPO modified polysiloxane, and functional filler to be uniformly dispersed in high-density polyethylene. The triazine ring structure in the triazine polycondensate in the functional reinforcing agent has high rigidity and stability, and can effectively resist external friction and wear. By modifying the olefin double bond on its molecular chain, its dispersibility in high-density polyethylene is enhanced, and then A physical barrier is formed in the material to reduce the slippage and breakage of the molecular chain during friction, thereby reducing mass wear. The triazine ring structure in the triazine condensation polymer has high rigidity, which can effectively transfer stress and improve the tensile strength and impact resistance of the material. The phosphorus heterobicyclic structure in the triazine condensation polymer can decompose and generate phosphorus-containing compounds during combustion, promote the formation of a carbon layer, and block the transfer of oxygen and heat, thereby improving the limiting oxygen index. The cross-linked network formed between the triazine condensation polymer and the high-density polyethylene matrix further improves the barrier properties of the material, slows down the transfer of oxygen and heat, and further improves the limiting oxygen index.

[0025] 3. The present invention prepares DOPO-modified polysiloxane by modifying DOPO on the polysiloxane after preparing polysiloxane. The siloxane segments in the polysiloxane have high flexibility and elasticity, can effectively absorb and dissipate energy during friction, reduce the slippage and breakage of high-density polyethylene molecular chains, and reduce quality wear. Moreover, the siloxane segments in the polysiloxane can undergo large deformation when impacted, absorb and dissipate impact energy, and improve the cantilever beam impact strength. The DOPO modified on the DOPO-modified polysiloxane molecule has good flame retardant properties and cooperates with the triazine polycondensate to further promote the formation of a carbon layer, block oxygen and heat transfer, and thus improve the limiting oxygen index of the material. Nano-silica has high rigidity and wear resistance, and can effectively It can effectively resist external friction and wear. Graphite has a layered structure and pores, which can form a lubricating layer during the friction process, reduce the direct contact between the high-density polyethylene molecular chain and the friction pair, and further reduce mass wear. After modification, organic groups are introduced on the surface of nano-silica and expanded graphite to improve their reactivity, so that the filler can be better dispersed in the matrix, reducing the aggravation of local wear caused by filler agglomeration, and with the rigid support of inorganic fillers, effectively transfer stress, improve the tensile strength of the material and resist impact loads. The expansion flame retardancy of graphite can rapidly expand during combustion to form a dense carbon layer. Nano-silica and polysiloxane further stabilize the carbon layer structure, improve the barrier properties of the carbon layer, and further improve the limiting oxygen index of the material. DETAILED DESCRIPTION

[0026] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0027] In this application, 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], CAS No. 1346128-00-4; In this application, D4 is octamethylcyclotetrasiloxane, CAS number 556-67-2; In this application, DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS number 35948-25-5; In this application, nano-silicon dioxide is spherical silicon dioxide selected from Qinghe Chaotai Metal Materials Co., Ltd., with a silicon content of ≥99.9%, model CY-SP30S, and a particle size of 30±5nm; In this application, the graphite is expanded flake graphite powder, selected from Shijiazhuang Fenghua Mineral Products Co., Ltd., with a composition of graphite carbon, an expansion degree of 200-500, and a particle size of 80 mesh; In this application, high-density polyethylene is selected from the brand Sinopec Maoming, brand HHM5502LW, melt flow rate 0.34g / 10min, specific gravity 0.955g / cm 3 .

[0028] Example 1 This embodiment provides a method for preparing a highly wear-resistant automotive interior decoration material, comprising the following steps: S1. Preparation of triazine polycondensate Weigh 160.8 g of 3-aminoethyl-4-aminobutyric acid and 321.6 mL of acetonitrile and mix them evenly to obtain a 3-aminoethyl-4-aminobutyric acid solution for later use. Weigh: 328.1 g of 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], 98.4 mL of triethylamine and 1640.5 mL of acetonitrile, add them into a 5 L reaction flask protected by nitrogen and stir. The temperature of the reaction flask is raised to 75 ° C and stirred until the system is dissolved. The pre-prepared 3-aminoethyl-4-aminobutyric acid solution is added dropwise to the reaction flask. , keep warm and react for 6h, add 16.6g of 3-isocyanate propylene to the reaction flask, keep warm and react for 50min, lower the temperature of the reaction flask to room temperature, add 2L of 2wt% sodium lauryl sulfate aqueous solution to the reaction flask, stir and disperse for 30min, filter, wash the filter cake with 50vol% ethanol aqueous solution 3 times and then dry, transfer the filter cake to a drying oven with a temperature of 60℃ and a negative pressure of 0.1MPa, and vacuum dry to constant weight to obtain a triazine polycondensate.

[0029] S2. Preparation of modified polysiloxane Weigh: 198.3 g of D4, 38.3 g of γ-aminopropylmethyldiethoxysilane, and 19.8 mL of a 3 wt% potassium hydroxide aqueous solution, add them to a 1 L reaction flask and stir, raise the temperature of the reaction flask to 95 ° C, keep the reaction warm for 2 h, add 17.2 g of diallyltetramethyldisiloxane to the reaction flask, keep the reaction warm for 3 h, lower the temperature of the reaction flask to room temperature, add 0.1 mol / L hydrochloric acid to the reaction flask, adjust the pH of the system to 7, let it stand and separate, wash the organic phase twice with a saturated sodium bicarbonate solution and then once with purified water, transfer the organic phase to a rotary evaporator with a water bath temperature of 75 ° C, a negative pressure of 0.1 MPa, and remove low-boiling substances under reduced pressure to obtain polysiloxane; Weigh 200 g of polysiloxane, 40 g of DOPO, 10 g of triethylamine, and 600 mL of N,N-dimethylformamide into a 1 L reaction flask and stir. Raise the temperature of the reaction flask to 85°C and keep the reaction warm for 4 h. Then raise the temperature of the reaction flask to 100°C, reduce the negative pressure to 0.1 MPa, and remove low-boiling substances under reduced pressure to obtain DOPO-modified polysiloxane.

[0030] S3. Preparation of functionalized fillers Weigh 50 g of nano-silica, 20 g of graphite, and 20 g of γ-methacryloxypropyltrimethoxysilane, add them into a ball mill, and ball mill for 60 min to obtain a mixed filler; Mix 3 mol / L hydrochloric acid and anhydrous ethanol in a volume ratio of 5:3 to obtain a hydrochloric acid solution for later use; Weigh: 600 mL of hydrochloric acid solution is added to a 1 L reaction flask and stirred. The temperature of the reaction flask is raised to 50°C. 100 g of mixed filler is added to the reaction flask and kept warm for 60 minutes. The temperature of the reaction flask is lowered to room temperature and filtered. The filter cake is washed with purified water until neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and vacuum dried to constant weight to obtain a functionalized filler.

[0031] S4. Preparation of functional reinforcing agent Vanadium trichloride, diethylaluminum chloride and ethyl trichloroacetate are mixed in a weight ratio of 1:10:5 to obtain a catalyst for later use; Weigh: 50 g of triazine polycondensate, 30 g of DOPO-modified polysiloxane, 70 g of functionalized filler, 2 g of catalyst and 500 mL of toluene and add them to a high-pressure reaction bottle. Ethylene is introduced into the reaction bottle to replace the air in the reaction bottle so that the reaction bottle is filled with ethylene. After the reaction bottle is sealed, ethylene is continuously introduced and the pressure of the reaction bottle is controlled to 0.7 MPa. The temperature of the reaction bottle is raised to 50°C and the reaction is maintained at this temperature and pressure for 60 minutes. The reaction bottle is returned to room temperature and pressure, 1 L of anhydrous ethanol is added to the reaction system, stirred and dispersed for 30 minutes, and filtered. The filter cake is washed three times with hydrochloric acid and then washed twice with a 10 vol% ethanol aqueous solution. The filter cake is transferred to a drying oven at a temperature of 60°C and vacuum dried to constant weight to obtain a functional reinforcing agent.

[0032] S5. Preparation of decorative materials High-density polyethylene and initiator dicumyl peroxide were added into an internal mixer at a weight ratio of 50:0.1 at a temperature of 175°C, and the mixer speed was set at 50 r / min and mixed for 9 minutes to obtain cross-linked polyethylene. The reinforcing agent dibutyl phthalate, the dispersant zinc stearate, the lubricant ethylene bisstearamide, the anti-ultraviolet agent UV-531, and the antioxidant H are mixed uniformly in a weight ratio of 7:3:2:1:1 to obtain an auxiliary additive; Weigh by weight: 10-20 parts of cross-linked polyethylene, 100 parts of high-density polyethylene, 30 parts of functional reinforcing agent, 0.5 parts of initiator dicumyl peroxide and 1 part of auxiliary additives, add them into an internal mixer at a temperature of 175°C, set the internal mixer speed to 50r / min, and mix for min. Then transfer it to a flat plate vulcanizer, set the pressing pressure to 10MPa, the vulcanization temperature to 180°C, the vulcanization time to 6min, and press it into 5mm thin sheets to obtain a decorative material.

[0033] Example 2 This embodiment provides a method for preparing a highly wear-resistant automotive interior decoration material, comprising the following steps: S1. Preparation of triazine polycondensate Weigh 160.8 g of 3-aminoethyl-4-aminobutyric acid and 321.6 mL of acetonitrile and mix them evenly to obtain a 3-aminoethyl-4-aminobutyric acid solution for later use. Weigh: 328.1 g of 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], 98.4 mL of triethylamine and 1640.5 mL of acetonitrile, add them into a 5 L reaction flask protected by nitrogen and stir. The temperature of the reaction flask is raised to 78 ° C and stirred until the system is dissolved. The pre-prepared 3-aminoethyl-4-aminobutyric acid solution is added dropwise to the reaction flask. , keep warm and react for 7h, add 16.6g of 3-isocyanate propylene to the reaction flask, keep warm and react for 55min, lower the temperature of the reaction flask to room temperature, add 2L of 2wt% sodium lauryl sulfate aqueous solution to the reaction flask, stir and disperse for 40min, filter, wash the filter cake with 50vol% ethanol aqueous solution 3 times and then dry, transfer the filter cake to a drying oven with a temperature of 65℃ and a negative pressure of 0.1MPa, and vacuum dry to constant weight to obtain a triazine polycondensate.

[0034] S2. Preparation of modified polysiloxane Weigh: 198.3 g of D4, 38.3 g of γ-aminopropylmethyldiethoxysilane, and 19.8 mL of a 3 wt% potassium hydroxide aqueous solution, add them to a 1 L reaction flask and stir, raise the temperature of the reaction flask to 98 ° C, keep the reaction warm for 2.5 h, add 17.2 g of diallyltetramethyldisiloxane to the reaction flask, keep the reaction warm for 4 h, lower the temperature of the reaction flask to room temperature, add 0.1 mol / L hydrochloric acid to the reaction flask, adjust the pH of the system to 7, let it stand and separate, wash the organic phase twice with a saturated sodium bicarbonate solution and then once with purified water, transfer the organic phase to a rotary evaporator with a water bath temperature of 80 ° C, a negative pressure of 0.1 MPa, and remove the low-boiling point under reduced pressure to obtain polysiloxane; Weigh 200 g of polysiloxane, 40 g of DOPO, 10 g of triethylamine, and 600 mL of N,N-dimethylformamide into a 1 L reaction flask and stir. The temperature of the reaction flask was raised to 88°C and kept warm for 4.5 h. The temperature of the reaction flask was then raised to 105°C, the negative pressure was reduced to 0.1 MPa, and the low-boiling substances were removed under reduced pressure to obtain DOPO-modified polysiloxane.

[0035] S3. Preparation of functionalized fillers Weigh 50 g of nano-silica, 20 g of graphite, and 20 g of γ-methacryloxypropyltrimethoxysilane, add them into a ball mill, and ball mill for 70 min to obtain a mixed filler; Mix 4 mol / L hydrochloric acid and anhydrous ethanol in a volume ratio of 5:3 to obtain a hydrochloric acid solution for later use; Weigh: 600 mL of hydrochloric acid solution is added to a 1 L reaction flask and stirred. The temperature of the reaction flask is raised to 55°C. 100 g of mixed filler is added to the reaction flask and kept warm for 70 minutes. The temperature of the reaction flask is lowered to room temperature and filtered. The filter cake is washed with purified water until neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 75°C and vacuum dried to constant weight to obtain a functionalized filler.

[0036] S4. Preparation of functional reinforcing agent Vanadium trichloride, diethylaluminum chloride and ethyl trichloroacetate are mixed in a weight ratio of 1:10:5 to obtain a catalyst for later use; Weigh: 50 g of triazine polycondensate, 30 g of DOPO-modified polysiloxane, 70 g of functionalized filler, 2 g of catalyst and 500 mL of toluene and add them to a high-pressure reaction bottle. Ethylene is introduced into the reaction bottle to replace the air in the reaction bottle so that the reaction bottle is filled with ethylene. After the reaction bottle is sealed, ethylene is continuously introduced and the pressure of the reaction bottle is controlled to 0.75 MPa. The temperature of the reaction bottle is raised to 55°C and the reaction is maintained at this temperature and pressure for 70 minutes. The reaction bottle is returned to room temperature and pressure, 1 L of anhydrous ethanol is added to the reaction system, stirred and dispersed for 40 minutes, and filtered. The filter cake is washed three times with hydrochloric acid and then washed twice with a 10 vol% ethanol aqueous solution. The filter cake is transferred to a drying oven at a temperature of 65°C and vacuum dried to constant weight to obtain a functional reinforcing agent.

[0037] S5. Preparation of decorative materials High-density polyethylene and initiator dicumyl peroxide were added into an internal mixer at a weight ratio of 50:0.1 at a temperature of 180°C, and the internal mixer speed was set at 55 r / min for 9.5 minutes to obtain cross-linked polyethylene. The reinforcing agent dibutyl phthalate, the dispersant zinc stearate, the lubricant ethylene bisstearamide, the anti-ultraviolet agent UV-531, and the antioxidant H are mixed uniformly in a weight ratio of 7:3:2:1:1 to obtain an auxiliary additive; Weigh by weight: 15 parts of cross-linked polyethylene, 100 parts of high-density polyethylene, 35 parts of functional reinforcing agent, 0.5 parts of initiator dicumyl peroxide and 1 part of auxiliary additives, add them into an internal mixer at a temperature of 180°C, set the internal mixer speed to 55 r / min, and mix for 9.5 minutes. Then transfer it to a flat plate vulcanizer, set the pressing pressure to 11 MPa, the vulcanization temperature to 185°C, the vulcanization time to 7 minutes, and press it into 5.5 mm thin sheets to obtain a decorative material.

[0038] Example 3 This embodiment provides a method for preparing a highly wear-resistant automotive interior decoration material, comprising the following steps: S1. Preparation of triazine polycondensate Weigh 160.8 g of 3-aminoethyl-4-aminobutyric acid and 321.6 mL of acetonitrile and mix them evenly to obtain a 3-aminoethyl-4-aminobutyric acid solution for later use. Weigh: 328.1 g of 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], 98.4 mL of triethylamine and 1640.5 mL of acetonitrile were added to a 5 L reaction flask protected by nitrogen and stirred. The temperature of the reaction flask was raised to 80 ° C and stirred until the system was dissolved. The pre-prepared 3-aminoethyl-4-aminobutyric acid solution was added dropwise to the reaction flask. , keep warm and react for 8h, add 16.6g of 3-isocyanate propylene to the reaction flask, keep warm and react for 60min, lower the temperature of the reaction flask to room temperature, add 2L of 2wt% sodium lauryl sulfate aqueous solution to the reaction flask, stir and disperse for 50min, filter, wash the filter cake with 50vol% ethanol aqueous solution 3 times and then dry, transfer the filter cake to a drying oven with a temperature of 70℃ and a negative pressure of 0.1MPa, and vacuum dry to constant weight to obtain a triazine polycondensate.

[0039] S2. Preparation of modified polysiloxane Weigh: 198.3 g of D4, 38.3 g of γ-aminopropylmethyldiethoxysilane, and 19.8 mL of a 3 wt% potassium hydroxide aqueous solution, add them to a 1 L reaction flask and stir, raise the temperature of the reaction flask to 100 ° C, keep warm and react for 3 h, add 17.2 g of diallyltetramethyldisiloxane to the reaction flask, keep warm and react for 5 h, lower the temperature of the reaction flask to room temperature, add 0.1 mol / L hydrochloric acid to the reaction flask, adjust the pH of the system to 7, let it stand and separate, wash the organic phase twice with a saturated sodium bicarbonate solution and then wash once with purified water, transfer the organic phase to a rotary evaporator with a water bath temperature of 85 ° C and a negative pressure of 0.1 MPa, and remove the low-boiling substances under reduced pressure to obtain polysiloxane; Weigh 200 g of polysiloxane, 40 g of DOPO, 10 g of triethylamine, and 600 mL of N,N-dimethylformamide into a 1 L reaction flask and stir. Raise the temperature of the reaction flask to 90°C and keep the reaction warm for 5 h. Then raise the temperature of the reaction flask to 110°C, reduce the negative pressure to 0.1 MPa, and remove low-boiling substances under reduced pressure to obtain DOPO-modified polysiloxane.

[0040] S3. Preparation of functionalized fillers Weigh 50 g of nano-silica, 20 g of graphite, and 20 g of γ-methacryloxypropyltrimethoxysilane, add them into a ball mill, and ball mill for 80 min to obtain a mixed filler; Mix 5 mol / L hydrochloric acid and anhydrous ethanol in a volume ratio of 5:3 to obtain a hydrochloric acid solution for later use; Weigh: 600 mL of hydrochloric acid solution is added to a 1 L reaction flask and stirred. The temperature of the reaction flask is raised to 60°C. 100 g of mixed filler is added to the reaction flask and kept warm for 80 minutes. The temperature of the reaction flask is lowered to room temperature and filtered. The filter cake is washed with purified water until neutral and then dried. The filter cake is transferred to a drying oven at 80°C and vacuum dried to constant weight to obtain a functionalized filler.

[0041] S4. Preparation of functional reinforcing agent Vanadium trichloride, diethylaluminum chloride and ethyl trichloroacetate are mixed in a weight ratio of 1:10:5 to obtain a catalyst for later use; Weigh: 50 g of triazine polycondensate, 30 g of DOPO-modified polysiloxane, 70 g of functionalized filler, 2 g of catalyst and 500 mL of toluene and add them to a high-pressure reaction bottle. Ethylene is introduced into the reaction bottle to replace the air in the reaction bottle so that the reaction bottle is filled with ethylene. After the reaction bottle is sealed, ethylene is continuously introduced and the pressure of the reaction bottle is controlled to 0.8 MPa. The temperature of the reaction bottle is raised to 60°C and the reaction is maintained at this temperature and pressure for 80 minutes. The reaction bottle is returned to room temperature and pressure, 1 L of anhydrous ethanol is added to the reaction system, stirred and dispersed for 50 minutes, and filtered. The filter cake is washed three times with hydrochloric acid and then washed twice with a 10 vol% ethanol aqueous solution. The filter cake is transferred to a drying oven at a temperature of 70°C and vacuum dried to constant weight to obtain a functional reinforcing agent.

[0042] S5. Preparation of decorative materials High-density polyethylene and initiator dicumyl peroxide were added into an internal mixer at a weight ratio of 50:0.1 at a temperature of 185°C, and the internal mixer speed was set at 60 r / min. The mixture was mixed for 10 minutes to obtain cross-linked polyethylene. The reinforcing agent dibutyl phthalate, the dispersant zinc stearate, the lubricant ethylene bisstearamide, the anti-ultraviolet agent UV-531, and the antioxidant H are mixed uniformly in a weight ratio of 7:3:2:1:1 to obtain an auxiliary additive; Weigh by weight: 20 parts of cross-linked polyethylene, 100 parts of high-density polyethylene, 40 parts of functional reinforcing agent, 0.5 parts of initiator dicumyl peroxide and 1 part of auxiliary additives, add them into an internal mixer at a temperature of 185°C, set the internal mixer speed to 60 r / min, and mix for 10 minutes. Then transfer it to a flat plate vulcanizer, set the pressing pressure to 12 MPa, the vulcanization temperature to 190°C, the vulcanization time to 8 minutes, and press it into 6 mm thin sheets to obtain a decorative material.

[0043] Comparative Example 1 The difference between this comparative example and Example 3 is that step S1 is omitted and no triazine polycondensate is added in step S4.

[0044] Comparative Example 2 The difference between this comparative example and Example 3 is that the DOPO-modified polysiloxane in step S4 is replaced by the polysiloxane in step S2.

[0045] Comparative Example 3 The difference between this comparative example and Example 3 is that the functional filler in step S4 is replaced by a mixture of nano-silicon dioxide and graphite in a weight ratio of 5:2 in step S3.

[0046] Comparative Example 4 The difference between this comparative example and Example 3 is that step S4 is omitted, and a mixture of triazine polycondensate, DOPO-modified polysiloxane, and functionalized filler in a weight ratio of 5:3:7 is used as the functional reinforcing agent.

[0047] Comparative Example 5 The difference between this comparative example and Example 3 is that no cross-linked polyethylene is added in step S5.

[0048] Performance testing: The quality wear, tensile strength, Izod impact strength and limiting oxygen index of the decorative material samples prepared in Examples 1-3 and Comparative Examples 1-5 were tested. The test methods are shown in Table 1 below, and the performance test results are shown in Table 2.

[0049] Table 1-Test methods for test items

[0050] Table 2 - Performance test data of samples

[0051] Data Analysis: Comparing and analyzing the data in Table 1 above, the mass wear of the decorative material prepared by the present invention is reduced to 0.028g, the tensile strength reaches 42.8MPa, and the cantilever beam impact strength reaches 24.8kJ / m 2, the limiting oxygen index reaches 36.5%, and all performance test data are better than the comparative example. The decorative material of the present application does not contain halogen and does not produce acidic corrosive toxic gases when burned. The present invention uses high-density polyethylene as raw material, performs banburying cross-linking on it, triggers the high-density polyethylene cross-linking reaction, increases the CC covalent bond network density in the high-density polyethylene, and then strengthens the high-density polyethylene with cross-linked polyethylene and functional reinforcing agent, which not only effectively improves the wear resistance, tensile strength and impact resistance of the decorative material, but also improves the flame retardant properties of the material.

[0052] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A highly wear-resistant automotive interior decoration material, characterized in that: The invention comprises the following components in parts by weight: 100 parts of high-density polyethylene, 10-20 parts of cross-linked polyethylene, 30-40 parts of functional reinforcing agent, 0.5 parts of initiator and 1 part of auxiliary additive; The cross-linked polyethylene is obtained by mixing and cross-linking high-density polyethylene; The preparation method of the functional reinforcing agent is as follows: triazine polycondensate, DOPO modified polysiloxane, functional filler, catalyst and toluene are placed in a closed environment filled with ethylene, mixed and stirred, ethylene is continuously introduced, the pressure of the reaction system is controlled at 0.7-0.8 MPa, the temperature of the reaction system is increased to 50-60°C, the temperature and pressure are maintained, the reaction is carried out for 60-80 minutes, and post-processing is performed to obtain the functional reinforcing agent.

2. The highly wear-resistant automotive interior decoration material according to claim 1, characterized in that: The triazine polycondensate, DOPO-modified polysiloxane, functionalized filler, catalyst and toluene are used in a ratio of 5 g:3 g:7 g:0.2 g:50 mL, and the catalyst is composed of vanadium trichloride, diethylaluminum chloride and ethyl trichloroacetate in a weight ratio of 1:10:

5.

3. The highly wear-resistant automobile interior decoration material according to claim 1, characterized in that: The preparation method of the triazine polycondensate comprises the following steps: under nitrogen protection, mixing 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], triethylamine and acetonitrile, raising the temperature of the reaction system to 75-80° C., stirring until the system is dissolved, adding dropwise a 3-aminoethyl-4-aminobutyric acid solution to the reaction system, keeping the temperature for reaction for 6-8 hours, adding 3-isocyanate propylene to the reaction system, keeping the temperature for reaction for 50-60 minutes, and performing post-treatment to obtain the triazine polycondensate.

4. The highly wear-resistant automotive interior decoration material according to claim 3, characterized in that: The amount ratio of the 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], triethylamine, and acetonitrile is 1 g:0.3 mL:5 mL, the amount ratio of the 1,3,5-triazine, 2,4-dichloro-6-[(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)methoxy], 3-aminoethyl-4-aminobutyric acid, and 3-isocyanate propylene is 1 mol:1.1 mol:0.2 mol, and the 3-aminoethyl-4-aminobutyric acid solution is composed of 3-aminoethyl-4-aminobutyric acid and acetonitrile at 1 g:2 mL.

5. The highly wear-resistant automobile interior decoration material according to claim 1, characterized in that: DOPO modified polysiloxane is obtained by the following steps: A1. D4, γ-aminopropylmethyldiethoxysilane, and a catalyst were mixed and stirred, the reaction system temperature was raised to 95-100°C, and the reaction was kept warm for 2-3 hours. Diallyltetramethyldisiloxane was added to the reaction system, and the reaction was kept warm for 3-5 hours. After post-treatment, polysiloxane was obtained. A2. Mix polysiloxane, DOPO, triethylamine and N,N-dimethylformamide, raise the temperature of the reaction system to 85-90°C, keep the reaction temperature for 4-5 hours, and post-treat to obtain DOPO-modified polysiloxane.

6. The highly wear-resistant automobile interior decoration material according to claim 5, characterized in that: In step A1, the amount ratio of D4, γ-aminopropylmethyldiethoxysilane and diallyltetramethyldisiloxane is 5 mol:2 mol:0.8 mol, the amount ratio of D4 and the catalyst is 1 g:0.1 mL, and the catalyst is a 3 wt% potassium hydroxide aqueous solution; in step A2, the amount ratio of the polysiloxane, DOPO, triethylamine and N,N-dimethylformamide is 10 g:2 g:0.5 g:30 mL.

7. The highly wear-resistant automobile interior decoration material according to claim 1, characterized in that: Functionalized fillers are processed by the following steps: B1. Add nano-silica, graphite, and γ-methacryloxypropyltrimethoxysilane into a ball mill and mill for 60-80 minutes to obtain a mixed filler; B2. Add the mixed filler into a hydrochloric acid solution at a temperature of 50-60° C., keep the temperature to react for 60-80 minutes, and perform post-treatment to obtain a functionalized filler.

8. The highly wear-resistant automobile interior decoration material according to claim 7, characterized in that: In step B1, the amount ratio of the nano-silica, graphite, and γ-methacryloxypropyltrimethoxysilane is 5g:2g:2g; in step B2, the amount ratio of the mixed filler and the hydrochloric acid solution is 1g:6mL, and the hydrochloric acid solution is composed of 3-5mol / L hydrochloric acid and anhydrous ethanol in a volume ratio of 5:

3.

9. The method for preparing a highly wear-resistant automobile interior decoration material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Add high-density polyethylene and initiator into an internal mixer and mix for 9-10 minutes to obtain cross-linked polyethylene; S2. Add cross-linked polyethylene, high-density polyethylene, functional reinforcing agent, initiator and auxiliary additives into an internal mixer, mix for 9-10 minutes, transfer to a flat plate vulcanizer, press into 5-6 mm thin sheets to obtain a decorative material.

10. The method for preparing a highly wear-resistant automobile interior decoration material according to claim 9, characterized in that: In step S1, the weight ratio of the high density polyethylene to the initiator is 50: 0.1, the initiator is dicumyl peroxide, the mixing temperature is 175-185° C., and the mixer speed is 50-60 r / min; in step S2, the mixer temperature is 175-185° C., the mixer speed is 50-60 r / min, the pressing pressure of the flat vulcanizer is 10-12 MPa, the vulcanization temperature is 180-190° C., and the vulcanization time is 6-8 min.

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