An ultrahigh-aging-resistant polypropylene composite material, a preparation method and application thereof

Abstract

The application discloses an ultrahigh anti-aging polypropylene composite material and a preparation method and application thereof. The composite material comprises the following components in parts by weight: 95-100 parts of polypropylene, 5-15 parts of ethylene-octene copolymer, 0.1-2 parts of an anti-aging compound, 2-5 parts of terpene resin, 2-5 parts of naphthenic oil, 0.5-5 parts of stearic acid and 0.5-5 parts of zinc stearate. The anti-aging compound comprises the following components in a weight ratio: 10-30% of modified graphene oxide / hydrotalcite, 10-30% of modified triazine charring agent, 20-40% of antioxidant and 20-40% of light stabilizer. The polypropylene composite material provided by the application has remarkably improved anti-aging properties, including heat-oxygen aging resistance, hot water aging resistance, light aging resistance and the like, and has good flowability and dispersibility, water resistance, yellowing resistance, good processing performance and mechanical properties and excellent comprehensive performance.

Description

Technical Field

[0001] This invention relates to a composite material, and more particularly to an ultra-high aging-resistant polypropylene composite material, its preparation method, and its application. Background Technology

[0002] Polypropylene (PP), as a general-purpose plastic, is widely used in industries such as home appliances, furniture, packaging, automobiles, and construction due to its excellent mechanical properties, processing performance, and low cost. However, because PP contains tertiary carbon atoms in its main chain, its hydrogen atoms are easily stripped by oxygen under long-term high-temperature conditions, triggering a chain degradation reaction that gradually leads to the loss of its basic mechanical properties, significantly limiting its application areas. PP is also susceptible to photo-oxidative degradation under ultraviolet light. In addition to the structure of the PP resin itself, the presence of other additives and impurities in the PP composite system makes it particularly sensitive to light. When used under light or in certain harsh environments, it is prone to brittleness, surface cracking, stickiness, yellowing, and fading, reducing the service life of PP materials and restricting their application in high-end fields such as automobiles and home appliances.

[0003] In recent years, the influence of various components in PP composites on the long-term aging resistance of PP materials has become a research hotspot in the application field of PP materials.

[0004] Current research has focused on improving the aging resistance of PP materials by enhancing their resistance to single thermo-oxidative or photo-aging conditions. However, no research has been conducted that can simultaneously meet the aging resistance requirements under complex weathering conditions, including thermo-oxidative, hot water, and photo-aging. This invention introduces a modified synergistic agent into the PP formulation system to form an aging-resistant compound, which is then compounded with PP to prepare an ultra-high aging-resistant polypropylene composite material. This composite material can meet the aging resistance requirements under complex aging conditions. The preparation method is simple, the performance is highly efficient, and it expands the application range of PP materials. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes an ultra-high aging-resistant polypropylene composite material, its preparation method, and its applications. The polypropylene composite material provided by this invention, through synergistic compounding of its components, exhibits significantly improved aging resistance, including resistance to heat-oxidative aging, hot water aging, and light aging, as well as good flowability and dispersibility, water resistance, and yellowing resistance. It also possesses excellent processing and mechanical properties, demonstrating superior overall performance and making it widely applicable in fields such as household appliances and automotive modification.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] An ultra-high aging-resistant polypropylene composite material, characterized in that, by weight, it comprises the following components:

[0008] 95-100 parts polypropylene, 5-15 parts ethylene-octene copolymer, 0.1-2 parts aging resistant compounding agent, 2-5 parts terpene resin, 2-5 parts naphthenic oil, 0.5-5 parts stearic acid, and 0.5-5 parts zinc stearate;

[0009] The anti-aging compound agent comprises the following components by weight:

[0010] Modified graphene oxide / hydrotalcite, 10-30%,

[0011] Modified triazine charring agent, 10-30%,

[0012] Antioxidant, 20-40%,

[0013] Light stabilizer, 20-40%.

[0014] As a preferred embodiment of the present invention, the polypropylene is isotactic or atactic copolymer polypropylene with a melt index of 3-30 g / 10 min and a weight-average molecular weight of 10 × 10⁻⁶. 4 -50×10 4 g / mol, preferably selected from one or more of WH-EP548R, WH-EP648V, WH-EP649U, WH-EP300H, WH-EP564M, WH-HP648T, WH-HP456J, and WH-RP340R.

[0015] As a preferred embodiment of the present invention, the ethylene-octene copolymer has a melt index of 0.5-5 g / 10 min and an octene insertion rate of 20-40%, preferably one of 8150 or 8200.

[0016] As a preferred embodiment of the present invention, the modified graphene oxide / hydrotalcite is prepared by the following method:

[0017] A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide.

[0018] A2. Disperse hydrotalcite in water and vigorously stir and break it into a white slurry at high temperature to obtain hydrotalcite emulsion;

[0019] A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is complete, filter, wash and dry to obtain modified graphene oxide / hydrotalcite.

[0020] In a preferred embodiment of the present invention, the diazotization reaction method in step A1 is as follows:

[0021] p-Aminobenzenesulfonic acid was dissolved in sodium hydroxide solution, sodium nitrite was added under ice bath and mixed evenly, hydrochloric acid solution was slowly added, and after the reaction, p-aminobenzenesulfonic acid diazonium salt was obtained.

[0022] Preferably, the amount of sodium hydroxide used is 30-50% of the mass of p-aminobenzenesulfonic acid;

[0023] Preferably, the mass ratio of sodium nitrite to p-aminobenzenesulfonic acid is (0.2-0.5):1;

[0024] Preferably, the mass ratio of hydrochloric acid to p-aminobenzenesulfonic acid is 1:(0.5-2).

[0025] In a preferred embodiment of the present invention, in step A1, the mass ratio of graphene oxide to p-aminobenzenesulfonic acid is (0.2-1):1.

[0026] Preferably, the reaction time of the graphene oxide and the diazonium salt of p-aminobenzenesulfonic acid is 2-10 h.

[0027] In a preferred embodiment of the present invention, in step A2, the hydrotalcite is dispersed by vigorous stirring at 80-120°C for 10-60 minutes.

[0028] In a preferred embodiment of the present invention, in step A3, the mass ratio of modified graphene oxide to hydrotalcite is 1:(0.5-2);

[0029] Preferably, the stirring reaction conditions in step A3 are: stirring reaction at 80-120℃ for 2-6 hours.

[0030] As a preferred embodiment of the present invention, the preparation method of the modified triazine charring agent is as follows:

[0031] B1. Allow cyanuric chloride and ethanolamine to react for a period of time first, then add ethylenediamine to continue the reaction;

[0032] B2. The product obtained in step B1 is reacted with L-2-aminohexanoic acid to obtain a modified triazine charring agent.

[0033] Preferably, the molar ratio of cyanuric chloride, ethanolamine, and ethylenediamine is 1:(0.8-1.2):(0.5-1);

[0034] Preferably, the amount of L-2-aminoadipic acid used is (0.2-0.5):1, calculated according to the molar ratio of cyanuric chloride to that in step B1.

[0035] Preferably, the reaction conditions in step B1 are as follows: cyanuric chloride and ethanolamine react at 3-10°C for 0.5-1 h, then a portion of ethylenediamine is added and the temperature is raised to 50-55°C for 0.5-1 h, and finally the remaining ethylenediamine is added and the temperature is raised to 95-100°C for 0.5-1 h; more preferably, the ethylenediamine added initially accounts for 30-50% of its total mass;

[0036] Preferably, the reaction conditions in step B2 are: reaction at room temperature for 0.5-1 h.

[0037] In a preferred embodiment of the present invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 3114;

[0038] Preferably, the light stabilizer is selected from one or more of light stabilizer 770, light stabilizer 944, and light stabilizer 622.

[0039] This invention also provides a method for preparing an ultra-high aging-resistant polypropylene composite material, comprising the following steps:

[0040] The above-mentioned polypropylene, ethylene-octene copolymer, anti-aging compounding agent, terpene resin, naphthenic oil, stearic acid, and zinc stearate are mixed and melt-blended to obtain a composite material;

[0041] Preferably, the melt mixing conditions are: mixing at 180-220℃ for 20-30 minutes.

[0042] An application of an ultra-high aging-resistant polypropylene composite material as described above in the modification of household appliances and automobiles.

[0043] In this invention, the modified additives help to improve the overall aging resistance, water resistance, and yellowing resistance of polypropylene composites, and can avoid agglomeration when added alone, resulting in good dispersion. Terpene resins have advantages such as good antioxidant properties, good thermal stability, and good system compatibility. When combined with ethylene-octene copolymers and naphthenic oils, they can not only improve the aging resistance of polypropylene composites, but also synergistically improve the dispersibility of other modified additives and enhance their compatibility in the matrix. Thus, while improving the aging resistance of the material, it also maintains excellent mechanical properties. Detailed Implementation

[0044] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0045] The main raw materials used in this invention are as follows:

[0046] Polypropylene WH-EP548R: Melt index 30g / 10min, weight average molecular weight 30×10 4g / mol, manufacturer: Wanhua Chemical;

[0047] Polypropylene WH-EP648VM: Melt index 100g / 10min, weight average molecular weight 15×10 4 g / mol, manufacturer: Wanhua Chemical;

[0048] Polypropylene WH-EP649UH: Melt index 60g / 10min, weight average molecular weight 20×10 4 g / mol, manufacturer: Wanhua Chemical;

[0049] Polypropylene WH-RP340R: Melt index 20g / 10min, weight average molecular weight 25×10 4 g / mol, manufacturer: Wanhua Chemical;

[0050] Ethylene-octene copolymer 8150, melt index 0.5 g / 10 min, octene insertion rate 30%, manufacturer: Dow Chemical;

[0051] Ethylene-octene copolymer 8200, melt index 5g / 10min, octene insertion rate 20%, manufacturer: Dow Chemical;

[0052] Unless otherwise specified, all other raw materials and actual products were obtained through regular commercial channels.

[0053] The main testing methods involved in this invention are as follows:

[0054] 1) Retention rate of yield strength after thermo-oxidative aging: The sample was first treated at 150℃ for 250h, and then the tensile yield strength was determined according to GB / T1840-1992.

[0055] 2) Retention rate of yield strength after hot water aging: The sample was first soaked in hot water at 95℃ for 300h, and then subjected to heat aging at 150℃ for 250h; the tensile yield strength was then determined according to GB / T 1840-1992.

[0056] 3) UV-aged yield strength retention rate: After the sample is UV-aged for 1000h, the tensile yield strength is determined according to GB / T1840-1992.

[0057] 4) Color difference ΔE after UV aging: After UV aging for 110 hours, the appearance color index of the plastic was determined according to HG / T 3862-2006.

[0058]

Example 1

[0059] An ultra-high aging-resistant polypropylene composite material, comprising the following components by weight:

[0060] 100 parts of polypropylene WH-EP548R, 5 parts of ethylene-octene copolymer 8150, 1 part of aging resistant compounding agent, 2 parts of terpene resin, 2 parts of naphthenic oil, 0.5 parts of stearic acid, and 0.5 parts of zinc stearate;

[0061] The anti-aging compound agent comprises the following components by weight:

[0062] Modified graphene oxide / hydrotalcite, 20%

[0063] Modified triazine charring agent, 20%

[0064] Antioxidant 3114, 15%

[0065] Antioxidant 168, 15%

[0066] Light stabilizer 944, 15%

[0067] Light stabilizer 770, 15%

[0068] In this embodiment, the modified graphene oxide / hydrotalcite is prepared by the following method:

[0069] A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide.

[0070] The method for diazotization reaction is as follows: Dissolve 1g of p-aminobenzenesulfonic acid in 8g of 5% sodium hydroxide solution, add 0.4g of sodium nitrite under ice bath and mix well, then slowly add 2g of 37% hydrochloric acid solution, and after the reaction, p-aminobenzenesulfonic acid diazonium salt is obtained.

[0071] The mass ratio of graphene oxide to p-aminobenzenesulfonic acid was 0.5:1; the reaction time was 2 hours.

[0072] A2. Disperse the hydrotalcite in water and stir vigorously at 100°C for 30 minutes to disperse it into a white slurry to obtain a hydrotalcite emulsion.

[0073] A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is completed, filter, wash and dry to obtain modified graphene oxide / hydrotalcite.

[0074] The mass ratio of modified graphene oxide to hydrotalcite was 1:2, and the reaction conditions were: stirring at 100℃ for 2 hours.

[0075] In this embodiment, the preparation method of the modified triazine charring agent is as follows:

[0076] B1, cyanuric chloride and ethanolamine react at 5°C for 0.5 h, then a portion of ethylenediamine is added and the temperature is raised to 50°C for another 0.5 h, and finally the remaining ethylenediamine is added and the temperature is raised to 95°C for another 0.5 h; the molar ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:1:0.5; the ethylenediamine added initially accounts for 30% of its total mass;

[0077] B2. The product obtained in step B1 is reacted with L-2-aminoadipic acid at room temperature for 0.5 h to obtain a modified triazine charring agent; the amount of L-2-aminoadipic acid used is 0.5:1 based on the molar ratio of L-2-aminoadipic acid to cyanuric chloride in step B1.

[0078] Polypropylene, ethylene-octene copolymer, anti-aging compounding agent, terpene resin, naphthenic oil, stearic acid, and zinc stearate were mixed and melt-blended to obtain a polypropylene composite material. The melt-blending conditions were: blending at 200℃ for 30 min.

[0079]

Example 2

[0080] An ultra-high aging-resistant polypropylene composite material, comprising the following components by weight:

[0081] 100 parts of polypropylene WH-EP649U, 7 parts of ethylene-octene copolymer 8200, 1 part of aging resistant compounding agent, 3 parts of terpene resin, 5 parts of naphthenic oil, 3 parts of stearic acid, and 5 parts of zinc stearate.

[0082] The anti-aging compound agent comprises the following components by weight:

[0083] Modified graphene oxide / hydrotalcite, 10%

[0084] Modified triazine charring agent, 30%

[0085] Antioxidant 3114, 10%

[0086] Antioxidant 168, 10%

[0087] Light stabilizer 944, 20%

[0088] Light stabilizer 770, 20%

[0089] In this embodiment, the modified graphene oxide / hydrotalcite is prepared by the following method:

[0090] A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide.

[0091] The method of diazotization reaction is as follows: Dissolve 1g of p-aminobenzenesulfonic acid in 5g of 10% sodium hydroxide solution, add 0.5g of sodium nitrite under ice bath and mix well, slowly add 3g of 37% hydrochloric acid solution, and after the reaction, p-aminobenzenesulfonic acid diazonium salt is obtained.

[0092] The mass ratio of graphene oxide to p-aminobenzenesulfonic acid was 1:1; the reaction time was 3 hours.

[0093] A2. Disperse the hydrotalcite in water and stir vigorously at 80°C for 40 minutes to disperse it into a white slurry to obtain a hydrotalcite emulsion.

[0094] A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is completed, filter, wash and dry to obtain modified graphene oxide / hydrotalcite.

[0095] The mass ratio of modified graphene oxide and hydrotalcite was 1:1, and the reaction conditions were: stirring at 80℃ for 2 hours.

[0096] In this embodiment, the preparation method of the modified triazine charring agent is as follows:

[0097] B1, cyanuric chloride and ethanolamine react at 3°C ​​for 0.5 h, then a portion of ethylenediamine is added and the temperature is raised to 50°C for 0.5 h, and finally the remaining ethylenediamine is added and the temperature is raised to 95°C for 0.5 h; the molar ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:1.2:0.8; the ethylenediamine added initially accounts for 40% of its total mass;

[0098] B2. The product obtained in step B1 is reacted with L-2-aminoadipic acid at room temperature for 0.5 h to obtain a modified triazine charring agent; the amount of L-2-aminoadipic acid used is 0.3:1 based on the molar ratio of L-2-aminoadipic acid to cyanuric chloride in step B1.

[0099] Polypropylene, ethylene-octene copolymer, anti-aging compounding agent, terpene resin, naphthenic oil, stearic acid, and zinc stearate were mixed and melt-blended to obtain a polypropylene composite material. The melt-blending conditions were: blending at 200℃ for 30 min.

[0100]

Example 3

[0101] An ultra-high aging-resistant polypropylene composite material, comprising the following components by weight:

[0102] 100 parts of polypropylene WH-EP648V, 10 parts of ethylene-octene copolymer 8150, 1.5 parts of aging resistant compounding agent, 3 parts of terpene resin, 3 parts of naphthenic oil, 3 parts of stearic acid, and 3 parts of zinc stearate;

[0103] The anti-aging compound agent comprises the following components by weight:

[0104] Modified graphene oxide / hydrotalcite, 30%

[0105] Modified triazine charring agent, 10%

[0106] Antioxidant 3114, 20%

[0107] Antioxidant 168, 20%

[0108] Light stabilizer 944, 10%

[0109] Light stabilizer 770, 10%

[0110] In this embodiment, the modified graphene oxide / hydrotalcite is prepared by the following method:

[0111] A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide.

[0112] The method of diazotization reaction is as follows: 1g of p-aminobenzenesulfonic acid is dissolved in 6g of 5% sodium hydroxide solution, 0.45g of sodium nitrite is added under ice bath and mixed evenly, and 5g of 36% hydrochloric acid solution is slowly added. After the reaction, p-aminobenzenesulfonic acid diazonium salt is obtained.

[0113] The mass ratio of graphene oxide to p-aminobenzenesulfonic acid was 0.5:1; the reaction time was 2 hours.

[0114] A2. Disperse the hydrotalcite in water and stir vigorously at 100°C for 30 minutes to disperse it into a white slurry to obtain a hydrotalcite emulsion.

[0115] A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is completed, filter, wash and dry to obtain modified graphene oxide / hydrotalcite.

[0116] The mass ratio of modified graphene oxide to hydrotalcite was 1:2, and the reaction conditions were: stirring at 100℃ for 2 hours.

[0117] In this embodiment, the preparation method of the modified triazine charring agent is as follows:

[0118] B1, cyanuric chloride and ethanolamine react at 5°C for 0.5 h, then a portion of ethylenediamine is added and the temperature is raised to 50°C for another 0.5 h, and finally the remaining ethylenediamine is added and the temperature is raised to 95°C for another 0.5 h; the molar ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:0.8:1; the ethylenediamine added initially accounts for 50% of its total mass;

[0119] B2. The product obtained in step B1 is reacted with L-2-aminoadipic acid at room temperature for 0.5 h to obtain a modified triazine charring agent; the amount of L-2-aminoadipic acid used is 0.2:1 based on the molar ratio of L-2-aminoadipic acid to cyanuric chloride in step B1.

[0120] Polypropylene, ethylene-octene copolymer, anti-aging compounding agent, terpene resin, naphthenic oil, stearic acid, and zinc stearate were mixed and melt-blended to obtain a polypropylene composite material. The melt-blending conditions were: blending at 200℃ for 30 min.

[0121]

Example 4

[0122] An ultra-high aging-resistant polypropylene composite material, comprising the following components by weight:

[0123] 100 parts of polypropylene WH-RP340R, 10 parts of ethylene-octene copolymer 8200, 2 parts of aging resistant compounding agent, 5 parts of terpene resin, 5 parts of naphthenic oil, 5 parts of stearic acid, and 5 parts of zinc stearate.

[0124] The anti-aging compound agent comprises the following components by weight:

[0125] Modified graphene oxide / hydrotalcite, 25%

[0126] Modified triazine charring agent, 15%

[0127] Antioxidant 3114, 15%

[0128] Antioxidant 168, 15%

[0129] Light stabilizer 944, 15%

[0130] Light stabilizer 770, 15%

[0131] In this embodiment, the modified graphene oxide / hydrotalcite is prepared by the following method:

[0132] A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide.

[0133] The method of diazotization reaction is as follows: dissolve 1g of p-aminobenzenesulfonic acid in 10g of 5% sodium hydroxide solution, add 0.5g of sodium nitrite under ice bath and mix well, slowly add 1.5g of 37% hydrochloric acid solution, and after the reaction, p-aminobenzenesulfonic acid diazonium salt is obtained.

[0134] The mass ratio of graphene oxide to p-aminobenzenesulfonic acid was 0.5:1; the reaction time was 2 hours.

[0135] A2. Disperse the hydrotalcite in water and stir vigorously at 100°C for 30 minutes to disperse it into a white slurry to obtain a hydrotalcite emulsion.

[0136] A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is completed, filter, wash and dry to obtain modified graphene oxide / hydrotalcite.

[0137] The mass ratio of modified graphene oxide to hydrotalcite was 1:2, and the reaction conditions were: stirring at 100℃ for 2 hours.

[0138] In this embodiment, the preparation method of the modified triazine charring agent is as follows:

[0139] B1, cyanuric chloride and ethanolamine react at 3°C ​​for 0.5 h, then a portion of ethylenediamine is added and the temperature is raised to 55°C for 1 h, and finally the remaining ethylenediamine is added and the temperature is raised to 95°C for 1 h; the molar ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:1.2:0.75; the ethylenediamine added initially accounts for 40% of its total mass;

[0140] B2. The product obtained in step B1 is reacted with L-2-aminoadipic acid at room temperature for 0.5 h to obtain a modified triazine charring agent; the amount of L-2-aminoadipic acid used is 0.8:1 based on the molar ratio of L-2-aminoadipic acid to cyanuric chloride in step B1.

[0141] Polypropylene, ethylene-octene copolymer, anti-aging compounding agent, terpene resin, naphthenic oil, stearic acid, and zinc stearate were mixed and melt-blended to obtain a polypropylene composite material. The melt-blending conditions were: blending at 200℃ for 30 min.

[0142] Comparative Example 1

[0143] Polypropylene composite materials were prepared using essentially the same method as in Example 1, except that no modified graphene oxide / hydrotalcite was added.

[0144] Comparative Example 2

[0145] Polypropylene composite materials were prepared using essentially the same method as in Example 1, except that the modified triazine charring agent was replaced with the flame retardant ammonium polyphosphate.

[0146] Comparative Example 3

[0147] The polypropylene composite material was prepared using essentially the same method as in Example 1, except that ethylene-octene copolymer and naphthenic oil were not added.

[0148] Comparative Example 4

[0149] The polypropylene composite material was prepared using essentially the same method as in Example 1, except that no terpene resin was added.

[0150] Comparative Example 5

[0151] The polypropylene composite material was prepared using essentially the same method as in Example 1, except that the modified graphene oxide / hydrotalcite was replaced with a mixed filler prepared by the following method:

[0152] A1. Disperse hydrotalcite in water and stir vigorously at 100°C for 30 minutes to disperse it into a white slurry to obtain a hydrotalcite emulsion.

[0153] A2. After mixing graphene oxide and hydrotalcite emulsion, the mixture was stirred and reacted. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a graphene oxide / hydrotalcite mixed filler. The mass ratio of graphene oxide to hydrotalcite was 1:2, and the reaction conditions were: stirring at 100℃ for 2 hours.

[0154] The polypropylene composite materials prepared in each example and comparative example were pressed into 3-5 mm sheets using a sheeting machine. After cutting, they were extruded and granulated using a twin-screw extruder at 200℃±5℃ to obtain polypropylene composite material products. The performance tests for each product were performed as shown in Table 1, and the results are as follows:

[0155] Table 1. Performance Test Results

[0156]

[0157] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A polypropylene composite material with ultra-high aging resistance, characterized in that, Based on parts by weight, it comprises the following components: 95-100 parts polypropylene, 5-15 parts ethylene-octene copolymer, 0.1-2 parts aging resistant compounding agent, 2-5 parts terpene resin, 2-5 parts naphthenic oil, 0.5-5 parts stearic acid, and 0.5-5 parts zinc stearate; The anti-aging compound agent comprises the following components by weight: Modified graphene oxide / hydrotalcite, 10-30%, Modified triazine charring agent, 10-30%, Antioxidant, 20-40%, Light stabilizer, 20-40%; The modified graphene oxide / hydrotalcite was prepared by the following method: A1. P-aminobenzenesulfonic acid is converted into p-aminobenzenesulfonic acid diazonium salt through a diazotization reaction; graphene oxide is fully dispersed and then mixed with p-aminobenzenesulfonic acid diazonium salt, and reacted under ice bath to obtain modified graphene oxide. A2. Disperse hydrotalcite in water and vigorously stir and break it into a white slurry at high temperature to obtain hydrotalcite emulsion; A3. After mixing the modified graphene oxide and hydrotalcite emulsion, stir and react. After the reaction is completed, filter, wash and dry to obtain modified graphene oxide / hydrotalcite. The preparation method of the modified triazine charring agent is as follows: B1. Allow cyanuric chloride and ethanolamine to react for a period of time first, then add ethylenediamine to continue the reaction; B2. The product obtained in step B1 is reacted with L-2-aminohexanoic acid to obtain a modified triazine charring agent.

2. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, The polypropylene is isotactic or atactic copolymer polypropylene with a melt index of 3-30 g / 10 min and a weight-average molecular weight of 10 × 10⁻⁶. 4 -50×10 4 g / mol.

3. The ultra-high aging resistance polypropylene composite material according to claim 2, characterized in that, The polypropylene is selected from one or more of WH-EP548R, WH-EP648V, WH-EP649U, WH-EP300H, WH-EP564M, WH-HP648T, WH-HP456J, and WH-RP340R.

4. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, The ethylene-octene copolymer has a melt index of 0.5-5 g / 10 min and an octene insertion rate of 20-40%.

5. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, In step A1, the diazotization reaction is performed as follows: p-Aminobenzenesulfonic acid was dissolved in sodium hydroxide solution, and sodium nitrite was added under ice bath and mixed thoroughly. Hydrochloric acid solution was then slowly added, and the reaction yielded diazonium salt of p-aminobenzenesulfonic acid.

6. The ultra-high aging resistance polypropylene composite material according to claim 5, characterized in that, In step A1, the amount of sodium hydroxide used is 30-50% of the mass of p-aminobenzenesulfonic acid.

7. The ultra-high aging resistance polypropylene composite material according to claim 5, characterized in that, In step A1, the mass ratio of sodium nitrite to p-aminobenzenesulfonic acid is (0.2-0.5):

1.

8. The ultra-high aging resistance polypropylene composite material according to claim 5, characterized in that, In step A1, the mass ratio of hydrochloric acid to p-aminobenzenesulfonic acid is (0.5-2):

1.

9. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, In step A1, the mass ratio of graphene oxide to p-aminobenzenesulfonic acid is (0.2-1):

1.

10. The ultra-high aging resistance polypropylene composite material according to claim 9, characterized in that, In step A1, the reaction time of the mixed graphene oxide and p-aminobenzenesulfonic acid diazonium salt is 2-10 h.

11. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, In step A2, the hydrotalcite is dispersed by vigorous stirring at 80-120℃ for 10-60 minutes.

12. The ultra-high aging resistance polypropylene composite material according to claim 1, characterized in that, In step A3, the mass ratio of modified graphene oxide to hydrotalcite is 1:(0.5-2).

13. The ultra-high aging resistance polypropylene composite material according to claim 12, characterized in that, The stirring reaction conditions in step A3 are: stirring at 80-120℃ for 2-6 hours.

14. The ultra-high aging resistance polypropylene composite material according to any one of claims 1-4, characterized in that, In step B1, the molar ratio of cyanuric chloride, ethanolamine, and ethylenediamine is 1:(0.8-1.2):(0.5-1).

15. The ultra-high aging resistance polypropylene composite material according to claim 14, characterized in that, The amount of L-2-aminoadipic acid used is (0.2-0.5):1, calculated according to the molar ratio of cyanuric chloride to that in step B1.

16. The ultra-high aging resistance polypropylene composite material according to claim 14, characterized in that, The reaction conditions in step B1 are as follows: cyanuric chloride and ethanolamine react at 3-10℃ for 0.5-1h, then a portion of ethylenediamine is added and the temperature is raised to 50-55℃ for 0.5-1h, and finally the remaining ethylenediamine is added and the temperature is raised to 95-100℃ for 0.5-1h.

17. The ultra-high aging resistance polypropylene composite material according to claim 14, characterized in that, In step B1, the ethylenediamine added initially accounts for 30-50% of its total mass.

18. The ultra-high aging resistance polypropylene composite material according to claim 14, characterized in that, The reaction conditions in step B2 are: react at room temperature for 0.5-1 h.

19. The ultra-high aging resistance polypropylene composite material according to any one of claims 1-4, characterized in that, The antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 3114.

20. The ultra-high aging resistance polypropylene composite material according to claim 19, characterized in that, The light stabilizer is selected from one or more of light stabilizer 770, light stabilizer 944, and light stabilizer 622.

21. The application of an ultra-high aging-resistant polypropylene composite material according to any one of claims 1-20 in the modification of household appliances and automobiles.

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