Anti-radiation flame-retardant antibacterial formaldehyde-free car foot mat

Abstract

The invention discloses an anti-radiation flame-retardant antibacterial formaldehyde-free automobile foot mat, and relates to the technical field of automobile interior materials, the anti-radiation flame-retardant antibacterial formaldehyde-free automobile foot mat comprises the following raw materials by weight: 50-60 parts of modified SBS, 10-20 parts of EVA, 10-15 parts of acrylate, 25-30 parts of a composite filler, 2-4 parts of an antioxidant, 3-5 parts of a plasticizer, and 1-1.5 parts of an auxiliary agent. The modified SBS is obtained by grafting SBS and a product a4 obtained by reacting hydroxyl-containing phosphaphenanthrene, dienoic acid, pyridine-containing carboxylic acid and other raw materials, and the modified SBS endows the automobile foot mat with high flame retardance and antibacterial property. The auxiliary agent used in the invention is a high-conductivity cross-linked network obtained by mixing graphene oxide and carboxylated carbon nanotubes, so that the foot pad has relatively strong electromagnetic radiation resistance. The used plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil, and the formaldehyde-free requirement of the foot pad is met.

Description

Technical Field

[0001] The present invention relates to the technical field of automotive interior materials, and particularly relates to an anti-radiation, flame-retardant, antibacterial and formaldehyde-free automotive floor mat. Background Art

[0002] TPE (thermoplastic elastomer) is a new type of environmentally friendly material that combines the easy processability of plastics and the elasticity of rubber. It has strong abrasion resistance and crack resistance, and is non-toxic and odorless, meeting the high standards of people for the air quality inside vehicles. It has good application prospects in the field of materials for automotive floor mats. However, the polarity of TPE materials (such as SBS) is very low, and their compatibility with materials with higher polarity is poor, and they do not have flame retardancy and antibacterial properties, which limits their use in automotive floor mat materials and urgently needs to be improved.

[0003] Electric vehicles generate low-frequency electromagnetic field radiation due to the operation of battery packs and motors. Long-term exposure may have an adverse impact on people's health. Therefore, higher requirements are put forward for the electromagnetic radiation protection of automotive floor mats. In addition, phthalate esters used as plasticizers may decompose into toxic substances such as formaldehyde during high-temperature processing, which does not meet the requirement of formaldehyde-free for automotive floor mats.

[0004] Based on this, a suitable modification method is urgently needed to improve the polarity, flame retardancy and antibacterial properties of SBS, apply it to automotive floor mats, and at the same time improve the electromagnetic radiation protection and formaldehyde-free properties of automotive floor mats to obtain automotive floor mats with excellent comprehensive performance. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides an anti-radiation, flame-retardant, antibacterial and formaldehyde-free automotive floor mat.

[0006] The object of the present invention can be achieved by the following technical solutions: An anti-radiation, flame-retardant, antibacterial and formaldehyde-free automotive floor mat, comprising the following raw materials in parts by weight: 50-60 parts of modified SBS, 10-20 parts of EVA, 10-15 parts of acrylate, 25-30 parts of composite filler, 2-4 parts of antioxidant, 3-5 parts of plasticizer, 1-1.5 parts of auxiliary agent; The preparation of the composite filler comprises the following steps: After mixing and stirring silane coupling agent, absolute ethanol and acetic acid for 10-15 min, adding nano-silica and nano-titanium dioxide and continuing to stir for 12-13 h to obtain a composite filler; the dosage ratio of nano-silica, nano-titanium dioxide, silane coupling agent, absolute ethanol and acetic acid is 1.3-1.5 g: 1-1.2 g: 0.3-0.5 g: 70-80 mL: 2.5-3.5 mL; the silane coupling agent is obtained by mixing KH550 and KH540 in a mass ratio of 1:1; Further, the antioxidant is obtained by mixing antioxidant 1010 and antioxidant 245 in a mass ratio of 3 - 4:1 - 1.5; Further, the plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil in a mass ratio of 1 - 1.5:2.5 - 3.5; Further, the auxiliary agent is obtained by mixing graphene oxide and carboxylated carbon nanotubes in a mass ratio of 1.5 - 2.5:2 - 3; Further, the acrylate is hydroxypropyl methacrylate; The radiation - resistant, flame - retardant, antibacterial and formaldehyde - free car floor mat is prepared by the following steps: mixing modified SBS, EVA, and acrylate at a rotation speed of 80 - 100 rpm for 1 - 1.5 h, then adding composite filler, antioxidant, plasticizer, and auxiliary agent and mixing at a rotation speed of 200 - 300 rpm and a temperature of 85 - 95 °C for 2.5 - 3 h, then extruding and pelletizing through a twin - screw extruder and extruding into a sheet through a single - screw machine, and finally thermoforming the sheet in a thermoforming mold at 180 - 220 °C to obtain the radiation - resistant, flame - retardant, antibacterial and formaldehyde - free car floor mat; The preparation of the modified SBS includes the following steps: Step A1: Mix and stir - react hydroxyphosphaphenanthrene and epichlorohydrin to obtain product a1; mix dienoic acid, DMSO, and 2,3 - dimethylpyridine, stir and heat up, then add product a1 and stir - react to obtain product a2; Step A2: Mix pyridinecarboxylic acid and oxalyl chloride, stir - react at room temperature to obtain product a3; mix product a2 and product a3 and stir - react to obtain product a4; Step A3: Mix SBS, toluene, and cyclohexane, then heat up in an atmosphere of protective gas, add initiator and product a4, and carry out constant - temperature stirring reaction to obtain modified SBS; The preparation of the modified SBS includes the following specific steps: Step A1: Mix hydroxyphosphaphenanthrene, toluene, and absolute ethanol, then add potassium carbonate solution and epichlorohydrin under stirring, stir - react at 50 - 60 °C for 6 - 6.5 h to obtain product a1; mix dienoic acid, DMSO, and 2,3 - dimethylpyridine, stir and heat up to 50 - 60 °C, then add product a1 and stir - react for 7 - 7.5 h to obtain product a2; Further, the dosage ratio of 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, absolute ethanol, potassium carbonate solution, and epichlorohydrin is 33 - 35 g : 50 - 60 mL : 30 - 40 mL : 5 - 7 mL : 20 - 22 g; the 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide is 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; the mass fraction of the potassium carbonate solution is 10 - 15%; the dosage ratio of dienoic acid, DMSO, 2,3-dimethylpyridine, and product a1 is 54 - 56 g : 120 - 130 mL : 1.5 - 2.5 g : 55 - 57 g; the dienoic acid is mevalonic acid; In the reaction process of step A1, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide reacts with epichlorohydrin to obtain a phosphaphenanthrene containing epoxy groups, namely product a1; the dienoic acid reacts with product a1 to obtain a graft product of phosphaphenanthrene containing ester groups and hydroxyl groups and the dienoic acid, namely product a2; Step A2: Mix pyridinecarboxylic acid and dichloromethane, add oxalyl chloride and DMF in an atmosphere of protective gas, stir overnight at room temperature to obtain product a3; mix product a2, dichloromethane, and ethyl acetate, stir for 30 - 40 min, add triethylamine and DMAP in an ice-water bath and stir for 10 - 15 min, then add product a3, and then stir and react at room temperature for 6 - 6.5 h, wash with dilute hydrochloric acid, dry, and perform vacuum distillation to obtain product a4; Further, the dosage ratio of pyridinecarboxylic acid, dichloromethane, oxalyl chloride, and DMF is 31 - 33 g : 125 - 135 mL : 26 - 28 g : 0.8 - 1 g; the pyridinecarboxylic acid is 5-vinylpyridinecarboxylic acid; the dosage ratio of product a2, dichloromethane, ethyl acetate, triethylamine, DMAP, and product a3 is 111 - 113 g : 300 - 310 mL : 40 - 50 mL : 22 - 24 g : 2.5 - 3.5 g : 38 - 40 g; In the reaction process of step A2, the pyridinecarboxylic acid reacts with oxalyl chloride to obtain an acyl chloride product, namely product a3; product a3 reacts with product a2 to obtain a product a4 containing phosphaphenanthrene, conjugated diene, pyridine, and terminal carbon-carbon double bonds; Step A3: Mix SBS, toluene, and cyclohexane, stir for 25 - 35 min, then heat to 55 - 60 °C in an atmosphere of protective gas, add an initiator and stir for 10 - 15 min, add product a4, stir and react at a constant temperature for 3 - 3.5 h, cool, precipitate in ethanol, filter and vacuum dry, and extract with acetone to obtain modified SBS; Further, the dosage ratio of SBS, toluene, cyclohexane, initiator, and product a4 is 10 - 12 g : 50 - 55 mL : 45 - 50 mL : 0.1 - 0.15 g : 2 - 2.2 g; the initiator is BPO; In the reaction process of step A3, product a4 grafts with SBS to obtain modified SBS.

[0007] Advantages of the present invention: The present invention discloses an anti-radiation, flame-retardant, antibacterial and formaldehyde-free car floor mat, which is prepared from raw materials such as modified SBS, EVA, acrylate, composite filler, antioxidant, plasticizer, and auxiliary agent. The auxiliary agent used in the present invention is a highly conductive cross-linked network obtained by mixing graphene oxide and carboxylated carbon nanotubes, which can shield electromagnetic waves by reflecting them and reduce the transmittance of electromagnetic radiation, thereby making the floor mat have strong anti-electromagnetic radiation properties. The plasticizer used in the present invention is a mixture of tributyl citrate and epoxidized soybean oil, and phthalate plasticizers are not used, meeting the formaldehyde-free requirement of the floor mat.

[0008] The synthesized modified SBS is obtained by grafting product a4, which is obtained by reacting raw materials such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, methylpentadienoic acid, and 5-vinylpyridinecarboxylic acid, with SBS; after 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide reacts with 5-vinylpyridinecarboxylic acid and is grafted with SBS, the flame retardancy of the car floor mat is synergistically improved through the carbonization solid-phase flame retardant effect of phosphorus elements in the molecule and the gas-phase flame retardant effect of a large amount of nitrogen elements; after methylpentadienoic acid and 5-vinylpyridinecarboxylic acid participate in the reaction and are grafted with SBS, the conjugated double bond of methylpentadienoic acid and the pyridine in 5-vinylpyridinecarboxylic acid produce a synergistic antibacterial effect, and after the carboxyl group of methylpentadienoic acid is converted into an ester group through the reaction, the deficiency that its antibacterial property is easily affected by pH is compensated; after product a4 is grafted with SBS, it also makes small molecule antibacterial agents and flame retardants not easily migrate and fail in the matrix, and at the same time enhances the polarity of modified SBS, making the compatibility between modified SBS and other raw materials with larger polarity enhanced. Specific embodiments

[0009] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0010] Example 1 A kind of modified SBS, and its preparation includes the following steps: Step A1: Mix 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, and absolute ethanol. While stirring, add potassium carbonate solution and epichlorohydrin, and stir and react at 50 °C for 6 h to obtain product a1. Heat the mixture of methylglutaconic acid, DMSO, and 2,3-dimethylpyridine to 50 °C while stirring, then add product a1 and stir and react for 7 h to obtain product a2. The dosage ratio of 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, absolute ethanol, potassium carbonate solution, and epichlorohydrin is 33 g: 50 mL: 30 mL: 5 mL: 20 g; the mass fraction of the potassium carbonate solution is 10%; the dosage ratio of methylglutaconic acid, DMSO, 2,3-dimethylpyridine, and product a1 is 54 g: 120 mL: 1.5 g: 55 g; Step A2: Mix 5-vinylpyridine formate and dichloromethane, add oxalyl chloride and DMF in a nitrogen atmosphere, and stir overnight at room temperature to obtain product a3. Mix product a2, dichloromethane, and ethyl acetate and stir for 30 min. Add triethylamine and DMAP in an ice-water bath and stir for 10 min, then add product a3, and then stir and react at room temperature for 6 h. Wash with dilute hydrochloric acid (concentration 1.5 mol / L), dry, and perform vacuum distillation to obtain product a4. The dosage ratio of 5-vinylpyridine formate, dichloromethane, oxalyl chloride, and DMF is 31 g: 125 mL: XXXX g: 0.8 g; the dosage ratio of product a2, dichloromethane, ethyl acetate, triethylamine, DMAP, and product a3 is 111 g: 300 mL: 40 mL: 22 g: 2.5 g: 38 g; Step A3: Mix SBS (supplier: Dongguan Zhangmutou Hengtai Plastic Raw Material Business Department, 25 kg / bag), toluene, and cyclohexane and stir for 25 min. Then heat to 55 °C in a nitrogen atmosphere, add BPO and stir for 10 min, add product a4, and stir and react at a constant temperature for 3 h. After cooling, precipitate in ethanol, filter and vacuum dry, and extract with acetone to obtain modified SBS. The dosage ratio of SBS, toluene, cyclohexane, BPO, and product a4 is 10 g: 50 mL: 45 mL: 0.1 g: 2 g.

[0011] Example 2 A modified SBS, the preparation of which comprises the following steps: It should be noted that there seems to be an unclear value "XXXX g" in the translation of Step A2. You may want to check and correct it according to the original content.Step A1: Mix 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, and absolute ethanol. While stirring, add potassium carbonate solution and epichlorohydrin, and stir and react at 55 °C for 6.3 h to obtain product a1. Heat the mixture of methylglutaconic acid, DMSO, and 2,3-dimethylpyridine to 55 °C while stirring, then add product a1 and stir and react for 7.3 h to obtain product a2. The dosage ratio of 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, absolute ethanol, potassium carbonate solution, and epichlorohydrin is 34 g: 55 mL: 35 mL: 6 mL: 21 g; the mass fraction of the potassium carbonate solution is 13%; the dosage ratio of methylglutaconic acid, DMSO, 2,3-dimethylpyridine, and product a1 is 55 g: 125 mL: 2.0 g: 56 g; Step A2: Mix 5-vinylpyridine formate and dichloromethane, add oxalyl chloride and DMF in a nitrogen atmosphere, and stir overnight at room temperature to obtain product a3. Mix product a2, dichloromethane, and ethyl acetate and stir for 35 min. Add triethylamine and DMAP in an ice-water bath and stir for 13 min, then add product a3, and then stir and react at room temperature for 6.3 h. Wash with dilute hydrochloric acid (concentration 1.5 mol / L), dry, and distill under reduced pressure to obtain product a4. The dosage ratio of 5-vinylpyridine formate, dichloromethane, oxalyl chloride, and DMF is 32 g: 130 mL: 27 g: 0.9 g; the dosage ratio of product a2, dichloromethane, ethyl acetate, triethylamine, DMAP, and product a3 is 112 g: 305 mL: 45 mL: 23 g: 3.0 g: 39 g; Step A3: Mix SBS (supplier: Dongguan Zhangmutou Hengtai Plastic Raw Material Business Department, 25 kg / bag), toluene, and cyclohexane and stir for 30 min. Then heat to 58 °C in a nitrogen atmosphere, add BPO and stir for 13 min, add product a4, and stir and react at a constant temperature for 3.3 h. After cooling, precipitate in ethanol, filter and dry in vacuo, and extract with acetone to obtain modified SBS. The dosage ratio of SBS, toluene, cyclohexane, BPO, and product a4 is 11 g: 53 mL: 48 mL: 0.13 g: 2.1 g.

[0012] Example 3 A modified SBS, the preparation of which comprises the following steps: Step A1: Mix 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, and absolute ethanol, and then add potassium carbonate solution and epichlorohydrin under stirring. Stir and react at 60 °C for 6.5 h to obtain product a1; heat the mixture of methylglutaconic acid, DMSO, and 2,3-dimethylpyridine to 60 °C under stirring, then add product a1 and stir and react for 7.5 h to obtain product a2; the dosage ratio of 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, absolute ethanol, potassium carbonate solution, and epichlorohydrin is 35 g: 60 mL: 40 mL: 7 mL: 22 g; the mass fraction of the potassium carbonate solution is 15%; the dosage ratio of methylglutaconic acid, DMSO, 2,3-dimethylpyridine, and product a1 is 56 g: 130 mL: 2.5 g: 57 g; Step A2: Mix pyridinecarboxylic acid and dichloromethane, and then add oxalyl chloride and DMF in a nitrogen atmosphere. Stir overnight at room temperature to obtain product a3; mix product a2, dichloromethane, and ethyl acetate and stir for 40 min. Add triethylamine and DMAP in an ice-water bath and stir for 15 min, then add product a3, and then stir and react at room temperature for 6.5 h. Wash with dilute hydrochloric acid (concentration 1.5 mol / L), dry, and distill under reduced pressure to obtain product a4; the dosage ratio of 5-vinylpyridinecarboxylic acid, dichloromethane, oxalyl chloride, and DMF is 33 g: 135 mL: 28 g: 1 g; the dosage ratio of product a2, dichloromethane, ethyl acetate, triethylamine, DMAP, and product a3 is 113 g: 310 mL: 50 mL: 24 g: 3.5 g: 40 g; Step A3: Mix SBS (supplier: Dongguan Zhangmutou Hengtai Plastic Raw Materials Business Department, 25 kg / bag), toluene, and cyclohexane and stir for 35 min, then heat to 60 °C in a nitrogen atmosphere, add BPO and stir for 15 min, add product a4, and stir and react at a constant temperature for 3.5 h. After cooling, precipitate in ethanol, filter and dry in vacuo, and extract with acetone to obtain modified SBS; the dosage ratio of SBS, toluene, cyclohexane, BPO, and product a4 is 12 g: 55 mL: 50 mL: 0.15 g: 2.2 g.

[0013] Example 4 A radiation-proof, flame-retardant, antibacterial, and formaldehyde-free car floor mat comprises the following raw materials in parts by weight: 50 parts of modified SBS, 10 parts of EVA (supplier: Shanghai Yousuhui Plasticization Co., Ltd., brand: ELVAX, specification: 25 kg / bag), 10 parts of acrylate, 25 parts of composite filler, 2 parts of antioxidant, 3 parts of plasticizer, and 1 part of auxiliary agent; The preparation of the composite filler comprises the following steps: After mixing and stirring silane coupling agent, absolute ethanol, and acetic acid for 10 min, add nano-silica and nano-titanium dioxide and continue stirring for 12 h to obtain the composite filler; the dosage ratio of nano-silica, nano-titanium dioxide, silane coupling agent, absolute ethanol, and acetic acid is 1.3 g: 1 g: 0.3 g: 70 mL: 2.5 mL; the silane coupling agent is obtained by mixing KH550 and KH540 in a mass ratio of 1:1; The antioxidant is obtained by mixing antioxidant 1010 and antioxidant 245 in a mass ratio of 3:1; the plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil in a mass ratio of 1:2.5; the auxiliary agent is obtained by mixing graphene oxide (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd., product number: 1034343-98-0) and carboxylated carbon nanotubes (supplier: Xianfeng Nano, product number: 100299) in a mass ratio of 1.5:2; the acrylate is hydroxypropyl methacrylate (supplier: Nanjing Aicai Procurement Technology Service Co., Ltd.); The preparation of the radiation-proof, flame-retardant, antibacterial, and formaldehyde-free car floor mat comprises the following steps: Mix the modified SBS, EVA, and acrylate obtained in Example 1 at a stirring speed of 80 rpm for 1 h, then add the composite filler, antioxidant, plasticizer, and auxiliary agent and stir and mix at a speed of 200 rpm and a temperature of 85 °C for 2.5 h, and then extrude and pelletize through a twin-screw extruder and extrude into a sheet through a single-screw machine, and heat-seal and form the sheet in a heat-sealing mold at 180 °C to obtain the radiation-proof, flame-retardant, antibacterial, and formaldehyde-free car floor mat.

[0014] Example 5 A radiation-proof, flame-retardant, antibacterial, and formaldehyde-free car floor mat comprises the following raw materials in parts by weight: 55 parts of modified SBS, 15 parts of EVA (supplier: Shanghai Yousuhui Plasticization Co., Ltd., brand: ELVAX, specification: 25 kg / bag), 13 parts of acrylate, 28 parts of composite filler, 3 parts of antioxidant, 4 parts of plasticizer, and 1.3 parts of auxiliary agent; The preparation of the composite filler comprises the following steps: After mixing and stirring silane coupling agent, absolute ethanol, and acetic acid for 13 min, add nano-silica and nano-titanium dioxide and continue stirring for 12.5 h to obtain the composite filler; the dosage ratio of nano-silica, nano-titanium dioxide, silane coupling agent, absolute ethanol, and acetic acid is 1.4 g: 1.1 g: 0.4 g: 75 mL: 3.0 mL; the silane coupling agent is obtained by mixing KH550 and KH540 in a mass ratio of 1:1; The antioxidant is obtained by mixing antioxidant 1010 and antioxidant 245 in a mass ratio of 3.5:1.3; the plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil in a mass ratio of 1.3:3.0; the auxiliary agent is obtained by mixing graphene oxide (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd., product number: 1034343-98-0) and carboxylated carbon nanotubes (supplier: Xianfeng Nano, product number: 100299) in a mass ratio of 2.0:2.5; the acrylate is hydroxypropyl methacrylate (supplier: Nanjing iCPtech Co., Ltd.). The preparation of the radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat includes the following steps: Mix the modified SBS, EVA and acrylate obtained in Example 2 at a stirring speed of 90 rpm for 1.3 h, then add the composite filler, antioxidant, plasticizer and auxiliary agent and stir and mix at a speed of 200 rpm and a temperature of 90 °C for 2.8 h, then extrude and granulate through a twin-screw extruder, extrude into a sheet through a single-screw machine, and thermoform the sheet at 200 °C in a thermoforming mold to obtain the radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat.

[0015] Example 6 A radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat, comprising the following raw materials in parts by weight: 60 parts of modified SBS, 20 parts of EVA (supplier: Shanghai Yousuhui Plasticizing Co., Ltd., brand: ELVAX, specification: 25 kg / bag), 15 parts of acrylate, 30 parts of composite filler, 4 parts of antioxidant, 5 parts of plasticizer, 1.5 parts of auxiliary agent; The preparation of the composite filler includes the following steps: Mix silane coupling agent, absolute ethanol and acetic acid and stir for 15 min, then add nano-silica and nano-titanium dioxide and continue to stir for 13 h to obtain the composite filler; the dosage ratio of nano-silica, nano-titanium dioxide, silane coupling agent, absolute ethanol and acetic acid is 1.5 g:1.2 g:0.5 g:80 mL:3.5 mL; the silane coupling agent is obtained by mixing KH550 and KH540 in a mass ratio of 1:1; The antioxidant is obtained by mixing antioxidant 1010 and antioxidant 245 in a mass ratio of 4:1.5; the plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil in a mass ratio of 1.5:3.5; the auxiliary agent is obtained by mixing graphene oxide (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd., product number: 1034343-98-0) and carboxylated carbon nanotubes (supplier: Xianfeng Nano, product number: 100299) in a mass ratio of 2.5:3; the acrylate is hydroxypropyl methacrylate (supplier: Nanjing iCPtech Co., Ltd.). The preparation of the radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat includes the following steps: Mix the modified SBS, EVA, and acrylate obtained in Example 3 at a stirring speed of 100 rpm for 1.5 h, then add composite filler, antioxidant, plasticizer, and additives and stir and mix at a speed of 200 rpm and a temperature of 95 °C for 3 h. Then, extrude and pelletize through a twin-screw extruder and extrude into a sheet through a single-screw machine. Blister-mold the sheet at 220 °C in a blister mold to obtain the radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat.

[0016] Comparative Example 1 Compared with Example 6, replace 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide in the preparation process of modified SBS with 2,6,7-trioxa-1-phosphabicyclo(2.2.2)octane-4-methanol-1-oxide, and the rest are completely the same as in Example 6 to prepare the car floor mat.

[0017] Comparative Example 2 Compared with Example 6, replace 5-vinylpyridine formate in the preparation process of modified SBS with 4-vinylbenzoic acid, and the rest are completely the same as in Example 6 to prepare the car floor mat.

[0018] Comparative Example 3 Compared with Example 6, replace methylglutaconic acid in the preparation process of modified SBS with sorbic acid, and the rest are completely the same as in Example 6 to prepare the car floor mat.

[0019] Comparative Example 4 Compared with Example 6, replace modified SBS with a mixture of SBS and product a4 in a ratio of 10:1, and the rest are completely the same as in Example 6 to prepare the car floor mat.

[0020] The following is a further effect test on the car floor mat prepared by the present invention, and the test results are as follows.

[0021] Flame retardancy: Refer to GB / T2406.2-2009 to measure the oxygen index of the obtained car floor mat; Antibacterial property: Use Escherichia coli and Staphylococcus aureus as the test strains to measure the antibacterial rate of the car floor mat; The results are recorded in Table 1; Table 1: Test Results

[0022] According to the data in Table 1, the car floor mat of the present invention has excellent flame retardancy and antibacterial properties. Comparing Example 6 with Comparative Example 1, it can be seen that when 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide in the preparation process of modified SBS is replaced by 2,6,7-trioxa-1-phosphabicyclo(2.2.2)octane-4-methanol-1-oxide, the flame retardancy of the car floor mat decreases. Comparing Example 6 with Comparative Example 2, it can be seen that when 5-vinylpyridine formate in the preparation process of modified SBS is replaced by 4-vinylbenzoic acid, the flame retardancy and antibacterial properties of the car floor mat decrease. Comparing Example 6 with Comparative Example 3, it can be seen that when mevalonic acid in the preparation process of modified SBS is replaced by sorbic acid, the antibacterial property of the car floor mat decreases. Comparing Example 6 with Comparative Example 4, it can be seen that modified SBS is obtained by mixing SBS and product a4 in proportion, and the flame retardancy and antibacterial properties of the car floor mat decrease more.

[0023] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. An anti-radiation, flame-retardant, antibacterial and formaldehyde-free car floor mat, characterized in that: It comprises the following raw materials in parts by weight: 50 - 60 parts of modified SBS, 10 - 20 parts of EVA, 10 - 15 parts of acrylate, 25 - 30 parts of composite filler, 2 - 4 parts of antioxidant, 3 - 5 parts of plasticizer, and 1 - 1.5 parts of auxiliary agent; For the preparation of the said modified SBS, the following steps are included: Step A1: Mix and stir react 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide containing hydroxyphosphaphenanthrene and epichlorohydrin to obtain product a1; Mix and stir 2,3-dimethylpyridine, dimethyl sulfoxide and dimethylallylacetic acid, heat up, and then add product a1, and stir react to obtain product a2; Step A2: Mix pyridinecarboxylic acid-containing compound and oxalyl chloride, and stir react at room temperature to obtain product a3; Mix and stir react product a2 and product a3 to obtain product a4; Step A3: Mix SBS, toluene and cyclohexane, heat up in an inert gas atmosphere, add initiator and product a4, and stir react at a constant temperature to obtain modified SBS.

2. The anti-radiation, flame-retardant, antibacterial and formaldehyde-free car floor mat according to claim 1, wherein: In step A1, the hydroxyphosphaphenanthrene is 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and the dienoic acid is dimethylallylacetic acid.

3. The automotive floor mat with anti-radiation, flame retardant, antibacterial and formaldehyde-free properties according to claim 1, characterized in that: In step A2, the pyridinecarboxylic acid-containing compound is 5-vinylpyridinecarboxylic acid.

4. A radiation-proof, flame-retardant, antibacterial and formaldehyde-free car floor mat according to claim 1, characterized in that: The preparation of the said composite filler comprises the following steps: Mix and stir silane coupling agent, absolute ethanol and acetic acid for 10 - 15 min, then add nano-silica and nano-titanium dioxide and continue to stir for 12 - 13 h to obtain the composite filler.

5. The anti-radiation, flame-retardant, antibacterial and formaldehyde-free car floor mat according to claim 4, wherein: The said silane coupling agent is obtained by mixing KH550 and KH540 in a mass ratio of 1:

1.

6. The anti-radiation, flame-retardant, antibacterial and formaldehyde-free car floor mat according to claim 4, characterized in that: The said antioxidant is obtained by mixing antioxidant 1010 and antioxidant 245 in a mass ratio of 3 - 4:1 - 1.

5.

7. The automotive floor mat with radiation protection, flame retardancy, antibacterial property and no formaldehyde according to claim 1, characterized in that: The said plasticizer is obtained by mixing tributyl citrate and epoxidized soybean oil in a mass ratio of 1 - 1.5:2.5 - 3.

5.

8. A radiation-proof, flame-retardant, antibacterial and formaldehyde-free car foot mat according to claim 1, characterized in that: The said auxiliary agent is obtained by mixing graphene oxide and carboxylated carbon nanotubes in a mass ratio of 1.5 - 2.5:2 - 3.

Images