Polypropylene compounded additive, preparation method thereof and application thereof

Abstract

This application relates to the field of polypropylene additives, specifically disclosing a polypropylene compound additive, its preparation method, and its application. The polypropylene compound additive comprises the following components in parts by weight: 2-5 parts antioxidant, 2-8 parts core-shell alumina, 0.1-4 parts fluorophosphate, 1-3 parts lubricant, 1-3 parts stearate, and 1-2 parts nucleating agent. The polypropylene compound additive of this application has the advantages of improving the toughness of polypropylene materials and mitigating the low-temperature brittleness of polypropylene.

Description

Technical Field

[0001] This application relates to the field of polypropylene additives, and more specifically, to a polypropylene compound additive, its preparation method, and its application. Background Technology

[0002] Polypropylene (PP) is abundant, has excellent processing properties, high yield strength, tensile strength, and elastic modulus, good electrical insulation properties, and excellent overall performance, making it widely used in various fields. However, PP has a large molding shrinkage rate, high brittleness, and low notched impact strength, which is particularly severe in low-temperature environments. This greatly limits the further promotion and application of PP.

[0003] Currently, the toughness of polypropylene is often improved by blending it with other polymers. For example, blending polypropylene with rubber-like elastomers can effectively improve the toughness of polypropylene materials, but it will significantly reduce the modulus of polypropylene materials.

[0004] In view of the above-mentioned related technologies, this application provides a polypropylene compound additive that can effectively improve the toughness of polypropylene, giving polypropylene better impact resistance at room temperature and low temperature, and giving polypropylene materials better flexural modulus. Summary of the Invention

[0005] To improve the toughness of polypropylene materials, this application provides a polypropylene compound additive, its preparation method, and its application.

[0006] In a first aspect, this application provides a polypropylene compound additive, which adopts the following technical solution:

[0007] A polypropylene compound additive, comprising the following components in parts by weight:

[0008] Antioxidant 2-5 parts

[0009] 2-8 parts of core-shell alumina

[0010] Fluorophosphate 0.1-4 parts

[0011] 1-3 parts lubricant

[0012] 1-3 parts stearate

[0013] Nucleating agent 1-2 parts.

[0014] By adopting the above technical solutions, this application effectively improves the room temperature and low temperature impact strength of polypropylene materials by adding core-shell alumina and fluorophosphates, and gives the polypropylene materials better flexural modulus. The addition of core-shell alumina can improve the toughness of polypropylene materials, playing a toughening and impact-resistant role, and effectively improving the low temperature brittleness of polypropylene materials. Fluorophosphates can improve the mechanical properties of polypropylene materials, which is beneficial to improving the elongation at break and impact strength of polypropylene materials, and can also improve rheological properties. Nucleating agents can significantly improve the crystallization behavior of polypropylene materials and improve the low temperature impact performance of polypropylene materials. Antioxidants help improve the stability and oxidation resistance of polypropylene materials. Stearates can act as acid absorbers to reduce the content of precipitates, and in combination with lubricants, improve the demolding performance of polypropylene materials.

[0015] Preferably, the core-shell alumina is PAC-CPAM-PAA-AL2O3, which is obtained by coating nano-alumina with an acrylic acid crosslinking layer, a polyacrylamide layer, and a polyanionic cellulose layer.

[0016] Preferably, the preparation method of the core-shell alumina specifically includes:

[0017] Step 1: Surface modification treatment of nano-alumina with silane coupling agent to obtain coupling-modified nano-alumina;

[0018] Step 2: After mixing the coupling-modified nano-alumina, functional monomers, and methacrylic acid, a crosslinking reaction is carried out in the presence of an initiator to obtain nano-alumina PAA-AL2O3 coated with an acrylic crosslinking layer; the functional monomers are selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxymethyl methacrylate, and hydroxyethyl methacrylate.

[0019] Step 3: Add cationic polyacrylamide and PAA-AL2O3 to the solvent and react in the presence of a condensing agent to obtain CPAM-PAA-AL2O3;

[0020] Step 4: Using water as a medium, CPAM-PAA-AL2O3 is coated with polyanionic cellulose to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

[0021] Preferably, the preparation method of the core-shell alumina specifically includes:

[0022] Step 1: Surface modification treatment of nano-alumina with silane coupling agent to obtain coupling-modified nano-alumina;

[0023] Step 2: Add 1 part by mass of coupling modified nano alumina, 0.01-0.2 parts by mass of functional monomer, and 0.01-0.1 parts by mass of methacrylic acid to an organic solution, disperse evenly by ultrasonication, add 0.01-0.05 parts by mass of initiator and heat to 60-95 degrees Celsius, stir and react for 1-3 hours, filter, wash, and dry to obtain PAA-AL2O3;

[0024] Step 3: Add 1 part by mass of PAA-AL2O3, 0.1-0.3 parts by mass of condensing agent, and 0.2-0.4 parts by mass of cationic polyacrylamide to the solvent, adjust the pH value to 4-6, stir and react at room temperature in the dark for 24-48 hours, separate, dry, and obtain CPAM-PAA-AL2O3;

[0025] Step 4: Add 1 part by mass of CPAM-PAA-AL2O3 into a ball rolling mill, spray 0.1-0.2 parts by mass of water under rolling conditions, add 0.2-0.5 parts by mass of polyanionic cellulose, granulate by ball rolling, disperse the product by ultrasonic vibration, and sieve to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

[0026] Preferably, the silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane.

[0027] Preferably, the condensing agent is 1-ethyl-(3-dimethylaminopropyl)carbodiimide.

[0028] By adopting the above technical solution, this application uses nano-alumina as the core, which is coupled with acrylic monomers under the action of a silane coupling agent. The acrylic monomers are cross-linked in the presence of an initiator to form nano-alumina coated with an acrylic cross-linked layer, denoted as PAA-AL2O3. Then, in the presence of a condensing agent, cationic polyacrylamide is used to coat PAA-AL2O3 to obtain CPAM-PAA-AL2O3. The surface of CPAM-PAA-AL2O3 is then moistened, and polyanionic cellulose is dissolved in water and connected to the cationic polyacrylamide coating layer through electrostatic forces. After granulation by rolling, a core-shell type alumina PAC-CPAM-PAA-AL2O3 with a multi-layer buffer structure is formed.

[0029] Polypropylene materials possess abundant chemical bonding sites, which effectively enhance the mechanical strength and stability of the core-shell structure, contributing to improved modulus and strength. The polyacrylamide layer provides excellent flexibility and water absorption, enhancing the toughness and impact resistance of polypropylene materials. In the presence of small amounts of water, it not only absorbs water to prevent adverse effects on material properties but also expands to form a buffer zone, absorbing impact energy. The polyanionic cellulose layer provides electrostatic forces, improving the dispersion of core-shell alumina within the polypropylene matrix, reducing particle aggregation, and thus more effectively transferring stress and enhancing the overall performance of the polypropylene material.

[0030] When subjected to external forces, the outer polyanionic cellulose layer absorbs some of the energy, followed by the polyacrylamide layer and the acrylic cross-linked layer, and finally the core nano-alumina disperses the stress. This multi-buffering mechanism can effectively absorb and dissipate energy, improving the toughness and low-temperature brittleness of polypropylene materials.

[0031] Preferably, the fluorophosphate is selected from one or a combination of several of dimethyl fluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, ethyl difluorophosphate, vinyl difluorophosphate, and propylene difluorophosphate.

[0032] Preferably, the fluorophosphate is selected from one or both of diethyl fluorophosphate and ethyl difluorophosphate.

[0033] By adopting the above technical solution, the fluorophosphate ester can serve as a dispersed phase, dispersed between the long chains of polypropylene molecules, reducing intermolecular entanglement, increasing the mobility of molecular chains, improving the fluidity and flexibility of polypropylene materials at low temperatures, reducing brittle fracture under low-temperature conditions, and improving the low-temperature brittleness of polypropylene materials. Furthermore, the fluorophosphate ester can act as a heterogeneous nucleating agent, improving the crystallization behavior of polypropylene, promoting the formation of the β-crystal form of polypropylene materials, reducing spherulite size, and improving the toughness and impact strength of polypropylene materials. Simultaneously, the fluorophosphate ester can impart certain surface hydrophobic properties to polypropylene materials, reducing water vapor penetration and improving corrosion resistance; and it can also impart certain flame-retardant properties to polypropylene materials, making it suitable for polypropylene materials in various application fields.

[0034] Preferably, the antioxidant includes a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:(1-3).

[0035] Preferably, the primary antioxidant is a hindered phenolic antioxidant, and the secondary antioxidant is a phosphite antioxidant.

[0036] Preferably, the lubricant is selected from at least one of oleamide and erucamide.

[0037] Preferably, the stearate is selected from at least one of zinc stearate, calcium stearate, and magnesium stearate.

[0038] Preferably, the polypropylene compound additive may further include antistatic agents, anti-adhesion agents, coupling agents, thermoplastic elastomers, and other additives, with each additive being added in the amount conventionally used in the art.

[0039] Secondly, this application provides a method for preparing polypropylene compound additives, using the following technical solution:

[0040] A method for preparing a polypropylene compound additive includes the following steps:

[0041] According to the formula, antioxidant, core-shell alumina, fluorophosphate, lubricant, stearate and nucleating agent are mixed and put into a high-speed disperser for high-speed dispersion to obtain a mixture;

[0042] The mixture is then fed into a ball mill for further refining and dispersion to obtain a refined and dispersed material.

[0043] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0044] Thirdly, this application provides an application of a polypropylene compound additive, employing the following technical solution:

[0045] An application of a polypropylene compound additive, the application method of which includes:

[0046] 100 parts by weight of polypropylene and 1-10 parts by weight of polypropylene compound additives are mixed and then melt-extruded and granulated to obtain a reinforced and toughened polypropylene material.

[0047] The polypropylene is selected from random copolymer polypropylene and homopolymer polypropylene.

[0048] In summary, this application has the following beneficial effects:

[0049] 1. The polypropylene compound additive of this application, by adding core-shell alumina and fluorophosphate, and the components working together, gives the polypropylene material excellent room temperature and low temperature impact strength and good flexural modulus, and is suitable for polypropylene materials in most application fields.

[0050] 2. This application uses nano-alumina coated with multiple polymer layers as a core-shell alumina. The nano-alumina dispersed in polypropylene material can effectively improve the toughness and strength of polypropylene. When subjected to stress, it can generate a stress concentration effect and play a pinning effect, hindering crack propagation and passivating, thereby improving the low-temperature impact performance of polypropylene material. The multiple polymer coating layers can play a bonding and buffering role. When subjected to external impact, the multiple buffering mechanisms can effectively absorb and dissipate energy, improving the toughness and low-temperature brittleness of polypropylene material.

[0051] 3. In this application, fluorophosphate can work in conjunction with nucleating agents to improve the crystallization behavior of polypropylene materials and enhance their toughness and impact resistance. Furthermore, as a dispersed phase in the polypropylene system, fluorophosphate can absorb and dissipate energy when subjected to external impact, which helps to improve the overall toughness. Detailed Implementation

[0052] To further aid in understanding the technical solution of this invention, several specific implementation examples are provided below to describe the technical solution of this invention in more detail. All of these described embodiments are only some embodiments of this invention, and not all of them.

[0053] The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be described again in some embodiments; and the reaction apparatus, monomer compounds, etc. involved in the following embodiments are all commercially available; wherein, diethyl fluorophosphate, CAS No. 358-74-7; ethyl difluorophosphate, CAS No.: 460-52-6; propylene difluorophosphate, CAS No.: 1009107-26-9; vinyl difluorophosphate, CAS No.: 2050472-43-8; polypropylene, commercially available product with CAS No. 9003-07-0; cationic polyacrylamide (CPAM), commercially available product with CAS No. 9003-05-8; 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), CAS No.: 1892-57-5.

[0054] The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be described again in some embodiments.

[0055] The following examples further illustrate the present invention, but the invention is not limited thereto. Unless otherwise specified in the examples, all percentages (%) are mass percentages.

[0056] Preparation Example

[0057] Preparation Example 1

[0058] This preparation example discloses a core-shell type alumina, and the preparation method is as follows:

[0059] Silane coupling agent KH570 was dissolved in 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; nano-alumina was dispersed in the coupling agent solution at a mass-volume ratio of 1:10, ultrasonically treated at 60℃ for 20 min, centrifuged, and dried to obtain coupling-modified alumina.

[0060] 1 part by mass of coupling modified alumina, 0.1 part by mass of hydroxyethyl acrylate, and 0.1 part by mass of methacrylic acid were added to 2 parts by mass of DMF and ultrasonically dispersed evenly. Then, 0.04 parts by mass of ammonium persulfate were added, and the mixture was stirred at 80°C for 3 hours. The mixture was then filtered, washed, and dried to obtain PAA-AL2O3.

[0061] 1 part by mass of PAA-AL2O3, 0.2 parts by mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 0.4 parts by mass of cationic polyacrylamide were added to 4 parts by mass of an aqueous ethanol solution (ethanol:water = 1:1 (v / v)). Sulfuric acid was added dropwise to adjust the pH to 6. The mixture was stirred and reacted at room temperature in the dark for 24 hours. After separation, the mixture was washed with acetone and water, and dried to obtain CPAM-PAA-AL2O3.

[0062] One part by mass of CPAM-PAA-AL2O3 was added to a ball rolling mill, and 0.1 parts by mass of water was sprayed in while the mill was rolling. After the mill was fully wetted, 0.2 parts by mass of polyanionic cellulose PAC-HV-2 was added. The mill rolling mill was then used for granulation. The product was dispersed by ultrasonic vibration and passed through a 500-mesh sieve to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

[0063] Preparation Example 2

[0064] The only difference between this preparation example and Preparation Example 1 is that the preparation method of core-shell alumina is as follows:

[0065] Silane coupling agent KH570 was dissolved in 90wt% ethanol aqueous solution to prepare a 4% coupling agent solution; nano-alumina was dispersed in the coupling agent solution at a mass-volume ratio of 1:10, ultrasonically treated at 60℃ for 20 min, centrifuged, and dried to obtain coupling-modified alumina.

[0066] 1 part by mass of coupling modified alumina, 0.2 parts by mass of hydroxyethyl acrylate, and 0.1 parts by mass of methacrylic acid were added to 2 parts by mass of DMF and ultrasonically dispersed evenly. Then, 0.04 parts by mass of ammonium persulfate were added, and the mixture was stirred at 80°C for 3 hours. The mixture was then filtered, washed, and dried to obtain PAA-AL2O3.

[0067] 1 part by mass of PAA-AL2O3, 0.2 parts by mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 0.4 parts by mass of cationic polyacrylamide were added to 4 parts by mass of an aqueous ethanol solution (ethanol:water = 1:1 (v / v)). Sulfuric acid was added dropwise to adjust the pH to 6. The mixture was stirred and reacted at room temperature in the dark for 24 hours. After separation, the mixture was washed with acetone and water, and dried to obtain CPAM-PAA-AL2O3.

[0068] One part by mass of CPAM-PAA-AL2O3 was added to a ball rolling mill, and 0.2 parts by mass of water was sprayed in while the mill was rolling. After the mill was fully wetted, 0.4 parts by mass of polyanionic cellulose PAC-HV-2 was added. The mill rolling mill was then used for granulation. The product was dispersed by ultrasonic vibration and passed through a 500-mesh sieve to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

[0069] Preparation Example 3

[0070] The only difference between this preparation example and Preparation Example 1 is that the preparation method of core-shell alumina is as follows:

[0071] Silane coupling agent KH570 was dissolved in 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; nano-alumina was dispersed in the coupling agent solution at a mass-volume ratio of 1:10, ultrasonically treated at 60℃ for 20 min, centrifuged, and dried to obtain coupling-modified alumina.

[0072] 1 part by mass of coupling-modified alumina, 0.1 part by mass of hydroxyethyl acrylate, and 0.1 part by mass of methacrylic acid were added to 2 parts by mass of DMF and ultrasonically dispersed evenly. Then, 0.04 parts by mass of ammonium persulfate were added, and the mixture was stirred at 80°C for 3 hours. After filtration, washing, and drying, core-shell alumina PAA-AL2O3 was obtained.

[0073] Preparation Example 4

[0074] The only difference between this preparation example and Preparation Example 1 is that the preparation method of core-shell alumina is as follows:

[0075] Silane coupling agent KH570 was dissolved in 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; nano-alumina was dispersed in the coupling agent solution at a mass-volume ratio of 1:10, ultrasonically treated at 60℃ for 20 min, centrifuged, and dried to obtain coupling-modified alumina.

[0076] One part by mass of coupling-modified alumina and 0.4 parts by mass of cationic polyacrylamide were added to a 90 wt% aqueous ethanol solution, stirred at 45°C for 2 h, filtered, washed, and dried to obtain core-shell alumina CPAM-AL2O3.

[0077] Preparation Example 5

[0078] The only difference between this preparation example and Preparation Example 1 is that the preparation method of core-shell alumina is as follows:

[0079] Silane coupling agent KH570 was dissolved in 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; nano-alumina was dispersed in the coupling agent solution at a mass-volume ratio of 1:10, ultrasonically treated at 60℃ for 20 min, centrifuged, and dried to obtain coupling-modified alumina.

[0080] 1 part by mass of coupling modified alumina and 0.4 parts by mass of cationic polyacrylamide were added to a 90 wt% aqueous ethanol solution, stirred at 45°C for 2 h, filtered, washed, and dried to obtain CPAM-AL2O3.

[0081] One part by mass of CPAM-AL2O3 was added to a ball rolling mill, and 0.1 parts by mass of water was sprayed in while the mill was rolling. After the mill was fully wetted, 0.2 parts by mass of polyanionic cellulose PAC-HV-2 was added. The mill rolling mill was then used to granulate the product. The product was then dispersed by ultrasonic vibration and passed through a 500-mesh sieve to obtain core-shell alumina PAC-CPAM-AL2O3.

[0082] Example

[0083] Example 1

[0084] This embodiment discloses a polypropylene compound additive, the preparation method of which is as follows:

[0085] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 1, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0086] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0087] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0088] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0089] Example 2

[0090] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0091] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 2, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0092] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0093] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0094] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0095] Example 3

[0096] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0097] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 3, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0098] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0099] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0100] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0101] Example 4

[0102] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0103] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 4, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0104] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0105] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0106] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0107] Example 5

[0108] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0109] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 5, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0110] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0111] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0112] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0113] Example 6

[0114] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0115] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 4.4 parts of core-shell alumina prepared in Preparation Example 1, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0116] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0117] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0118] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0119] Example 7

[0120] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0121] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 8 parts of core-shell alumina prepared in Preparation Example 1, 0.1 part of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0122] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0123] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0124] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0125] Example 8

[0126] The only difference between this embodiment and Example 6 is that the preparation method of the polypropylene compound additive is as follows:

[0127] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 4.4 parts of core-shell alumina prepared in Preparation Example 1, 2.5 parts of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0128] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0129] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0130] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0131] Example 9

[0132] The only difference between this embodiment and Example 6 is that the preparation method of the polypropylene compound additive is as follows:

[0133] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 4.4 parts of core-shell alumina prepared in Preparation Example 1, 4 parts of diethyl fluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0134] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0135] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0136] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0137] Example 10

[0138] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0139] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 1, 0.1 parts of propylene difluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0140] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0141] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0142] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0143] Example 11

[0144] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0145] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 1, 0.1 parts of vinyl difluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0146] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0147] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0148] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0149] Example 12

[0150] The only difference between this embodiment and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0151] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 1, 0.1 parts of ethyl difluorophosphate, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0152] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0153] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0154] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0155] Comparative Example

[0156] Comparative Example 1

[0157] The only difference between this comparative example and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0158] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 1 part of erucamide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 are mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0159] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a polypropylene compound additive.

[0160] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0161] Comparative Example 2

[0162] The only difference between this comparative example and Example 1 is that the preparation method of the polypropylene compound additive is as follows:

[0163] By weight, 1 part of antioxidant 1010, 1.5 parts of antioxidant 168, 2 parts of core-shell alumina prepared in Preparation Example 1, 1 part of erucamide, 2 parts of zinc stearate, and 1.1 parts of nucleating agent SKC-Y5988 were mixed and added into a high-speed disperser and dispersed at high speed for 60 minutes to obtain a mixture.

[0164] The mixture is then fed into a ball mill for further refining and dispersion for 60 minutes to obtain a refined dispersion.

[0165] The refined and dispersed material is fed into a granulator for granulation to obtain polypropylene compound additives.

[0166] Polypropylene compound additives are mixed with 100 times the mass of polypropylene in a high-speed mixer, then fed into a twin-screw extruder for melt extrusion, stretching, cooling, and pelletizing to obtain reinforced and toughened polypropylene material.

[0167] Performance testing

[0168] Polypropylene materials from each embodiment and comparative example were injection molded into standard samples. The flexural modulus was tested according to the national standard GB / T9341-2008. The cantilever beam impact strength at 23℃ and -20℃ was tested according to the national standard GB / T 1843-2008. The elongation at break was tested according to the standard GB / T 1040-2006.

[0169] The test results are summarized in Table 1.

[0170] Table 1

[0171]

[0172]

[0173] As can be seen from Examples 1-12 and Comparative Example 1, and Table 1, the addition of core-shell alumina and fluorophosphate can effectively improve the toughness of polypropylene materials, and the polypropylene materials still have good impact resistance under low temperature conditions.

[0174] As can be seen from Examples 1 and 3-5 and Table 1, the mechanical properties of polypropylene materials can be further improved by coating alumina with a multi-layer polymer structure. This may be because the multiple polymer layers can disperse and buffer impact energy, reduce the chance of silver streaks developing into cracks under stress, and can effectively cooperate with the pinning effect of nano-alumina, which can further promote the improvement of the impact resistance of polypropylene materials.

[0175] Based on Examples 1, 8-12, and Comparative Example 2, and in conjunction with Table 1, it can be seen that fluorophosphates can improve the toughness of polypropylene materials and reduce their low-temperature brittleness. This may be because fluorophosphates can act as a dispersed phase in the polypropylene system to absorb and dissipate energy, thus helping to improve overall toughness. Furthermore, fluorophosphates containing alkyl segments can further promote the improvement of the toughness of polypropylene materials, which may be due to the better flexibility of fluorophosphates with alkyl segments.

[0176] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A polypropylene compounding additive, characterized in that, The polypropylene compounded additive comprises the following components by mass fraction: antioxidant 2-5 parts, core-shell alumina 2-8 parts, fluorinated phosphate 0.1-4 parts, lubricant 1-3 parts, stearate 1-3 parts, nucleating agent 1-2 parts. The core-shell alumina is PAC-CPAM-PAA-Al2O3, which is obtained by coating nano-alumina with an acrylic cross-linking layer, a polyacrylamide layer and a polyanionic cellulose layer. The preparation method of the core-shell alumina specifically comprises the following steps: Step 1: surface modification treatment of nano-alumina with a silane coupling agent to obtain coupling-modified nano-alumina; Step 2: mixing the coupling-modified nano-alumina, a functional monomer and methyl methacrylate, and then performing cross-linking reaction in the presence of an initiator to obtain nano-alumina coated with an acrylic cross-linking layer PAA-Al2O3; the functional monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxymethyl methacrylate and hydroxyethyl methacrylate; Step 3: adding cationic polyacrylamide and PAA-AL2O3 into a solvent and performing reaction in the presence of a condensing agent to obtain CPAM-PAA-AL2O3; Step 4: coating CPAM-PAA-AL2O3 with polyanionic cellulose in water as a medium to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

2. The polypropylene compounding additive according to claim 1, characterized in that, The fluorinated phosphate is selected from one or a combination of two or more of dimethyl fluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, ethyl difluorophosphate, vinyl difluorophosphate and propylene difluorophosphate.

3. The polypropylene compounding additive according to claim 2, characterized in that, The fluorinated phosphate is selected from one or both of diethyl fluorophosphate and ethyl difluorophosphate.

4. The polypropylene compounding additive according to claim 1, characterized in that, The lubricant is selected from at least one of oleamide and erucamide.

5. The polypropylene compounding additive according to claim 1, characterized in that, The stearate is selected from at least one of zinc stearate, calcium stearate and magnesium stearate.

6. The polypropylene compounding additive according to claim 1, characterized in that, The antioxidant comprises a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:(1-3).

7. A process for the preparation of a polypropylene compounding additive as claimed in any one of claims 1 to 6, characterized in that The application method comprises the following steps: According to the proportion, the antioxidant, the core-shell alumina, the fluorinated phosphate, the lubricant, the stearate and the nucleating agent are mixed and put into a high-speed disperser for high-speed dispersion to obtain a mixture; The mixture is then put into a ball mill for fine dispersion to obtain a fine dispersion material; The fine dispersion material is put into a granulator for granulation to obtain the polypropylene compounded additive.

8. Use of a polypropylene compounding additive as claimed in any of claims 1 to 6, characterized in that The application method comprises: 100 parts by mass of polypropylene and 1-10 parts by mass of the polypropylene compounded additive are mixed and then melt-extruded and granulated to obtain a reinforced and toughened polypropylene material.

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