Polypropylene compound additive as well as preparation method and application thereof

Abstract

The invention relates to the field of polypropylene auxiliaries, and particularly discloses a polypropylene compound additive as well as a preparation method and application thereof. The polypropylene compound additive comprises the following components in parts by mass: 2-5 parts of an antioxidant, 2-8 parts of core-shell aluminum oxide, 0.1-4 parts of fluorophosphate, 1-3 parts of a lubricant, 1-3 parts of stearate and 1-2 parts of a nucleating agent. The polypropylene compound additive has the advantages of improving the toughness of a polypropylene material and improving the low-temperature brittleness of polypropylene.

Description

Technical Field

[0001] The present application relates to the field of polypropylene additives, and more specifically, to a polypropylene compound additive, a preparation method thereof, and an application thereof. Background Art

[0002] Polypropylene (PP) is a material with abundant sources, excellent processing performance, high yield strength, tensile strength and elastic modulus, good electrical insulation performance and good comprehensive performance. It is widely used in many fields. However, PP has large molding shrinkage, high brittleness and low notched impact strength, which is particularly serious in low temperature environments. This has greatly limited the further promotion and application of PP.

[0003] At present, the toughness of polypropylene is often improved by adding other polymers for blending and modification. For example, adding rubber elastomers to polypropylene for blending and modification 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, the present application provides a polypropylene compound additive, which can effectively improve the toughness of polypropylene, make the polypropylene have better impact resistance at room temperature and low temperature, and make the polypropylene material have better bending modulus. Summary of the invention

[0005] In order to improve the toughness of polypropylene materials, the present application provides a polypropylene compound additive, a preparation method thereof, and an application thereof.

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

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

[0008] 2-5 parts of antioxidant,

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

[0010] Fluorinated phosphoric acid ester 0.1-4 parts,

[0011] 1-3 parts of lubricant,

[0012] 1-3 parts of stearate,

[0013] 1-2 parts of nucleating agent.

[0014] By adopting the above technical scheme, the present application effectively improves the room temperature and low temperature impact strength of the polypropylene material by adding core-shell alumina and fluorophosphate, and makes the polypropylene material have a better bending modulus; the addition of core-shell alumina can improve the toughness of the polypropylene material, play a toughening and impact resistance effect, and effectively improve the low-temperature brittleness of the polypropylene material; fluorophosphate can improve the mechanical properties of the polypropylene material, which is beneficial to improve the elongation at break and impact strength of the polypropylene material, and can improve the rheological properties; the nucleating agent can significantly improve the crystallization behavior of the polypropylene material and improve the low-temperature impact performance of the polypropylene material; the antioxidant helps to improve the stability and antioxidant performance of the polypropylene material; the stearate can be used as an acid absorbent to reduce the precipitate content, and cooperate with the lubricant to improve the demoulding performance of the polypropylene material.

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

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

[0017] Step 1: using a silane coupling agent to perform surface modification on nano-alumina to obtain coupled modified nano-alumina;

[0018] Step 2: After mixing the coupled modified nano-alumina, functional monomers and methacrylic acid, a cross-linking reaction is carried out in the presence of an initiator to obtain nano-alumina PAA-AL2O3 coated with an acrylic acid cross-linking layer; the functional monomer is 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 into a solvent, and react in the presence of a condensation agent to obtain CPAM-PAA-AL2O3;

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

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

[0022] Step 1: using a silane coupling agent to perform surface modification on nano-alumina to obtain coupled modified nano-alumina;

[0023] Step 2: Add 1 part by mass of coupled modified nano-alumina, 0.01-0.2 parts by mass of functional monomers, and 0.01-0.1 parts by mass of methacrylic acid to the 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 a condensing agent, and 0.2-0.4 parts by mass of a cationic polyacrylamide to a solvent, adjust the pH value to 4-6, react with stirring at room temperature in the dark for 24-48 hours, separate, and dry to obtain CPAM-PAA-AL2O3;

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

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

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

[0028] By adopting the above technical scheme, the present application uses nano-alumina as the core, couples with acrylic acid monomers under the action of a silane coupling agent, and the acrylic acid monomers are cross-linked in the presence of an initiator to form nano-alumina coated with an acrylic acid cross-linking layer, which is recorded as PAA-AL2O3; then, cationic polyacrylamide is used to coat PAA-AL2O3 in the presence of a condensing agent to obtain CPAM-PAA-AL2O3; then, the surface of CPAM-PAA-AL2O3 is moistened, polyanionic cellulose is dissolved in water and connected to the cationic polyacrylamide coating layer through electrostatic force, and after ball rolling granulation, a core-shell alumina PAC-CPAM-PAA-AL2O3 with a multi-layer buffer structure is formed.

[0029] The polypropylene material has abundant chemical bond connection sites, which can effectively enhance the mechanical strength of the core-shell structure stability and help improve the modulus and strength of the polypropylene material; the polyacrylamide layer can provide good flexibility and water absorption, which helps to improve the toughness and impact resistance of the polypropylene material. When a small amount of water is present, it can not only absorb water to prevent the material performance from being affected, but also absorb water to swell to form a buffer area to absorb impact energy; the polyanionic cellulose layer can provide electrostatic force, improve the dispersibility of the core-shell alumina in the polypropylene matrix, reduce the aggregation of particles, thereby more effectively transmitting stress and improving the overall performance of the polypropylene material;

[0030] When subjected to external force, the outer polyanionic cellulose layer absorbs part of the energy, followed by the polyacrylamide layer and the acrylic cross-linking layer, and finally the stress is dispersed by the nano-aluminum oxide in the inner core. This multiple buffering mechanism can effectively absorb and dissipate energy, and improve the toughness and low-temperature brittleness of polypropylene materials.

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

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

[0033] By adopting the above technical scheme, the above fluorophosphate ester can be used as a dispersed phase, dispersed between the long chains of polypropylene molecules, reduce intermolecular entanglement, increase the mobility of the molecular chain, improve the fluidity and flexibility of the polypropylene material at low temperature, reduce the brittle fracture under low temperature conditions, and improve the low-temperature brittleness of the polypropylene material; and the fluorophosphate ester can be used as a heterogeneous nucleating agent to improve the crystallization behavior of polypropylene, promote the formation of β crystal form of polypropylene material, reduce the size of spherulites, and improve the toughness and impact strength of polypropylene material; at the same time, the fluorophosphate ester can give the polypropylene material a certain surface hydrophobicity, reduce the penetration of water vapor, and improve the corrosion resistance; and can give the polypropylene material a certain flame retardant property, and is suitable for polypropylene materials in various application fields.

[0034] Preferably, 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).

[0035] Preferably, the primary antioxidant is a hindered phenol 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 also include auxiliary agents such as antistatic agent, anti-adhesive agent, coupling agent, thermoplastic elastomer, etc., and the amount of each auxiliary agent is the conventional addition amount in the art.

[0039] In a second aspect, the present application provides a method for preparing a polypropylene compound additive, using the following technical solution:

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

[0041] According to the proportion, the 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] Then the mixed material is put into a ball mill for fine dispersion to obtain fine dispersed material;

[0043] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0044] In a third aspect, the present application provides an application of a polypropylene compound additive, using the following technical solution:

[0045] An application of a polypropylene compound additive, and the application method thereof comprises:

[0046] 100 parts by mass of polypropylene and 1-10 parts by mass 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 the present application adds core-shell alumina and fluorophosphate, and the components cooperate with each other, so that the polypropylene material has excellent room temperature and low temperature impact strength, and has a better bending modulus, and is suitable for polypropylene materials in most application fields;

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

[0051] 3. In the present application, fluorophosphate can be combined with a nucleating agent to improve the crystallization behavior of polypropylene materials, and to increase the toughness and impact strength of polypropylene materials; and as a dispersed phase in the polypropylene system, fluorophosphate can absorb and dissipate energy when impacted by external forces, which helps to improve the overall toughness. DETAILED DESCRIPTION

[0052] To further help understand the technical solution of the present invention, the technical solution of the present invention is described in more detail below by providing several specific implementation examples. All of these described embodiments are only partial embodiments of the present invention, 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 repeated in some embodiments; and the reaction devices, monomer compounds, etc. involved in the following embodiments are all commercially available; among them, 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, a commercial product with CAS No. 9003-07-0, cationic polyacrylamide (CPAM), a commercial product with CAS No. 9003-05-8; 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), CAS No.: 1892-57-5.

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

[0055] The following examples are further explanations of the present invention, but the present invention is not limited thereto. Unless otherwise specified in the examples, the percentages are all by mass.

[0056] Preparation Example

[0057] Preparation Example 1

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

[0059] The silane coupling agent KH570 is dissolved in a 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; the nano-alumina is dispersed in the coupling agent solution at a mass volume ratio of 1:10, ultrasonically treated at 60°C for 20 minutes, centrifuged and dried to obtain coupled 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 ultrasonic dispersion was performed uniformly. Then, 0.04 part by mass of ammonium persulfate was added, and the mixture was stirred at 80°C for 3 hours, and 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 ethanol aqueous solution (ethanol: water = 1:1 (v / v)), sulfuric acid was added dropwise to adjust the pH value to 6, and 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 respectively, and dried to obtain CPAM-PAA-AL2O3;

[0062] Put 1 part by mass of CPAM-PAA-AL2O3 into a ball rolling machine, spray 0.1 parts by mass of water while rolling, add 0.2 parts by mass of polyanionic cellulose PAC-HV-2 after fully moistening, roll and granulate, disperse the product by ultrasonic vibration, and pass it 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] The silane coupling agent KH570 is dissolved in a 90wt% ethanol aqueous solution to prepare a 4% coupling agent solution; the nano-alumina is dispersed in the coupling agent solution at a mass volume ratio of 1:10, ultrasonically treated at 60°C for 20 minutes, centrifuged and dried to obtain coupled modified alumina;

[0066] 1 part by mass of coupling modified alumina, 0.2 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 ultrasonic dispersion was performed uniformly. Then, 0.04 part by mass of ammonium persulfate was added, and the mixture was stirred at 80°C for 3 hours, and 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 ethanol aqueous solution (ethanol: water = 1:1 (v / v)), sulfuric acid was added dropwise to adjust the pH value to 6, and 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 respectively, and dried to obtain CPAM-PAA-AL2O3;

[0068] Put 1 part by mass of CPAM-PAA-AL2O3 into a ball rolling machine, spray 0.2 parts by mass of water while rolling, add 0.4 parts by mass of polyanionic cellulose PAC-HV-2 after sufficient wetting, roll and granulate, disperse the product by ultrasonic vibration, and pass it 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] The silane coupling agent KH570 is dissolved in a 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; the nano-alumina is dispersed in the coupling agent solution at a mass volume ratio of 1:10, ultrasonically treated at 60°C for 20 minutes, centrifuged and dried to obtain a coupled modified alumina;

[0072] 1 part by mass of coupled 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 dispersed evenly by ultrasonication. Then 0.04 part by mass of ammonium persulfate was added and the reaction was stirred at 80°C for 3 hours. The reaction was filtered, washed and dried to obtain core-shell alumina PAA-AL2O3.

[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] The silane coupling agent KH570 is dissolved in a 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; the nano-alumina is dispersed in the coupling agent solution at a mass volume ratio of 1:10, ultrasonically treated at 60°C for 20 minutes, centrifuged and dried to obtain a coupled modified alumina;

[0076] 1 part by mass of coupled modified alumina and 0.4 part by mass of cationic polyacrylamide were added to a 90 wt % ethanol aqueous 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] The silane coupling agent KH570 is dissolved in a 90wt% ethanol aqueous solution to prepare a 2% coupling agent solution; the nano-alumina is dispersed in the coupling agent solution at a mass volume ratio of 1:10, ultrasonically treated at 60°C for 20 minutes, centrifuged and dried to obtain coupled modified alumina;

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

[0081] Put 1 mass part of CPAM-AL2O3 into a ball rolling machine, spray 0.1 mass part of water in the rolling state, add 0.2 mass part of polyanionic cellulose PAC-HV-2 after fully moistening, roll and granulate, disperse the product by ultrasonic vibration, pass through a 500-mesh sieve, and obtain core-shell alumina PAC-CPAM-AL2O3.

[0082] Example

[0083] Example 1

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

[0085] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0086] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0087] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0088] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0089] Example 2

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

[0091] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0092] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0093] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0094] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0095] Example 3

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

[0097] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0098] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0099] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0100] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0101] Example 4

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

[0103] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0104] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0105] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0106] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0107] Example 5

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

[0109] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0110] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0111] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0112] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0113] Example 6

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

[0115] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0116] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0117] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0118] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0119] Example 7

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

[0121] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0122] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0123] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0124] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0125] Example 8

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

[0127] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0128] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0129] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0130] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0131] Example 9

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

[0133] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0134] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0135] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0136] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0137] Example 10

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

[0139] By mass, 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 propylene difluorophosphate, 1 part of erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0140] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0141] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0142] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0143] Embodiment 11

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

[0145] By mass, 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 vinyl difluorophosphate, 1 part of erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0146] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0147] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0148] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0149] Example 12

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

[0151] By mass, 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 ethyl difluorophosphate, 1 part of erucic acid amide, 2 parts of zinc stearate, and 1 part of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0152] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0153] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0154] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0155] Comparative Example

[0156] Comparative Example 1

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

[0158] 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 were mixed by mass and put into a high-speed disperser for high-speed dispersion for 60 minutes to obtain a mixture;

[0159] The mixed material was then put into a ball mill for fine dispersion for 60 minutes to obtain a polypropylene compound additive.

[0160] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0161] Comparative Example 2

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

[0163] By mass, 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 erucic acid amide, 2 parts of zinc stearate, and 1.1 parts of nucleating agent SKC-Y5988 were mixed and put into a high-speed disperser, and dispersed at high speed for 60 minutes to obtain a mixture;

[0164] The mixed material is then put into a ball mill for fine dispersion for 60 minutes to obtain a fine dispersed material;

[0165] The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

[0166] The polypropylene compound additive and 100 times the mass of polypropylene are put into a high-speed mixer for mixing, and then put into a twin-screw extruder for melt extrusion, pulling, cooling, and pelletizing to obtain a reinforced and toughened polypropylene material.

[0167] Performance testing

[0168] The polypropylene materials of each embodiment and each comparative example were injection molded into standard samples, and the flexural modulus was tested according to the national standard GB / T9341-2008; the cantilever beam impact strength at 23°C and -20°C was tested according to the national standard GB / T 1843-2008, and 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] It can be seen from Examples 1-12 and Comparative Example 1 and Table 1 that the addition of core-shell alumina and fluorophosphate can effectively improve the toughness of the polypropylene material, and the polypropylene material still has good impact resistance under low temperature conditions.

[0174] It can be seen from Example 1, Examples 3-5 and Table 1 that the mechanical properties of the polypropylene material can be further improved by coating alumina with a multi-layer polymer layer structure; this may be because the multiple polymer layers can disperse and buffer the impact energy, reduce the chance of silver streaks developing into cracks due to stress, and can effectively cooperate with the pinning effect of nano-alumina, thereby further promoting the improvement of the impact resistance of the polypropylene material.

[0175] It can be seen from Example 1, Examples 8-12, Comparative Example 2 and Table 1 that fluorophosphates can improve the toughness of polypropylene materials and improve the low-temperature brittleness of polypropylene materials; this may be because fluorophosphates can absorb and dissipate energy as a dispersed phase in the polypropylene system, which helps to improve the overall toughness; and 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 the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A polypropylene compound additive, characterized in that: The composition comprises the following components in parts by weight: 2-5 parts of antioxidant, 2-8 parts of core-shell alumina, Fluorinated phosphoric acid ester 0.1-4 parts, 1-3 parts of lubricant, 1-3 parts of stearate, 1-2 parts of nucleating agent.

2. The polypropylene compound additive according to claim 1, characterized in that: The core-shell alumina is PAC-CPAM-PAA-Al2O3, which is nano-alumina coated with an acrylic acid cross-linking layer, a polyacrylamide layer, and a polyanionic cellulose layer.

3. The polypropylene compound additive according to claim 2, characterized in that: The preparation method of the core-shell alumina specifically comprises: Step 1: using a silane coupling agent to perform surface modification on nano-alumina to obtain coupled modified nano-alumina; Step 2: After mixing the coupled modified nano-alumina, functional monomers and methacrylic acid, a cross-linking reaction is carried out in the presence of an initiator to obtain nano-alumina PAA-Al2O3 coated with an acrylic acid cross-linking layer; the functional monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxymethyl methacrylate and hydroxyethyl methacrylate; Step 3: Add cationic polyacrylamide and PAA-AL2O3 into a solvent, and react in the presence of a condensation agent to obtain CPAM-PAA-AL2O3; Step 4: Using water as a medium, polyanionic cellulose is used to coat CPAM-PAA-AL2O3 to obtain core-shell alumina PAC-CPAM-PAA-AL2O3.

4. The polypropylene compound additive according to claim 1, characterized in that: The fluorophosphate ester is selected from the group consisting of dimethyl fluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, ethyl difluorophosphate, vinyl difluorophosphate, and propylene difluorophosphate, or a combination thereof.

5. The polypropylene compound additive according to claim 4, characterized in that: The fluorophosphate is selected from one or both of diethyl fluorophosphate and ethyl difluorophosphate.

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

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

8. The polypropylene compound 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).

9. A method for preparing the polypropylene compound additive according to any one of claims 1 to 8, characterized in that: The following steps are involved: According to the proportion, the 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; Then the mixed material is put into a ball mill for fine dispersion to obtain fine dispersed material; The refined dispersed material is put into a granulator for granulation to obtain a polypropylene compound additive.

10. A use of the polypropylene compound additive according to any one of claims 1 to 8, characterized in that: Application methods include: 100 parts by mass of polypropylene and 1-10 parts by mass of polypropylene compound additives are mixed and then melt-extruded and granulated to obtain a reinforced and toughened polypropylene material.

Images