Anti-aging and yellowing-resistant foamed polyester material and preparation method thereof

Abstract

The application discloses an anti-aging and yellowing-resistant foamed polyester material and a preparation method thereof, and relates to the technical field of polyester materials. The anti-aging and yellowing-resistant foamed polyester material is prepared from the following raw material components in proportion by weight: 3-5 parts of anti-ultraviolet SEBS, 3.6-7 parts of triethylamine, 4-6 parts of a flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9-1.1 parts of a polymer wax, and 0.6-0.8 parts of a foaming agent. The anti-ultraviolet SEBS is obtained by copolymerization grafting of an unsaturated benzophenone ultraviolet absorber, SEBS and maleic anhydride. The flame-retardant and wear-resistant filler is obtained by mixing and reacting carboxylated nano silicon dioxide, pentaerythritol and phosphorus oxychloride. The polymer wax is EVA wax. The foaming agent is azodicarbonamide. The anti-aging and yellowing-resistant foamed polyester material has good mechanical properties, anti-aging performance, flame-retardant performance and compression resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester materials, in particular to an anti-aging and anti-yellowing foamed polyester material and a preparation method thereof. BACKGROUND

[0002] Thermoplastic polyester elastomer (TPEE) is a unique block copolymer composed of aromatic polyester hard segments (crystalline phase) and aliphatic polyester or polyether soft segments (continuous phase), which combines the softness and elasticity of rubber with the rigidity and processability of thermoplastic plastic. TPEE has attracted wide attention due to its high mechanical strength, good elasticity, strong impact resistance, and excellent resistance to creep, cold, bending fatigue, oil, chemicals, and solvent erosion. These properties enable it to be widely used in various fields such as automotive parts, hydraulic hoses, cables and wires, sports equipment, and construction.

[0003] Foamed materials, as a new type of composite material with light weight, material saving, and high specific strength, have been widely used in industrial, agricultural, transportation, information technology, high-speed railway, aerospace, and other fields due to their excellent thermal and sound insulation, and cushioning properties. With the advancement of science and technology, the related scientific and technological achievements of foamed materials have attracted the attention of polymer processing professionals.

[0004] TPEE foamed materials aim to combine the excellent properties of TPEE and the advantages of foamed materials to form a new material with high strength, high elasticity, and the ability to effectively absorb stress and cushion vibration. However, the structural characteristics of TPEE determine that its resin melt has high flowability and low melt strength, which significantly decreases at the foaming temperature, making it difficult to maintain uniform cell formation in the resin, resulting in problems such as stringing and cell rupture.

[0005] To solve this problem, star-shaped block copolymer SEBS (styrene-ethylene / butylene-styrene) can be used to improve the melt strength of TPEE. SEBS has high physical crosslinking effect, high modulus, and is not easily degraded, thus having high melt strength. However, the lack of polar and reactive groups on the SEBS molecular chain limits its compatibility with TPEE. Combining SEBS and TPEE not only fails to form a more uniform cell structure, but also causes the performance of TPEE to decline.

[0006] In addition, factors such as anti-oxidation and anti-yellowing properties, and flame retardancy need to be considered in the design and production process of TPEE foamed materials. Anti-oxidation and anti-yellowing properties are very important for prolonging the service life of the material and maintaining the appearance, while flame retardancy is a necessary safety requirement in many application fields, especially in building and transportation interior parts.

[0007] Therefore, the applicant prepares an anti-aging and yellowing-resistant foamed polyester material to solve the above problems. SUMMARY

[0008] To solve the existing technical problems, the application provides an anti-aging and yellowing-resistant foamed polyester material, and raw material components include, in terms of weight fractions, 3-5 parts of anti-ultraviolet SEBS, 3.6-7 parts of triethylamine, 4-6 parts of flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9-1.1 parts of polymer wax, and 0.6-0.8 parts of foaming agent.

[0009] Further, the anti-ultraviolet SEBS is obtained by copolymerization grafting of an unsaturated benzophenone ultraviolet absorber, SEBS, and maleic anhydride.

[0010] Further, the unsaturated benzophenone ultraviolet absorber is obtained by mixed reaction of 2,4,4-trihydroxybenzophenone and acryloyl chloride.

[0011] Further, the flame-retardant and wear-resistant filler is obtained by mixed reaction of carboxylated nanosilica, pentaerythritol, and phosphorus oxychloride.

[0012] Further, the carboxylated nanosilica is obtained by reaction of nanosilica with p-terephthalic acid and silane coupling agent KH550 in sequence.

[0013] Further, the polymer wax is EVA wax.

[0014] Further, the foaming agent is azodicarbonamide.

[0015] The application also provides an anti-aging and yellowing-resistant foamed polyester material, including the following preparation steps:

[0016] (1) Preparing materials, and preparing materials in the following weight fractions: 3-5 parts of anti-ultraviolet SEBS, 3.6-7 parts of triethylamine, 2.5-3.5 parts of flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9-1.1 parts of polymer wax, and 0.6-0.8 parts of foaming agent;

[0017] (2) Under the condition of nitrogen protection, the anti-ultraviolet SEBS and toluene are mixed in a mass ratio of 1:20-40, stirred at 500-900 rpm for 2-4 h, then triethylamine and flame-retardant wear-resistant filler are added, and stirring is continued at 90°C for 13-15 h. After natural cooling to room temperature, the mixture is filtered, washed with ethyl acetate and deionized water for 3-5 times, and dried in a vacuum drying oven at 100°C overnight until the weight is constant. Then, the TPEE and EVA wax are put into a high-speed stirrer together with the anti-ultraviolet SEBS, and stirred at 70°C for 2-4 min. After the foaming agent azodicarbonamide is added and mixed uniformly, the mixture is discharged and extruded into a single-screw extruder with a metering section temperature of 220-230°C, a die head mold temperature of 195°C, and a screw rotation speed of 60 rpm. After cooling, traction and calendering by a calender machine, a sheet is obtained.

[0018] Further, the preparation method of the anti-ultraviolet SEBS is as follows: maleic anhydride is dried in a vacuum drying oven at 120°C for more than 12 h. First, maleic anhydride, an unsaturated benzophenone ultraviolet absorber, dicumyl peroxide, and acetone are stirred and dissolved in a mass ratio of 1:1.2-1.4:0.09-0.11:10. Then, the mixture is uniformly sprinkled on the surface of SEBS powder with a mass of 90-100 times that of the maleic anhydride. Then, the mixture is put into a high-speed stirrer and stirred at 1000-2000 rpm for 5 min, with the stirring temperature set to 80°C. After mixing is completed, the mixture is extruded by a twin-screw extruder, with the temperature of each zone of the extruder set to 220, 245, 265, 285, and 270°C, respectively, and the screw rotation speed set to 40 r / min.

[0019] Further, the preparation method of the unsaturated benzophenone ultraviolet absorber is as follows: 1M / L sodium hydroxide aqueous solution and 2,4,4-trihydroxybenzophenone are mixed and dissolved completely at 300-500 rpm. Then, the mixture is stirred at 1200-1500 rpm in an ice water bath, and acryloyl chloride is added dropwise. The reaction is carried out for 1.5-2.5 h, and the unsaturated benzophenone ultraviolet absorber is obtained by filtration. The molar ratio of 2,4,4-trihydroxybenzophenone, acryloyl chloride, and sodium hydroxide is 1:0.9-1.1:1.

[0020] Further, the preparation method of the flame-retardant wear-resistant filler is as follows: the carboxylated nano-silica is dispersed in 20-40 times of toluene by mass, then 0.5-0.6 times of pentaerythritol of the material amount of the carboxyl group in the carboxylated nano-silica is added, stirring at 300-500 rpm for 20-40 min, then 0.2-0.4 times of concentrated sulfuric acid of the mass of the carboxylated nano-silica is added, heating refluxing for 2-4 h, filtering, washing with acetone and deionized water for 2-4 times in sequence, drying in an oven at 80 DEG C for 48 h, then mixing with phosphorus oxychloride, wherein the molar ratio of pentaerythritol and phosphorus oxychloride is 1:6-6.5, heating to 80 DEG C and reacting for 1.8-2.2 h, then heating to 110 DEG C, stirring at 1300-1700 rpm and reacting overnight until no hydrogen chloride gas is generated, then cooling to room temperature, filtering and drying in a vacuum drying oven at 80 DEG C to constant weight to obtain the flame-retardant wear-resistant filler; wherein the filtering process is washing with dichloromethane and diethyl ether for 3 times respectively.

[0021] Further, the preparation method of the carboxylated nano-silica is as follows: the nano-silica is ultrasonically dispersed in 20-40 times of N,N-dimethylformamide by mass for 20-40 min, then 6% of the hydrolysis solution of KH550 is added, wherein the mass of the hydrolysis solution of KH550 is 1-2 times of the mass of the nano-silica, then ultrasonic stirring for 5 h, then pouring into 50-100 times of deionized water of the mass of the nano-silica, standing for 24 h, filtering, drying in an oven at 120 DEG C for 48 h and naturally cooling to room temperature, then dispersing into 40-60 times of benzene of the mass of the nano-silica and adding terephthalic acid in an equal molar amount of KH550, heating to 85-95 DEG C, continuing to obtain ultrasonic stirring for 1-2 h, filtering, washing with acetone and deionized water for 2-4 times in sequence, drying in an oven at 80 DEG C for 48 h to obtain the carboxylated nano-silica.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] The anti-aging and yellowing-resistant foamed polyester material of the present application is prepared by the following steps: first, obtaining anti-ultraviolet SEBS by grafting unsaturated benzophenone ultraviolet absorber, SEBS and maleic anhydride; then, obtaining flame-retardant wear-resistant filler by mixing carboxylated nano-silica, pentaerythritol and phosphorus oxychloride; finally, obtaining the anti-aging and yellowing-resistant foamed polyester material by mixing anti-ultraviolet SEBS, triethylamine, flame-retardant wear-resistant filler, TPEE, polymer wax and foaming agent and foaming; wherein, the unsaturated benzophenone ultraviolet absorber is obtained by mixing 2,4,4-trihydroxybenzophenone and acryloyl chloride; the carboxylated nano-silica is obtained by reacting silane coupling agent KH550 and terephthalic acid with nano-silica in sequence.

[0024] Firstly, the unsaturated benzophenone ultraviolet absorber, maleic anhydride and SEBS are copolymerized and grafted, the maleic anhydride and the unsaturated benzophenone ultraviolet absorber are introduced into the SEBS molecular chain, the polar groups and the ultraviolet absorber are introduced into the SEBS molecular chain, the ultraviolet oxidation resistance and the compatibility with TPEE of the SEBS are enhanced, and then the foaming performance, the mechanical property and the ultraviolet oxidation resistance of the TPEE foaming material are enhanced.

[0025] Secondly, the carboxylated nano-silica, pentaerythritol and phosphorus oxychloride are mixed to obtain the flame-retardant and wear-resistant filler, the hydroxyl groups on the pentaerythritol are reacted with the carboxylated nano-silica and the phosphorus oxychloride respectively, a layer of chlorinated pentaerythritol phosphate ester derivative is formed on the surface of the carboxylated nano-silica, the presence of the nano-silica can promote the decomposition of the chlorinated pentaerythritol phosphate ester derivative at high temperature, accelerate the generation of phosphides, and thus improve the carbonization efficiency, meanwhile, the nano-silica and the chlorinated pentaerythritol phosphate ester derivative jointly act, can form a more dense physical barrier and carbon layer during combustion, effectively prevent the transmission of heat and oxygen, reduce the generation of combustible gas, and thus improve the flame-retardant performance of the flame-retardant and wear-resistant filler.

[0026] Subsequently, the anti-aging and yellowing-resistant foaming polyester material is obtained by mixing and reacting the anti-ultraviolet SEBS, triethylamine, the flame-retardant and wear-resistant filler, TPEE, polymer wax and foaming agent; the anti-ultraviolet performance and the foaming performance of the anti-aging and yellowing-resistant foaming polyester material can be effectively improved by adding the anti-ultraviolet SEBS in the TPEE; the flame-retardant and wear-resistant filler provides nucleating agent for polyester material foaming, so that a more uniform and uniform cell structure is obtained, and thus the mechanical property of the anti-aging and yellowing-resistant foaming polyester material is ensured; the flame-retardant and wear-resistant filler, the anti-ultraviolet SEBS and the triethylamine are mixed first, and then the TPEE, the polymer wax and the foaming agent are added for mixing, the chlorine on the chlorinated pentaerythritol phosphate ester derivative on the flame-retardant and wear-resistant filler reacts with the hydroxyl on the anti-ultraviolet SEBS to graft the flame-retardant and wear-resistant filler on the anti-ultraviolet SEBS, so that the flame-retardant and wear-resistant filler is stably grafted on the anti-ultraviolet SEBS and uniformly dispersed in the TPEE, and thus the anti-ultraviolet performance and the flame-retardant performance of the anti-aging and yellowing-resistant foaming polyester material are enhanced, the foaming performance of the anti-aging and yellowing-resistant foaming polyester material is enhanced, and thus the mechanical property of the anti-aging and yellowing-resistant foaming polyester material is enhanced. DETAILED DESCRIPTION

[0027] The application will be further described in detail below in combination with examples, but the following examples should not be understood as limiting the application.

[0028] The TPEE used in the examples and comparative examples of the application is TPEE resin-H63DMG; the SEBS is SEBS YH501 produced by Balin Petrochemical Co., Ltd.; and the EVA wax is obtained from Beijing Dongfang Shihua Chemical Co., Ltd.

[0029] The following table is the performance of the TPEE resin:

[0030] Example 1

[0031] A method for preparing an anti-aging and yellowing-resistant foamed polyester material, the preparation steps are as follows:

[0032] (1) Prepare materials according to the following weight proportions: 3 parts of anti-ultraviolet SEBS, 3.6 parts of triethylamine, 4 parts of flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9 parts of polymer wax, and 0.6 parts of foaming agent;

[0033] (2) Under nitrogen protection, mix anti-ultraviolet SEBS and toluene at a mass ratio of 1:20, stir at 500 rpm for 2 h, then add triethylamine and flame-retardant and wear-resistant filler, continue to stir at 90°C for 13 h, after natural cooling to room temperature, filter, wash with ethyl acetate and deionized water for 3 times respectively, and place in a vacuum drying oven at 100°C overnight until constant weight, then put TPEE and EVA wax into a high-speed stirrer at 70°C and stir for 2 min, then add foaming agent azodicarbonamide, mix uniformly, and then put into a single screw extruder with a metering section temperature of 220°C, a die head mold temperature of 195°C, and a screw rotation speed of 60 rpm, and then extrude, cool, pull and calender into a sheet through a calender.

[0034] Further, the preparation method of the anti-ultraviolet SEBS is as follows: dry maleic anhydride in a vacuum drying oven at 120°C for more than 12 h, first stir and dissolve maleic anhydride, unsaturated benzophenone ultraviolet absorber, dicumyl peroxide and acetone at a mass ratio of 1:1.2:0.09:10, then evenly sprinkle on the surface of SEBS powder with a mass of 90 times maleic anhydride, then put into a high-speed stirrer and stir at 1000 rpm for 5 min, set the stirring temperature to 80°C, after mixing, extrude by using a twin-screw extruder, set the temperature of each zone of the extruder to 220, 245, 265, 285 and 270°C respectively, and set the screw rotation speed to 40 r / min.

[0035] Further, the preparation method of the unsaturated benzophenone ultraviolet absorber is as follows: mix 1M / L sodium hydroxide aqueous solution and 2,4,4-trihydroxybenzophenone, completely dissolve at 300 rpm, then stir in an ice water bath at 1200 rpm, and add acryloyl chloride dropwise, react for 1.5 h, filter, and obtain the unsaturated benzophenone ultraviolet absorber; wherein the molar ratio of 2,4,4-trihydroxybenzophenone, acryloyl chloride and sodium hydroxide is 1:0.9:1.

[0036] Further, the preparation method of the flame-retardant wear-resistant filler is as follows: the carboxylated nano-silica is dispersed in 20 times of toluene by mass, then 0.5 times of pentaerythritol of the material amount of the carboxyl group in the carboxylated nano-silica is added, stirred at 300 rpm for 20 min, then 0.2 times of concentrated sulfuric acid of the mass of the carboxylated nano-silica is added, heated to reflux for 2 h, filtered, washed with acetone and deionized water for 2 times in sequence, placed in a drying oven at 80°C for 48 h, then mixed with phosphorus oxychloride, wherein the molar ratio of pentaerythritol and phosphorus oxychloride is 1:6, heated to 80°C and reacted for 1.8 h, then heated to 110°C, stirred at 1300 rpm overnight until substantially no hydrogen chloride gas is generated, then cooled to room temperature, filtered and placed in a vacuum drying oven at 80°C for drying to constant weight, to obtain the flame-retardant wear-resistant filler; wherein, during the filtration process, dichloromethane and diethyl ether are used for washing 3 times, respectively.

[0037] Further, the preparation method of the carboxylated nano-silica is as follows: the nano-silica is ultrasonically dispersed in 20 times of N,N-dimethylformamide by mass for 20 min, then 6% of the KH550 hydrolysate by mass fraction is added, wherein the mass of the KH550 hydrolysate is 1 times of the mass of the nano-silica, then ultrasonic stirring is continued for 5 h, then poured into 50 times of deionized water by mass of the nano-silica, left to stand for 24 h, filtered, placed in a drying oven at 120°C for 48 h, then naturally cooled to room temperature, then dispersed into 40 times of benzene by mass of the nano-silica, and added with terephthalic acid in an equal molar amount of KH550, heated to 85°C, and continued to be ultrasonic stirring for 1 h, filtered, washed with acetone and deionized water for 2 times in sequence, placed in a drying oven at 80°C for 48 h, to obtain the carboxylated nano-silica. Example 2

[0038] A preparation method of an anti-aging and yellowing-resistant foamed polyester material, the preparation steps are as follows:

[0039] (1) Preparation, the following weight parts are prepared: anti-ultraviolet SEBS 4 parts, triethylamine 5.3 parts, flame-retardant wear-resistant filler 5 parts, TPEE 100 parts, polymer wax 1 part, foaming agent 0.7 part;

[0040] (2) Under the condition of nitrogen protection, anti-ultraviolet SEBS and toluene were mixed in a mass ratio of 1:30, stirred at 700 rpm for 3 h, then triethylamine and flame-retardant wear-resistant filler were added, and stirring was continued at 90°C for 14 h. After natural cooling to room temperature, filtration was performed, and then the product was washed with ethyl acetate and deionized water four times, and then dried in a vacuum drying oven at 100°C overnight until the weight was constant. Then, TPEE and EVA wax were put into a high-speed stirrer and stirred at 70°C for 3 min. After the foaming agent azodicarbonamide was added and mixed uniformly, the product was discharged and then extruded into a single-screw extruder with a metering section temperature of 225°C, a die head temperature of 195°C, and a screw rotation speed of 60 rpm. After cooling, traction and calendering by a calendering machine, the product was formed into a sheet.

[0041] Further, the preparation method of the anti-ultraviolet SEBS is as follows: maleic anhydride is dried in a vacuum drying oven at 120°C for more than 12 h. Maleic anhydride, an unsaturated benzophenone ultraviolet absorber, dicumyl peroxide and acetone are stirred and dissolved in a mass ratio of 1:1.3:0.1:10, and then uniformly sprinkled on the surface of SEBS powder with a mass of 95 times that of the maleic anhydride. Then, the mixture is put into a high-speed stirrer and stirred at 1500 rpm for 5 min, with the stirring temperature set to 80°C. After mixing is completed, the product is extruded by a twin-screw extruder, with the temperature of each zone of the extruder set to 220, 245, 265, 285 and 270°C, respectively, and the screw rotation speed set to 40 r / min.

[0042] Further, the preparation method of the unsaturated benzophenone ultraviolet absorber is as follows: 1M / L sodium hydroxide aqueous solution and 2,4,4-trihydroxybenzophenone are mixed and dissolved completely at 400 rpm, and then stirred at 1400 rpm in an ice water bath. Acryloyl chloride is added dropwise, and the reaction is carried out for 2 h. After filtration, the unsaturated benzophenone ultraviolet absorber is obtained. The molar ratio of 2,4,4-trihydroxybenzophenone, acryloyl chloride and sodium hydroxide is 1:1:1.

[0043] Further, the preparation method of the flame-retardant wear-resistant filler is as follows: carboxylated nano-silicon dioxide is dispersed in toluene with a mass of 30 times that of the carboxylated nano-silicon dioxide. Then, pentaerythritol with a substance amount of 0.55 times that of the carboxyl groups in the carboxylated nano-silicon dioxide is added, and stirred at 400 rpm for 30 min. Then, concentrated sulfuric acid with a mass of 0.3 times that of the carboxylated nano-silicon dioxide is added, and heated to reflux for 3 h. After filtration, the product is washed with acetone and deionized water three times, respectively, and then dried in an oven at 80°C for 48 h. Then, the product is mixed with phosphorus oxychloride, with the molar ratio of pentaerythritol and phosphorus oxychloride being 1:6.3. After the temperature is raised to 80°C and reacted for 2 h, the temperature is further raised to 110°C, and the product is stirred at 1500 rpm overnight until basically no hydrogen chloride gas is generated. After cooling to room temperature, the product is filtered and then dried in a vacuum drying oven at 80°C until the weight is constant. Thus, the flame-retardant wear-resistant filler is obtained. During the filtration process, the product is washed with dichloromethane and diethyl ether three times, respectively.

[0044] Further, the preparation method of the carboxylated nano-silica is as follows: Nano-silica is ultrasonically dispersed in 30 times its mass of N,N-dimethylformamide for 30 min, then 6% KH550 hydrolysate is added, wherein the mass of KH550 hydrolysate is 1.5 times the mass of nano-silica, and then ultrasonically stirred for 5 h, then poured into 80 times its mass of deionized water, allowed to stand for 24 h, filtered, dried in an oven at 120℃ for 48 h, and then naturally cooled to room temperature, then dispersed in 50 times its mass of benzene, and equimolar amounts of terephthalic acid of KH550 are added, heated to 90℃, and ultrasonically stirred for 1.5 h, filtered, washed three times with acetone and deionized water, and dried in an oven at 80℃ for 48 h to obtain carboxylated nano-silica. Example 3

[0045] A method for preparing an anti-aging and yellowing-resistant foamed polyester material, comprising the following steps:

[0046] (1) Prepare materials according to the following weight proportions: 5 parts of anti-ultraviolet SEBS, 7 parts of triethylamine, 6 parts of flame retardant and wear-resistant filler, 100 parts of TPEE, 1.1 parts of polymer wax, and 0.8 parts of foaming agent;

[0047] (2) Under nitrogen protection, UV-resistant SEBS and toluene were mixed at a mass ratio of 1:40 and stirred at 900 rpm for 4 hours. Then, triethylamine and flame-retardant and wear-resistant filler were added and stirred at 90°C for 15 hours. After naturally cooling to room temperature, the mixture was filtered and washed 5 times with ethyl acetate and deionized water. It was then placed in a vacuum drying oven and dried overnight at 100°C until constant weight. Then, it was mixed with TPEE and EVA wax and placed in a high-speed mixer and stirred at 70°C for 4 minutes. Azodicarbonamide was added as a foaming agent and mixed evenly before being discharged. The mixture was then fed into a single-screw extruder with a metering section temperature of 230°C, a die head temperature of 195°C, and a screw speed of 60 rpm. The mixture was cooled by a calender, drawn, and calendered into sheets.

[0048] Furthermore, the preparation method of the UV-resistant SEBS is as follows: Maleic anhydride is dried in a vacuum drying oven at 120°C for more than 12 hours. First, maleic anhydride, unsaturated benzophenone-based UV absorber, dicumyl peroxide, and acetone are stirred and dissolved in a mass ratio of 1:1.4:0.11:10. Then, the solution is evenly sprinkled on the surface of SEBS powder with a mass of 100 times that of maleic anhydride. Next, it is placed in a high-speed mixer and stirred at 2000 rpm for 5 minutes. The stirring temperature is set to 80°C. After mixing, it is extruded using a twin-screw extruder. The temperatures of each zone of the extruder are set to 220, 245, 265, 285, and 270°C, respectively, and the screw speed is set to 40 r / min.

[0049] Further, the preparation method of the unsaturated benzophenone type ultraviolet absorber is as follows: 1M / L sodium hydroxide aqueous solution and 2,4,4-trihydroxybenzophenone are mixed, dissolved completely at 500 rpm, then stirred at 1500 rpm in an ice water bath, and acryloyl chloride is added dropwise, reacted for 2.5h, filtered, and the unsaturated benzophenone type ultraviolet absorber is obtained; wherein the molar ratio of 2,4,4-trihydroxybenzophenone, acryloyl chloride and sodium hydroxide is 1:1.1:1.

[0050] Further, the preparation method of the flame-retardant wear-resistant filler is as follows: carboxylated nano-silica is dispersed in toluene with a mass of 40 times that of the carboxylated nano-silica, then 0.6 times the amount of substance of pentaerythritol corresponding to the carboxyl groups in the carboxylated nano-silica is added, stirred at 500 rpm for 40 min, then 0.4 times the mass of concentrated sulfuric acid corresponding to the carboxylated nano-silica is added, heated to reflux for 4h, filtered, washed with acetone and deionized water 4 times in turn, dried in an oven at 80℃ for 48h, then mixed with phosphorus oxychloride, wherein the molar ratio of pentaerythritol and phosphorus oxychloride is 1:6.5, heated to 80℃ and reacted for 2.2h, then heated to 110℃, stirred at 1700 rpm overnight until substantially no hydrogen chloride gas is generated, then cooled to room temperature, filtered and dried to constant weight in a vacuum drying oven at 80℃, to obtain the flame-retardant wear-resistant filler; wherein during the filtration process, dichloromethane and diethyl ether are used for washing 3 times, respectively.

[0051] Further, the preparation method of the carboxylated nano-silica is as follows: nano-silica is ultrasonically dispersed in N,N-dimethylformamide with a mass of 40 times that of the nano-silica for 40 min, then a 6% mass fraction of KH550 hydrolysate is added, wherein the mass of the KH550 hydrolysate is 2 times the mass of the nano-silica, then ultrasonic stirring is continued for 5h, then the mixture is poured into deionized water with a mass of 100 times that of the nano-silica, left to stand for 24h, filtered, dried in an oven at 120℃ for 48h, then naturally cooled to room temperature, dispersed in benzene with a mass of 60 times that of the nano-silica, and added with an equal molar amount of terephthalic acid, heated to 95℃, and continued to be ultrasonically stirred for 2h, filtered, washed with acetone and deionized water 4 times in turn, and dried in an oven at 80℃ for 48h, to obtain the carboxylated nano-silica.

[0052] Comparative Example 1

[0053] The difference between Comparative Example 1 and Example 2 is that only UV-0, SEBS and maleic anhydride are blended and extruded to obtain an anti-ultraviolet SEBS; the remaining steps and ingredients are the same as those of Example 2.

[0054] Comparative Example 2

[0055] The difference between Comparative Example 2 and Example 2 is only that only the unsaturated benzophenone ultraviolet absorber, SEBS copolymerization grafting is obtained to obtain the anti-ultraviolet SEBS; the rest of the steps and ingredients are the same as Example 2.

[0056] Comparative Example 3

[0057] The difference between Comparative Example 3 and Example 2 is only that the UV-0, SEBS is blended and extruded to obtain the anti-ultraviolet SEBS, and the mercury chloride and iodine are not introduced; the rest of the steps and ingredients are the same as Example 2.

[0058] Comparative Example 4

[0059] The difference between Comparative Example 4 and Example 2 is only that only the nanosilica, pentaerythritol, and phosphorus oxychloride are mixed and reacted to obtain the flame-retardant and wear-resistant filler; the rest of the steps and ingredients are the same as Example 2.

[0060] Comparative Example 5

[0061] The difference between Comparative Example 5 and Example 2 is only that only the carboxylated nanosilica and pentaerythritol phosphate are mixed and reacted to obtain the flame-retardant and wear-resistant filler; the pentaerythritol phosphate is 10 parts by mass; the rest of the steps and ingredients are the same as Example 2.

[0062] Comparative Example 6

[0063] The difference between Comparative Example 6 and Example 2 is only that only the UV-0, triethylamine, flame-retardant and wear-resistant filler, TPEE, polymer wax, and foaming agent are mixed and reacted to obtain the anti-aging and yellowing-resistant foamed polyester material; the rest of the steps and ingredients are the same as Example 2.

[0064] Comparative Example 7

[0065] The difference between Comparative Example 7 and Example 2 is only that only the anti-ultraviolet SEBS, triethylamine, nanometer titanium dioxide, pentaerythritol phosphate, TPEE, polymer wax, and foaming agent are mixed and reacted to obtain the anti-aging and yellowing-resistant foamed polyester material; the nanometer titanium dioxide is 5 parts by mass, and the pentaerythritol phosphate is 10 parts by mass; the rest of the steps and ingredients are the same as Example 2.

[0066] Effect Example

[0067] Oxygen Index: The anti-aging and yellowing-resistant foamed polyester material prepared in the examples and comparative examples is prepared into a sample with a size of 130 mm x 10 mm x 3 mm, and the oxygen index is tested by using the oxygen index tester of the British FTT company according to the test standard GB / T 2406.2-2009.

[0068] Vertical burning performance: the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were prepared into samples with a size of 130 mm x 13 mm x 4 mm, and the vertical burning performance was determined by referring to ASTM D3801-1996 and using a vertical burning instrument of UL94 type from the British FTT Company.

[0069] Apparent density: the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were tested for the apparent density according to GB / T6343-1995.

[0070] Tensile strength: the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were tested for the tensile strength according to GB / T528-2009, using a type 1 sample and a tensile speed of 500 mm / min.

[0071] Compression permanent deformation: the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were tested for the compression permanent deformation according to GB / T10653-2001; the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were processed into regular square shapes and stacked together, so as to ensure that the thickness of the samples before compression was ≥25 mm, the side length was 50 mm±1 mm, and the thickness was 25 mm±1 mm; the test conditions were as follows: the compression amount was controlled to be 30%, the temperature was 70℃±1℃, and the time was 22 h.

[0072] Anti-ultraviolet aging performance: the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples and the comparative examples were tested for the tensile strength retention rate after irradiation for 5 days according to GB / T16422.3-2014; the tensile strength retention rate = (the tensile strength after aging for 5 d) *100% / the tensile strength before aging.

[0073] The following table 1 shows the test and analysis results of various performances of the anti-aging and yellowing-resistant foamed polyester materials prepared from the examples 1-3 and the comparative examples 1-7 of the present application.

[0074] Table 1

[0075] Apparent density (g*cm -3 ) Tensile strength (MPa) Compression set (%) Tensile strength retention (%) Limiting oxygen index (%) Vertical burning performance (UL-94) Example 1 0.674 14.32 13.42 91.2 30.2 V-1 Example 2 0.658 17.01 12.01 94.5 30.8 V-1 Example 3 0.669 16.65 13.23 92.4 30.6 V-1 Comparative Example 1 0.754 6.23 15.75 82.3 30.6 V-1 Comparative Example 2 0.806 5.75 16.54 85.2 30.1 V-1 Comparative Example 3 0.744 5.63 16.73 81.5 30.2 V-1 Comparative Example 4 0.813 6.32 17.22 91.4 27.2 V-2 Comparative Example 5 0.726 13.43 14.14 91.8 27.4 V-2 Comparative Example 6 0.889 5.52 19.22 86.4 27.2 V-2 Comparative Example 7 0.665 8.23 14.78 92.3 26.6 RT

[0076] It can be found from Table 1 that the anti-aging and yellowing-resistant foamed polyester material prepared in the examples has good foaming performance, mechanical property, flame retardant property and anti-UV aging property; it can be found by comparing Example 2 with Comparative Example 1 that the anti-aging and yellowing-resistant foamed polyester material prepared by using the unsaturated benzophenone ultraviolet absorber to prepare antioxidant SEBS has good foaming performance, anti-UV aging property and mechanical property; it can be found by comparing Example 2 with Comparative Example 2 that the anti-aging and yellowing-resistant foamed polyester material prepared by using maleic anhydride to prepare antioxidant SEBS has good foaming performance and mechanical property; it can be found by comparing Example 2 with Comparative Example 3 that the anti-aging and yellowing-resistant foamed polyester material prepared by using the unsaturated benzophenone ultraviolet absorber and maleic anhydride to graft copolymerize SEBS to prepare antioxidant SEBS has good mechanical property, anti-UV aging property and foaming performance; it can be found by comparing Example 2 with Comparative Example 4 that the anti-aging and yellowing-resistant foamed polyester material prepared by using carboxylated nano-silicon dioxide to prepare the flame-retardant and wear-resistant filler has good flame retardant property, foaming property and mechanical property; it can be found by comparing Example 2 with Comparative Example 5 that the anti-aging and yellowing-resistant foamed polyester material prepared by using carboxylated nano-silicon dioxide, pentaerythritol and phosphorus oxychloride to prepare the flame-retardant and wear-resistant filler has good flame retardant property, foaming property and mechanical property; it can be found by comparing Example 2 with Comparative Example 6 that the anti-aging and yellowing-resistant foamed polyester material prepared by using anti-UV SEBS has good mechanical property, foaming property, flame retardant property and anti-UV aging property; it can be found by comparing Example 2 with Comparative Example 7 that the anti-aging and yellowing-resistant foamed polyester material prepared by using carboxylated nano-silicon dioxide to prepare the flame-retardant filler has good mechanical property, foaming property and flame retardant property.

[0077] In addition, it should be noted that various specific technical features described in the foregoing embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present application.

Claims

1. An anti-aging and yellowing resistant foamed polyester material, characterized in that, The raw material components, by weight, include: 3-5 parts of UV-resistant SEBS, 3.6-7 parts of triethylamine, 4-6 parts of flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9-1.1 parts of polymer wax, and 0.6-0.8 parts of foaming agent; the UV-resistant SEBS is obtained by copolymer grafting of unsaturated benzophenone-based UV absorber, SEBS, and maleic anhydride.

2. The anti-aging and yellowing-resistant foamed polyester material according to claim 1, characterized in that, The flame-retardant and wear-resistant filler is obtained by mixing and reacting carboxylated nano-silica, pentaerythritol, and phosphorus oxychloride.

3. The anti-aging and yellowing-resistant foamed polyester material according to claim 1, characterized in that, The polymer wax is EVA wax.

4. The anti-aging and yellowing-resistant foamed polyester material according to claim 1, characterized in that, The foaming agent used is azodicarbonamide.

5. A method for preparing an anti-aging and yellowing-resistant foamed polyester material as described in any one of claims 1 to 4, characterized in that, The preparation steps include the following: (1) Prepare materials according to the following weight proportions: 3~5 parts of UV-resistant SEBS, 3.6~7 parts of triethylamine, 4~6 parts of flame-retardant and wear-resistant filler, 100 parts of TPEE, 0.9~1.1 parts of polymer wax, and 0.6~0.8 parts of foaming agent; (2) Under nitrogen protection, UV-resistant SEBS and toluene are mixed at a mass ratio of 1:20~40 and stirred at 500~900 rpm for 2~4 hours. Then, triethylamine and flame-retardant and wear-resistant filler are added and stirred at 90°C for 13~15 hours. After naturally cooling to room temperature, the mixture is filtered and washed with ethyl acetate and deionized water 3~5 times in sequence. It is then placed in a vacuum drying oven and dried at 100°C overnight until constant weight. Then, it is mixed with TPEE and EVA wax in a high-speed mixer and stirred at 70°C for 2~4 minutes. The foaming agent azodicarbonamide is added, and after mixing evenly, the mixture is discharged. It is then extruded in a single-screw extruder with a metering section temperature of 220~230°C, a die head temperature of 195°C, and a screw speed of 60 rpm. The mixture is cooled by a calender, drawn, and calendered into sheets.

6. The method for preparing the anti-aging and yellowing-resistant foamed polyester material according to claim 5, characterized in that, The method for preparing the UV-resistant SEBS is as follows: Maleic anhydride is dried in a vacuum drying oven at 120°C for more than 12 hours. First, maleic anhydride, unsaturated benzophenone-based UV absorber, dicumyl peroxide, and acetone are stirred and dissolved in a mass ratio of 1:1.2~1.4:0.09~0.11:

10. Then, the solution is evenly sprinkled on the surface of SEBS powder with a mass of 90~100 times that of maleic anhydride. Next, the solution is placed in a high-speed mixer and stirred at 1000~2000 rpm for 5 minutes. The stirring temperature is set to 80°C. After mixing, the solution is extruded using a twin-screw extruder. The temperatures of each zone of the extruder are set to 220, 245, 265, 285, and 270°C, respectively, and the screw speed is set to 40 r / min.

7. The method for preparing the anti-aging and yellowing-resistant foamed polyester material according to claim 6, characterized in that, The preparation method of the unsaturated benzophenone-based ultraviolet absorber is as follows: 1 M / L sodium hydroxide aqueous solution and 2,4,4-trihydroxybenzophenone are mixed and completely dissolved at 300-500 rpm. Then, the mixture is stirred at 1200-1500 rpm in an ice-water bath, and acryloyl chloride is added dropwise. The reaction is carried out for 1.5-2.5 h, filtered, and the unsaturated benzophenone-based ultraviolet absorber is obtained. The molar ratio of 2,4,4-trihydroxybenzophenone, acryloyl chloride, and sodium hydroxide is 1:0.9-1.1:

1.

8. The method for preparing the anti-aging and yellowing-resistant foamed polyester material according to claim 5, characterized in that, The preparation method of the flame-retardant and wear-resistant filler is as follows: Carboxylated nano-silica is dispersed in toluene at 20-40 times its mass, followed by the addition of pentaerythritol at 0.5-0.6 times the amount of carboxyl groups in the carboxylated nano-silica. The mixture is stirred at 300-500 rpm for 20-40 minutes. Then, concentrated sulfuric acid at 0.2-0.4 times its mass is added, and the mixture is heated under reflux for 2-4 hours. After filtration, the mixture is washed 2-4 times successively with acetone and deionized water, and then placed in an 80℃ oven. The mixture was dried in a medium-density state for 48 hours, then mixed with phosphorus oxychloride, wherein the molar ratio of pentaerythritol to phosphorus oxychloride was 1:6~6.

5. The mixture was heated to 80℃ and reacted for 1.8~2.2 hours, then heated to 110℃ and stirred at 1300~1700 rpm overnight until almost no hydrogen chloride gas was produced. The mixture was then cooled to room temperature, filtered, and dried in a vacuum drying oven at 80℃ to constant weight to obtain flame-retardant and wear-resistant filler. During the filtration process, the filler was washed three times with dichloromethane and diethyl ether, respectively.

9. The method for preparing the anti-aging and yellowing-resistant foamed polyester material according to claim 8, characterized in that, The preparation method of the carboxylated nano-silica is as follows: Nano-silica is ultrasonically dispersed in 20-40 times its mass of N,N-dimethylformamide for 20-40 min, then 6% KH550 hydrolysate is added, wherein the mass of KH550 hydrolysate is 1-2 times the mass of nano-silica, and then ultrasonically stirred for 5 h. After that, it is poured into 50-100 times its mass of deionized water, allowed to stand for 24 h, filtered, and dried in an oven at 120℃ for 48 h. After naturally cooling to room temperature, it is dispersed in 40-60 times its mass of benzene, and equimolar amounts of terephthalic acid of KH550 are added. The temperature is raised to 85-95℃, and ultrasonically stirred for 1-2 h is continued. After filtration, it is washed 2-4 times with acetone and deionized water, and then dried in an oven at 80℃ for 48 h to obtain carboxylated nano-silica.

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