High-toughness anti-aging PP material and preparation method thereof

Abstract

The invention relates to the technical field of polypropylene, and discloses a high-toughness anti-aging PP material and a preparation method thereof.The high-toughness anti-aging PP material is obtained by evenly mixing polypropylene resin, nylon resin, epoxy oleic acid tris (2-acylaminoethyl) amine and an antioxidant and conducting melt blending and extrusion granulation through a double-screw extruder. Epoxy oleic acid tri (2-acylaminoethyl) amine contains a plurality of oleic acid aliphatic chains and forms a physical interpenetrating network with polypropylene, and meanwhile, a molecular chain contains an epoxy group and can react with an amino-terminated group of nylon in a high-temperature melting process, so that the compatibility between the polypropylene and the nylon is improved, the melt flow rate is increased, and the processing performance is improved; meanwhile, the impact strength and the bending strength of the material are improved, the toughness is excellent, the mass loss temperature of the material is increased, the heat resistance is changed, and the thermal aging performance is improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of polypropylene, in particular to a high-toughness anti-aging PP material and a preparation method thereof. BACKGROUND

[0002] Polypropylene is a common thermoplastic plastic, and the mechanical strength, wear resistance, cold resistance and other properties of polypropylene can be improved by modifying polypropylene with high-performance resins such as nylon. However, the solubility parameters of polypropylene and nylon are quite different, and the two belong to incompatible systems, which will affect the toughness, heat resistance, aging resistance and other properties of the material. Therefore, it is usually necessary to add compatibilizers, lubricants and other additives, such as maleic anhydride grafted polypropylene, glycidyl methacrylate grafted polypropylene and the like, to improve the compatibility and processing performance of the two.

[0003] Oleic acid is mainly derived from animals and plants in nature, is cheap and easy to obtain, has good biocompatibility, and can be made into compatibilizers, plasticizers, lubricants and the like, and has good practical application in the processing aids of high polymer materials. The development and utilization of oleic acid is a research hotspot. The application aims to improve the compatibility of polypropylene and nylon, improve the processing performance and the toughness of the material by using oleic acid tris(2-amidoethyl)amine. SUMMARY

[0004] (I) The technical problem solved by the application is that the polypropylene material has poor toughness, temperature resistance and aging resistance.

[0005] (II) To solve the above technical problems, the technical scheme adopted by the application is as follows: a preparation method of a high-toughness anti-aging PP material:

[0006] (1) Water and tris(2-aminoethyl)amine are added to acetone, oleoyl chloride is added dropwise in an ice water bath, and sodium hydroxide aqueous solution is added dropwise, then the acetone is removed by distillation under reduced pressure after the reaction, the product is washed with acetone after filtration, and the product is separated by silica gel column chromatography to obtain oleic acid tris(2-amidoethyl)amine.

[0007] (2) Oleic acid tris(2-amidoethyl)amine, formic acid and sodium bisulfate are stirred and mixed, and hydrogen peroxide aqueous solution is added dropwise, then the mixture is filtered after the reaction, and then the mixture is washed with sodium hydroxide aqueous solution and ethanol aqueous solution in sequence, and then the mixture is dried to obtain epoxy oleic acid tris(2-amidoethyl)amine.

[0008] (3) Polypropylene resin, nylon resin, epoxy oleic acid tris(2-amidoethyl)amine and antioxidant are mixed in a proportion of 100g:(15-50)g:(2-7)g:(0.2-0.4)g in a high-speed mixer, and then the mixture is melt-blended by a double-screw extruder, and then the mixture is extruded and granulated to obtain the high-toughness anti-aging PP material.

[0009] The ratio of tri(2-aminoethyl)amine and oleoyl chloride is 1 mol:(2.2-2.6) mol.

[0010] The pH of the reaction solution is maintained at 8-10 by adding sodium hydroxide solution dropwise.

[0011] The temperature during the reaction in (1) is 10-20 DEG C, and the reaction time is 7-10 h.

[0012] The ratio of tri(2-aminoethyl)amine, formic acid, sodium bisulfate and hydrogen peroxide solution is 100 g:(60-85) g:(3-5) g:(150-200) mL, and the mass fraction of the hydrogen peroxide solution is 30%.

[0013] The temperature during the reaction in (2) is 50-65 DEG C, and the reaction time is 6-12 h.

[0014] During the melt blending, the screw rotation speed of the double-screw extruder is set to 100-150 r / min, and the temperature of each section is 160-240 DEG C.

[0015] The antioxidant is a hindered phenol antioxidant, including antioxidant 1010, antioxidant 1076, antioxidant 245; or a phosphite antioxidant, including antioxidant 168, P-EPQ.

[0016] (III) Beneficial technical effects: The tri(2-aminoethyl)amine oleate in the application is used as a processing aid to melt blend polypropylene resin and nylon resin. The tri(2-aminoethyl)amine oleate contains multiple oleic acid fatty chains, which have high similarity with polypropylene molecular chains. The multiple oleic acid fatty chains form a physical interpenetrating network with polypropylene, and the molecular chains contain epoxy groups, which can react with the terminal amino groups of nylon during high-temperature melting, thereby improving the compatibility between polypropylene and nylon, increasing the melt flow rate, improving the processing performance, and improving the impact strength and bending strength of the material, and the material has excellent toughness. At the same time, the mass loss temperature of the material is increased, the heat resistance is changed, and the thermal aging performance is improved. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0018] Example 1:

[0019] (1) To 100 mL of acetone, 50 mL of water, 30 mmol of tri(2-aminoethyl)amine were added, and 78 mmol of oleoyl chloride was added dropwise in an ice water bath. During the reaction, 20% sodium hydroxide aqueous solution was added dropwise to maintain the pH of the reaction solution at 8. The reaction was carried out at 10°C for 10 hours. Acetone was removed by distillation under reduced pressure, and the product was washed with acetone after filtration. The product was separated by silica gel column chromatography using a mixture of ethyl acetate and petroleum ether as the eluent to obtain tri(2-amidoethyl)amine oleate. The reaction formula is as follows:

[0020]

[0021] (2) 40 g of tri(2-amidoethyl)amine oleate, 24 g of formic acid, and 2 g of sodium bisulfate were stirred and mixed, and 60 mL of 30% hydrogen peroxide aqueous solution was added dropwise. The mixture was heated to 65°C and reacted for 6 hours. After filtration, the product was washed with sodium hydroxide aqueous solution and ethanol aqueous solution in sequence, and then dried to obtain tri(2-amidoethyl)amine epoxy oleate. The reaction formula is as follows:

[0022]

[0023] (3) 1 kg of polypropylene resin (brand 1100NK, same below), 150 g of nylon resin (type PA12), 20 g of tri(2-amidoethyl)amine epoxy oleate, and 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then melt blended by a twin-screw extruder. The screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was set to 160°C, 190°C, 210°C, 225°C, 240°C, and 240°C. The mixture was extruded and granulated to obtain a high-toughness and anti-aging PP material.

[0024] Example 2:

[0025] (1) To 150 mL of acetone, 70 mL of water, and 30 mmol of tri(2-aminoethyl)amine were added, and 66 mmol of oleoyl chloride was added dropwise in an ice water bath. During the reaction, 30% sodium hydroxide aqueous solution was added dropwise to maintain the pH of the reaction solution at 10. The reaction was carried out at 20°C for 7 hours. Acetone was removed by distillation under reduced pressure, and the product was washed with acetone after filtration. The product was separated by silica gel column chromatography to obtain tri(2-amidoethyl)amine oleate.

[0026] (2) 40 g of tri(2-amidoethyl)amine oleate, 34 g of formic acid, and 1.2 g of sodium bisulfate were stirred and mixed, and 80 mL of 30% hydrogen peroxide aqueous solution was added dropwise. The mixture was heated to 50°C and reacted for 12 hours. After filtration, the product was washed with sodium hydroxide aqueous solution and ethanol aqueous solution in sequence, and then dried to obtain tri(2-amidoethyl)amine epoxy oleate.

[0027] (3) 1 kg of polypropylene resin, 250 g of nylon resin, 35 g of epoxy oleic acid tris (2-amidoethyl) amine, 2 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then melt blended by a twin-screw extruder, and the screw rotation speed of the twin-screw extruder was set to 100 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, and extrusion granulation was performed, thereby obtaining a high-toughness anti-aging PP material.

[0028] Example 3

[0029] (1) Epoxy oleic acid tris (2-amidoethyl) amine was prepared according to the method of Example 1.

[0030] (2) 1 kg of polypropylene resin, 350 g of nylon resin, 50 g of epoxy oleic acid tris (2-amidoethyl) amine, 4 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then melt blended by a twin-screw extruder, and the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, and extrusion granulation was performed, thereby obtaining a high-toughness anti-aging PP material.

[0031] Example 4

[0032] (1) Epoxy oleic acid tris (2-amidoethyl) amine was prepared according to the method of Example 1.

[0033] (2) 1 kg of polypropylene resin, 500 g of nylon resin, 70 g of epoxy oleic acid tris (2-amidoethyl) amine, 2 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then melt blended by a twin-screw extruder, and the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, and extrusion granulation was performed, thereby obtaining a high-toughness anti-aging PP material.

[0034] Comparative Example 1

[0035] (1) 1 kg of polypropylene resin, 150 g of nylon resin, 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then melt blended by a twin-screw extruder, and the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, and extrusion granulation was performed, thereby obtaining a PP material.

[0036] Comparative Example 2

[0037] (1) 1 kg of polypropylene resin, 150 g of nylon resin, 20 g of epoxy oleic acid methyl ester, 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then passed through a twin-screw extruder, the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, melt blending, extrusion granulation, to obtain a PP material.

[0038] Comparative Example 3

[0039] (1) 40 g of ethylene bis-oleic acid amide (CAS No. 110-31-6), 24 g of formic acid, 2 g of sodium bisulfate were stirred and mixed, 60 mL of 30% mass fraction hydrogen peroxide aqueous solution was added dropwise, heated to 65℃, reacted for 6 h, filtered, washed with sodium hydroxide aqueous solution and ethanol aqueous solution in turn, and dried to obtain epoxy ethylene bis-oleic acid amide.

[0040] (3) 1 kg of polypropylene resin (brand 1100NK, same below), 150 g of nylon resin (model PA12), 20 g of epoxy ethylene bis-oleic acid amide, 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then passed through a twin-screw extruder, the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, melt blending, extrusion granulation, to obtain a high-toughness anti-aging PP material.

[0041] Comparative Example 4

[0042] (1) 1 kg of polypropylene resin, 150 g of nylon resin, 20 g of glycidyl methacrylate grafted polypropylene, 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then passed through a twin-screw extruder, the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, melt blending, extrusion granulation, to obtain a PP material.

[0043] Comparative Example 5

[0044] (1) 1 kg of polypropylene resin, 150 g of nylon resin, 20 g of maleic anhydride grafted polypropylene, 2.6 g of antioxidant 1076 were uniformly mixed in a high-speed mixer, and then passed through a twin-screw extruder, the screw rotation speed of the twin-screw extruder was set to 150 r / min, and the temperature of each section was 160℃, 190℃, 210℃, 225℃, 240℃, 240℃, melt blending, extrusion granulation, to obtain a PP material.

[0045] The PP material was injection molded into a test strip for performance testing. The thermal performance was tested in a thermal gravimetric analyzer, nitrogen intensity, the heating rate was 10℃ / min, and the maximum test temperature was 700℃.

[0046] Table 1 Properties of PP materials

[0047]

[0048]

[0049] The polypropylene resin and the nylon resin of Comparative Example 1 have poor compatibility, resulting in low melt flow rate, poor processing performance, low impact strength and flexural strength of the material, poor toughness, and low mass loss temperature, poor heat resistance.

[0050] The epoxy oleic acid tri(2-amidoethyl) amine added in each embodiment contains multiple oleic acid fatty chains, has high similarity with the polypropylene molecular chain, and the molecular chain contains an epoxy group, which can react with the terminal amino group of nylon during high-temperature melting, thereby improving the compatibility between the polypropylene and the nylon, increasing the melt flow rate, improving the processing performance, and the nylon / polypropylene material has higher toughness and mechanical properties, high impact strength and flexural strength, and the mass loss temperature is increased, the heat resistance is changed, which is beneficial to improve the heat aging performance.

[0051] Comparative Example 2 added epoxy methyl oleate containing one oleic acid fatty chain, and Comparative Example 3 added epoxy ethylene bis-oleic acid amide containing two fatty chains, and the properties of the materials are lower than those of Example 1.

[0052] Comparative Example 4 and Comparative Example 5 respectively used conventional glycidyl methacrylate grafted polypropylene and maleic anhydride grafted polypropylene as the compatibilizer, and the compatibilization and promotion of the two examples were lower than that of the epoxy oleic acid tri(2-amidoethyl) amine, resulting in lower impact strength, flexural strength, and mass loss temperature of the material.

Claims

1. A method for preparing a high-toughness, anti-aging PP material, characterized in that, The preparation method of the PP material is as follows: polypropylene resin, nylon resin, epoxy oleic acid tris(2-amidoethyl)amine and antioxidant are mixed in a high-speed mixer in a ratio of 100g:(15-50)g:(2-7)g:(0.2-0.4)g, and then melt-blended and extruded by a twin-screw extruder to obtain a high-toughness and anti-aging PP material.

2. The method for preparing the high-toughness and anti-aging PP material according to claim 1, characterized in that, During the melt blending process, the screw speed of the twin-screw extruder is set to 100-150 r / min, and the temperature of each section is set to 160-240℃.

3. The method for preparing the high-toughness and anti-aging PP material according to claim 1, characterized in that, The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

4. The method for preparing the high-toughness and anti-aging PP material according to claim 1, characterized in that, The preparation method of the epoxy oleic acid tris(2-amidoethyl)amine includes: (1) Add water and tris(2-aminoethyl)amine to acetone, add oleyl chloride dropwise in an ice-water bath, and add sodium hydroxide aqueous solution dropwise. After the reaction, distill under reduced pressure, filter and wash with acetone. Separate the product by silica gel column chromatography to obtain tris(2-amidoethyl)amine oleate. (2) Mix tri(2-amidoethyl)amine oleate, formic acid and sodium bisulfate, add hydrogen peroxide aqueous solution dropwise, filter after reaction, wash with sodium hydroxide aqueous solution and ethanol aqueous solution in sequence, and dry to obtain epoxy oleate tri(2-amidoethyl)amine.

5. The method for preparing the high-toughness and anti-aging PP material according to claim 4, characterized in that, The ratio of (1) tris(2-aminoethyl)amine to oleoyl chloride is 1 mol: (2.2-2.6) mol.

6. The method for preparing the high-toughness and anti-aging PP material according to claim 4, characterized in that, The addition of sodium hydroxide aqueous solution maintains the pH of the reaction solution between 8 and 10.

7. The method for preparing the high-toughness and anti-aging PP material according to claim 4, characterized in that, The temperature during the reaction in (2) is 10-20℃ and the reaction time is 7-10h.

8. The method for preparing the high-toughness and anti-aging PP material according to claim 4, characterized in that, The ratio of oleic acid tris(2-amidoethyl)amine, formic acid, sodium bisulfate, and hydrogen peroxide aqueous solution in (2) is 100g:(60-85)g:(3-5)g:(150-200)mL.

9. The method for preparing the high-toughness and anti-aging PP material according to claim 4, characterized in that, The temperature during the reaction in (2) is 50-65℃ and the reaction time is 6-12h.

10. A high-toughness, anti-aging PP material obtained by the preparation method according to any one of claims 1-9.

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